CN102658070A - Method for preparing core-shell reversible heat-sensitive temperature indicating composite microspheres - Google Patents
Method for preparing core-shell reversible heat-sensitive temperature indicating composite microspheres Download PDFInfo
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- CN102658070A CN102658070A CN2012101480505A CN201210148050A CN102658070A CN 102658070 A CN102658070 A CN 102658070A CN 2012101480505 A CN2012101480505 A CN 2012101480505A CN 201210148050 A CN201210148050 A CN 201210148050A CN 102658070 A CN102658070 A CN 102658070A
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- emulsion
- reversible heat
- temperature indicating
- polyvinyl alcohol
- microballoon
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Abstract
The invention relates to a method for preparing core-shell reversible heat-sensitive temperature indicating composite microspheres. The method is characterized by comprising the following steps of: adding MCM-41 silicon-based mesoporous microspheres into a CoCl2 aqueous solution to prepare reversible heat-sensitive temperature indicating microspheres, and adding an emulsifier Span80 into cyclohexane to prepare an oil phase; adding the reversible heat-sensitive temperature indicating microspheres into the oil phase to prepare S/O1 emulsion; adding an emulsifier Tween80 into a polyvinyl alcohol aqueous solution to prepare a water phase; dripping the S/O1 emulsion into the water phase to prepare S/O1/W inner emulsion; adding the emulsifier Span80 into the cyclohexane to prepare a dispersed phase, and dripping the S/O1/W inner emulsion and a cross-linking agent glutaraldehyde into the dispersed phase to prepare S/O1/W/O2 composite emulsion; and reacting the composite emulsion with stirring, performing suction filtering, washing, and drying to obtain the core-shell reversible heat-sensitive temperature indicating composite microspheres. The microspheres sensitively indicate temperature and are high in reversibility, environmental adaptability and reusability.
Description
Technical field
The present invention relates to technical field of function materials, particularly a kind of preparation method of hud typed reversible heat-sensible temperature indicating complex microsphere is inorganic reversible heat-sensible thermally indicating material cobalt chloride hexahydrate (CoCl
26H
2O) preparation method of hud typed complex microsphere.
Background technology
Since the eighties in 20th century, the developing trend of thermally indicating material is in low temperature, reversible both direction.Particularly inorganic reversible heat-sensible thermally indicating material because of have good thermochromatism and invertibity, in bright gay color, synthesis technique simply, advantage such as cost is lower, have a wide range of applications at numerous areas such as industry, publication and printing, textile garment, medical treatment and daily lifes.CoCl wherein
26H
2O is a kind of inorganic reversible heat-sensible thermally indicating material of representational low temperature that has.When being heated to 40 ℃, promptly losing the crystallization water and become blueness by redness; Naturally after the cooling, from environment, absorb water and the generation secondary color.The thermal discoloration of this material (as becoming the temperature of secondary color time, change secondary color) very easily receives the influence of factors such as air humidity, solvent, heat time heating time, firing rate, heating number of times, and the temperature indicating precision is not high, uses to be restricted yet.Have than big-difference because of air humidity is different like the secondary color time, need about 40min usually.In the organic solvent environment, often lose discoloration because of the variation of structure; Relatively poor with the macromolecular material compatibility, when being used as the base lacquer of organic coating or printing ink, be prone to separating out of solids, influence coating performance.
With the mesoporous nano microballoon is carrier, and adsorbed water dissolubility reversible heat-sensible thermally indicating material is processed reversible heat-sensible temperature indicating microballoon; Wrap up with macromolecular material again; Process the complex microsphere of nucleocapsid structure; The protection of the specific area that mesoporous microsphere capable of using is high, adsorption capacity and shell; Make the thermochromism process of material not receive the influence of environment and service condition, greatly improve its thermochromic properties and environmental suitability, enlarge its scope of application.
For many years, the Research of Microencapsulation of reversible heat-sensible thermally indicating material is influenced thermally indicating material reducing external environment, shorten the secondary color time, the aspects such as compatibility of improvement and organic material and solvent have obtained some achievements.But prepared temperature-sensitive temperature indicating microcapsules are core with the aqueous solution droplets of thermo-sensitive material all at present, and hydroxyethylcellulose or polyvinyl alcohol are produced for the shell material.Require shell material to form seamless material membrane, the control of shell material self performance and experiment condition is required harsh, be prone to cyst wall porous, broken shell and cause the phenomenon of core loss and sex change in polymerization around the core.Be the microcapsules of core with liquid simultaneously, mechanical strength is low, not anti-extruding, and active force is prone to break when big, uses and receives certain limitation.Hud typed reversible temperature indicating complex microsphere particle diameter is easy to control, and the influence of shell material reduces, and mechanical strength is high, environmental suitability is strong, and the variable color secondary color is sensitiveer.
Through the document retrieval, do not find that as yet adopting the mesoporous nano microballoon is carrier, reversible heat-sensible temperature indicating microballoon is a core, the relevant report of macromolecular material hud typed reversible heat-sensible temperature indicating complex microsphere for the shell material prepares.
Summary of the invention
The technical problem that solves
Weak point for fear of prior art; The present invention proposes a kind of preparation method of hud typed reversible heat-sensible temperature indicating complex microsphere; To solve in the prior art with liquid is that the temperature indicating microcapsules of core are harsh to shell material self performance and requirement for experiment condition; Mechanical strength is low, not anti-extruding, is prone to deficiencies such as cyst wall porous, broken shell phenomenon.
Technical scheme
A kind of preparation method of hud typed reversible heat-sensible temperature indicating complex microsphere is characterized in that step is following:
Step 1: it is 0.5gml that the silicon-based mesoporous microballoon of MCM-41 is joined concentration
-1CoCl
2In the aqueous solution, adsorb after 1～2 hour, carry out centrifugally, vacuum drying makes reversible heat-sensible temperature indicating microballoon (S); Silicon-based mesoporous microballoon of said MCM-41 and CoCl
2Mass ratio be 1: 25;
Step 2: with emulsifying agent Span80, join at 1: 20 in the cyclohexane, process oil phase (O according to volume ratio
1);
Step 3: reversible heat-sensible temperature indicating microballoon (S) is joined oil phase (O
1) in, process stable S/O
1Emulsion;
Step 4: with emulsifying agent Tween80, join in the polyvinyl alcohol water solution, process water (W); The volume ratio of said emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20～25; Said polyvinyl alcohol water solution concentration is 0.8%～1.0% (g/g), regulates acidity with concentrated hydrochloric acid, makes pH less than 2;
Step 5: splash into the prepared S/O of step 3 to aqueous phase (W)
1Emulsion is processed stable S/O
1Emulsion in the/W;
Step 6: emulsifying agent Span80 joined process decentralized photo (O in the cyclohexane
2), under 1200～1500r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step 5
1Emulsion in the/W adds the crosslinking agent glutaraldehyde at last, processes stable S/O
1/ W/O
2Double emulsion; The volume ratio of said cyclohexane and Span80 is 20: 1; The mol ratio of said glutaraldehyde and polyvinyl alcohol is 1: 2～2.5; Said S/O
1Emulsion and decentralized photo (O in/the W
2) volume ratio be 1: 3～4;
Step 7: the S/O that step 6 is obtained
1/ W/O
2Double emulsion stirs with 1200～1500r/min, makes S/O
1/ W/O
2Condensation reaction takes place at water oil interface in double emulsion; After 2～3 hours, carry out suction filtration, washing and drying, obtain hud typed reversible heat-sensible temperature indicating complex microsphere then.
Beneficial effect
The preparation method of a kind of hud typed reversible heat-sensible temperature indicating complex microsphere that the present invention proposes has prepared hud typed reversible heat-sensible temperature indicating complex microsphere, and temperature indicating is sensitive, good reversibility, and environmental suitability is strong, reusability good.For application and the exploitation of novel thermally indicating material of inorganic reversible heat-sensible thermally indicating material in printing ink, coating provides method.
It is easy to control that the inventive method has particle diameter, and experiment condition is gentle, characteristics such as clad ratio height.Prepared composite microballoon mechanical strength is high, environmental suitability is strong, and temperature indicating is functional, stable, good reproducibility.
The specific embodiment
Combine embodiment that the present invention is further described at present:
Embodiment 1: it is 0.5gml that the silicon-based mesoporous microballoon of 0.3gMCM-41 is joined 15ml concentration
-1CoCl
2In the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying makes reversible heat-sensible temperature indicating microballoon (S).Silicon-based mesoporous microballoon of MCM-41 and CoCl
2Amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, join at 1: 20 in the 5ml cyclohexane, process oil phase (O according to volume ratio
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, process stable S/O
1Emulsion.Configuration concentration is the polyvinyl alcohol water solution of 0.8% (g/g), regulates acidity with concentrated hydrochloric acid, makes pH less than 2.1m1Tween80 is joined in this polyvinyl alcohol water solution of 20ml, process water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20.Splash into the prepared S/O of step (c) to aqueous phase (W)
1Emulsion is processed stable S/O
1Emulsion in the/W.Measure 4.0mlSpan80, join in the 80ml cyclohexane, process decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under the 1200r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1Emulsion in the/W adds the crosslinking agent glutaraldehyde at last, processes stable S/O
1/ W/O
2Double emulsion.Wherein the amount ratio of glutaraldehyde and polyvinyl alcohol is 1: 2.5 (mol ratio), S/O
1Emulsion and decentralized photo (O in/the W
2) amount ratio be 1: 3.2 (volume ratio).S/O
1/ W/O
2Condensation reaction takes place at water oil interface in double emulsion, and suction filtration, washing, drying after 3 hours obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
Through measuring prepared hud typed reversible heat-sensible complex microsphere average grain diameter 20 μ m, variable color time 220s, secondary color time 310s, 41 ° of C of discoloring temperature.Measure 41 ° of C of discoloring temperature, variable color time 210s, secondary color time 330s repeatedly after the heating and cooling 60 times.In methyl alcohol, ethanol, acetone, toluene, oxolane, acetate (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent, soak after 24 hours and measure; 41 ° of C of discoloring temperature; The variable color time remains on 200s ± 10s, secondary color time 330s ± 10s.
Embodiment 2: it is 0.5gml that the silicon-based mesoporous microballoon of 0.2gMCM-41 is joined 10ml concentration
-1CoCl
2In the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying makes reversible heat-sensible temperature indicating microballoon (S).Silicon-based mesoporous microballoon of MCM-41 and CoCl
2Amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, join at 1: 20 in the 5ml cyclohexane, process oil phase (O according to volume ratio
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, process stable S/O
1Emulsion.Configuration concentration is the polyvinyl alcohol water solution of 0.9% (g/g), regulates acidity with concentrated hydrochloric acid, makes pH less than 2.1m1Tween80 is joined in this polyvinyl alcohol water solution of 20ml, process water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20.Splash into the prepared S/O of step (c) to aqueous phase (W)
1Emulsion is processed stable S/O
1Emulsion in the/W.Measure 4.0mlSpan80, join in the 80ml cyclohexane, process decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under the 1200r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1Emulsion in the/W adds the crosslinking agent glutaraldehyde at last, processes stable S/O
1/ W/O
2Double emulsion.Wherein the amount ratio of glutaraldehyde and polyvinyl alcohol is 1: 2.2 (mol ratio), S/O
1Emulsion and decentralized photo (O in/the W
2) amount ratio be 1: 3.2 (volume ratio).S/O
1/ W/O
2Condensation reaction takes place at water oil interface in double emulsion, and suction filtration, washing, drying after 2 hours obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
Through measuring prepared hud typed reversible heat-sensible complex microsphere average grain diameter 20 μ m, variable color time 250s, secondary color time 350s, 41 ° of C of discoloring temperature.Measure 41 ° of C of discoloring temperature, variable color time 260s, secondary color time 360s repeatedly after the heating and cooling 60 times.In methyl alcohol, ethanol, acetone, toluene, oxolane, acetate (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent, soak after 24 hours and measure; 41 ° of C of discoloring temperature; The variable color time remains on 270s ± 10s, secondary color time 360s ± 10s.
Embodiment 3: it is 0.5gml that the silicon-based mesoporous microballoon of 0.2gMCM-41 is joined 10ml concentration
-1CoCl
2In the aqueous solution, adsorb after 1 hour, centrifugal, vacuum drying makes reversible heat-sensible temperature indicating microballoon (S).Silicon-based mesoporous microballoon of MCM-41 and CoCl
2Amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, join at 1: 20 in the 5ml cyclohexane, process oil phase (O according to volume ratio
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, process stable S/O
1Emulsion.Configuration concentration is the polyvinyl alcohol water solution of 0.8% (g/g), regulates acidity with concentrated hydrochloric acid, makes pH less than 2.1ml Tween80 is joined in this polyvinyl alcohol water solution of 25ml, process water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 25.Splash into the prepared S/O of step (c) to aqueous phase (W)
1Emulsion is processed stable S/O
1Emulsion in the/W.Measure 4.5mlSpan80, join in the 90ml cyclohexane, process decentralized photo (O
2), the amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under the 1400r/min stirring action, in decentralized photo, splash into the prepared S/O of step (e)
1Emulsion in the/W adds the crosslinking agent glutaraldehyde at last, processes stable S/O
1/ W/O
2Double emulsion.Wherein the amount ratio of glutaraldehyde and polyvinyl alcohol is 1: 2.2 (mol ratio), S/O
1Emulsion and decentralized photo (O in/the W
2) amount ratio be 1: 3 (volume ratio).S/O
1/ W/O
2Condensation reaction takes place at water oil interface in double emulsion, and suction filtration, washing, drying after 3 hours obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
Through measuring prepared hud typed reversible heat-sensible complex microsphere average grain diameter 15 μ m, variable color time 280s, secondary color time 320s, 41 ° of C of discoloring temperature.Measure 41 ° of C of discoloring temperature, variable color time 230s, secondary color time 340s repeatedly after the heating and cooling 60 times.In methyl alcohol, ethanol, acetone, toluene, oxolane, acetate (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent, soak after 24 hours and measure; 41 ° of C of discoloring temperature; The variable color time remains on 280s ± 10s, secondary color time 310s ± 10s.
Embodiment 4: it is 0.5gml that the silicon-based mesoporous microballoon of 0.3gMCM-41 is joined 15ml concentration
-1CoCl
2In the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying makes reversible heat-sensible temperature indicating microballoon (S).Silicon-based mesoporous microballoon of MCM-41 and CoCl
2Amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, join at 1: 20 in the 5ml cyclohexane, process oil phase (O according to volume ratio
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, process stable S/O
1Emulsion.Configuration concentration is the polyvinyl alcohol water solution of 1.0% (g/g), regulates acidity with concentrated hydrochloric acid, makes pH less than 2.1ml Tween80 is joined in this polyvinyl alcohol water solution of 20ml, process water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20.Splash into the prepared S/O of step (c) to aqueous phase (W)
1Emulsion is processed stable S/O
1Emulsion in the/W.Measure 5.0mlSpan80, join in the 100ml cyclohexane, process decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under the 1400r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1Emulsion in the/W adds the crosslinking agent glutaraldehyde at last, processes stable S/O
1/ W/O
2Double emulsion.Wherein the amount ratio of glutaraldehyde and polyvinyl alcohol is 1: 2 (mol ratio), S/O
1Emulsion and decentralized photo (O in/the W
2) amount ratio be 1: 4 (volume ratio).S/O
1/ W/O
2Condensation reaction takes place at water oil interface in double emulsion, and suction filtration, washing, drying after 3 hours obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
Through measuring prepared hud typed reversible heat-sensible complex microsphere average grain diameter 35 μ m, variable color time 330s, secondary color time 370s, 41 ° of C of discoloring temperature.Measure 41 ° of C of discoloring temperature, variable color time 300s, secondary color time 380s repeatedly after the heating and cooling 60 times.In methyl alcohol, ethanol, acetone, toluene, oxolane, acetate (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent, soak after 24 hours and measure; 41 ° of C of discoloring temperature; The variable color time remains on 280s ± 10s, secondary color time 390s ± 10s.
Embodiment 5: it is 0.5gml that the silicon-based mesoporous microballoon of 0.4gMCM-41 is joined 20ml concentration
-1CoCl
2In the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying makes reversible heat-sensible temperature indicating microballoon (S).Silicon-based mesoporous microballoon of MCM-41 and CoCl
2Amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, join at 1: 20 in the 5ml cyclohexane, process oil phase (O according to volume ratio
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, process stable S/O
1Emulsion.Configuration concentration is the polyvinyl alcohol water solution of 1.0% (g/g), regulates acidity with concentrated hydrochloric acid, makes pH less than 2.1m1Tween80 is joined in this polyvinyl alcohol water solution of 25ml, process water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 25.Splash into the prepared S/O of step (c) to aqueous phase (W)
1Emulsion is processed stable S/O
1Emulsion in the/W.Measure 5.0mlSpan80, join in the 100ml cyclohexane, process decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under the 1500r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1Emulsion in the/W adds the crosslinking agent glutaraldehyde at last, processes stable S/O
1/ W/O
2Double emulsion.Wherein the amount ratio of glutaraldehyde and polyvinyl alcohol is 1: 2 (mol ratio), S/O
1Emulsion and decentralized photo (O in/the W
2) amount ratio be 1: 3.4 (volume ratio).S/O
1/ W/O
2Condensation reaction takes place at water oil interface in double emulsion, and suction filtration, washing, drying after 3 hours obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
Through measuring prepared hud typed reversible heat-sensible complex microsphere average grain diameter 22 μ m, variable color time 260s, secondary color time 320s, 41 ° of C of discoloring temperature.Measure 41 ° of C of discoloring temperature, variable color time 250s, secondary color time 330s repeatedly after the heating and cooling 60 times.In methyl alcohol, ethanol, acetone, toluene, oxolane, acetate (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent, soak after 24 hours and measure; 41 ° of C of discoloring temperature; The variable color time remains on 250s ± 10s, secondary color time 330s ± 10s.
Embodiment 6: it is 0.5gm1 that the silicon-based mesoporous microballoon of 0.3gMCM-41 is joined 15ml concentration
-1CoCl
2In the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying makes reversible heat-sensible temperature indicating microballoon (S).Silicon-based mesoporous microballoon of MCM-41 and CoCl
2Amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, join at 1: 20 in the 5ml cyclohexane, process oil phase (O according to volume ratio
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, process stable S/O
1Emulsion.Configuration concentration is the polyvinyl alcohol water solution of 0.9% (g/g), regulates acidity with concentrated hydrochloric acid, makes pH less than 2.1m1Tween80 is joined in this polyvinyl alcohol water solution of 25ml, process water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 25.Splash into the prepared S/O of step (c) to aqueous phase (W)
1Emulsion is processed stable S/O
1Emulsion in the/W.Measure 4.5mlSpan80, join in the 90ml cyclohexane, process decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under the 1300r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1Emulsion in the/W adds the crosslinking agent glutaraldehyde at last, processes stable S/O
1/ W/O
2Double emulsion.Wherein the amount ratio of glutaraldehyde and polyvinyl alcohol is 1: 2.5 (mol ratio), S/O
1Emulsion and decentralized photo (O in/the W
2) amount ratio be 1: 3 (volume ratio).S/O
1/ W/O
2Condensation reaction takes place at water oil interface in double emulsion, and suction filtration, washing, drying after 3 hours obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
Through measuring prepared hud typed reversible heat-sensible complex microsphere average grain diameter 20 μ m, variable color time 240s, secondary color time 350s, 41 ° of C of discoloring temperature.Measure 41 ° of C of discoloring temperature, variable color time 220s, secondary color time 360s repeatedly after the heating and cooling 60 times.In methyl alcohol, ethanol, acetone, toluene, oxolane, acetate (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent, soak after 24 hours and measure; 41 ° of C of discoloring temperature; The variable color time remains on 230s ± 10s, secondary color time 370s ± 10s.
Claims (1)
1. the preparation method of a hud typed reversible heat-sensible temperature indicating complex microsphere is characterized in that step is following:
Step 1: it is 0.5gml that the silicon-based mesoporous microballoon of MCM-41 is joined concentration
-1CoCl
2In the aqueous solution, adsorb after 1～2 hour, carry out centrifugally, vacuum drying makes reversible heat-sensible temperature indicating microballoon (S); Silicon-based mesoporous microballoon of said MCM-41 and CoCl
2Mass ratio be 1: 25;
Step 2: with emulsifying agent Span80, join at 1: 20 in the cyclohexane, process oil phase (O according to volume ratio
1);
Step 3: reversible heat-sensible temperature indicating microballoon (S) is joined oil phase (O
1) in, process stable S/O
1Emulsion;
Step 4: with emulsifying agent Tween80, join in the polyvinyl alcohol water solution, process water (W); The volume ratio of said emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20～25; Said polyvinyl alcohol water solution concentration is 0.8%～1.0% (g/g), regulates acidity with concentrated hydrochloric acid, makes pH less than 2;
Step 5: splash into the prepared S/O of step 3 to aqueous phase (W)
1Emulsion is processed stable S/O
1Emulsion in the/W;
Step 6: emulsifying agent Span80 joined process decentralized photo (O in the cyclohexane
2), under 1200～1500r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step 5
1Emulsion in the/W adds the crosslinking agent glutaraldehyde at last, processes stable S/O
1/ W/O
2Double emulsion; The volume ratio of said cyclohexane and Span80 is 20: 1; The mol ratio of said glutaraldehyde and polyvinyl alcohol is 1: 2～2.5; Said S/O
1Emulsion and decentralized photo (O in/the W
2) volume ratio be 1: 3～4;
Step 7: the S/O that step 6 is obtained
1/ W/O
2Double emulsion stirs with 1200～1500r/min, makes S/O
1/ W/O
2Condensation reaction takes place at water oil interface in double emulsion; After 2～3 hours, carry out suction filtration, washing and drying, obtain hud typed reversible heat-sensible temperature indicating complex microsphere then.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862709A (en) * | 2019-11-22 | 2020-03-06 | 济南大学 | Reversible thermochromic metal complex microcapsule and preparation method and application thereof |
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|---|---|---|---|---|
| US4479911A (en) * | 1982-01-28 | 1984-10-30 | Sandoz, Inc. | Process for preparation of microspheres and modification of release rate of core material |
| CN1069750A (en) * | 1992-09-08 | 1993-03-10 | 金柽华 | Heat-sensitive ink for temperature indication |
| CN1648623A (en) * | 2004-01-21 | 2005-08-03 | 上海腾泰应用科技有限公司 | Thermal sensitive composition and disposable thermometer made therefrom |
| CN101665677A (en) * | 2009-09-01 | 2010-03-10 | 苏州纳米技术与纳米仿生研究所 | Thermosensitive chromotropic material and manufacturing method and application thereof |
-
2012
- 2012-05-14 CN CN201210148050.5A patent/CN102658070B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4479911A (en) * | 1982-01-28 | 1984-10-30 | Sandoz, Inc. | Process for preparation of microspheres and modification of release rate of core material |
| CN1069750A (en) * | 1992-09-08 | 1993-03-10 | 金柽华 | Heat-sensitive ink for temperature indication |
| CN1648623A (en) * | 2004-01-21 | 2005-08-03 | 上海腾泰应用科技有限公司 | Thermal sensitive composition and disposable thermometer made therefrom |
| CN101665677A (en) * | 2009-09-01 | 2010-03-10 | 苏州纳米技术与纳米仿生研究所 | Thermosensitive chromotropic material and manufacturing method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862709A (en) * | 2019-11-22 | 2020-03-06 | 济南大学 | Reversible thermochromic metal complex microcapsule and preparation method and application thereof |
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