CN102658070B - 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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- CN102658070B CN102658070B CN201210148050.5A CN201210148050A CN102658070B CN 102658070 B CN102658070 B CN 102658070B CN 201210148050 A CN201210148050 A CN 201210148050A CN 102658070 B CN102658070 B CN 102658070B
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- temperature indicating
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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 the thermochromatism that had and invertibity, the advantage such as in bright gay color, synthesis technique simple, cost is lower, has 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 representational low-temperature inorganic reversible heat-sensible thermally indicating material that has.When being heated to 40 ℃, losing the crystallization water and become blueness from redness; Naturally, after cooling, from environment, absorb water and generation secondary color.The thermal discoloration of this material (as become the temperature of secondary color time, change secondary color) is very easily subject to the impact of the factors such as air humidity, solvent, heat time, firing rate, heating times, and temperature indicating precision is not high, and application is also restricted.As there is larger difference the secondary color time because air humidity is different, conventionally need 40min left and right.In organic solvent environment, often because discoloration is lost in the variation of structure; Poor with macromolecular material compatibility, while being used as the base paint of organic coating or ink, be prone to separating out of solids, affect coating performance.
Take mesoporous nano microballoon as carrier, and adsorbed water dissolubility reversible heat-sensible thermally indicating material, makes reversible heat-sensible temperature indicating microballoon; With macromolecular material, wrap up again; make the complex microsphere of nucleocapsid structure; can utilize the protection of specific area, adsorption capacity and shell that mesoporous microsphere is high; make the thermochromism process of material not be subject to the impact of environment and service condition; greatly improve its thermochromic properties and environmental suitability, expand its scope of application.
For many years, the Research of Microencapsulation of reversible heat-sensible thermally indicating material is affected thermally indicating material in minimizing external environment, shorten the secondary color time, the aspects such as compatibility of improvement and organic material and solvent have obtained some achievements.But at present all to take the aqueous solution droplets of thermo-sensitive material be core to prepared temperature-sensitive temperature indicating microcapsules, hydroxyethylcellulose or polyvinyl alcohol are that shell material is produced.Require shell material to form seamless material membrane in core polymerization around, the control of shell material self performance and experiment condition is required harsh, be prone to cyst wall porous, broken shell and cause core to run off and the phenomenon of sex change.The microcapsules that the liquid of take is core simultaneously, mechanical strength is low, and not resistance to extruding, easily breaks when active force is larger, and application is subject to certain limitation.Hud typed reversible temperature indicating complex microsphere particle diameter is easy to control, and the impact of shell material reduces, and mechanical strength is high, environmental suitability is strong, and variable color secondary color is sensitiveer.
By literature search, not yet find that adopting mesoporous nano microballoon is carrier, reversible heat-sensible temperature indicating microballoon is core, and macromolecular material is the relevant report that shell material is prepared hud typed reversible heat-sensible temperature indicating complex microsphere.
Summary of the invention
The technical problem solving
For fear of the deficiencies in the prior art part, the present invention proposes a kind of preparation method of hud typed reversible heat-sensible temperature indicating complex microsphere, to solve, in prior art, to take the temperature indicating microcapsules that liquid is core harsh to shell material self performance and requirement for experiment condition, mechanical strength is low, not resistance to extruding, is prone to the deficiencies such as cyst wall porous, broken shell phenomenon.
Technical scheme
A preparation method for hud typed reversible heat-sensible temperature indicating complex microsphere, is characterized in that step is as follows:
Step 1: it is 0.5gml that the silicon-based mesoporous microballoon of MCM-41 is joined to concentration
-1coCl
2in the aqueous solution, adsorb after 1～2 hour, carry out centrifugally, vacuum drying, makes reversible heat-sensible temperature indicating microballoon (S); The silicon-based mesoporous microballoon of described MCM-41 and CoCl
2mass ratio be 1: 25;
Step 2: by emulsifying agent Span80, join at 1: 20 in cyclohexane according to volume ratio, make oil phase (O
1);
Step 3: reversible heat-sensible temperature indicating microballoon (S) is joined to oil phase (O
1) in, make stable S/O
1emulsion;
Step 4: by emulsifying agent Tween80, join in polyvinyl alcohol water solution, make water (W); The volume ratio of described emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20～25; Described polyvinyl alcohol water solution concentration is 0.8%～1.0% (g/g), with concentrated hydrochloric acid, regulates acidity, makes pH be less than 2;
Step 5: (W) splashes into the prepared S/O of step 3 in water
1emulsion, makes stable S/O
1emulsion in/W;
Step 6: emulsifying agent Span80 is joined and makes decentralized photo (O in 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/W, finally adds crosslinking agent glutaraldehyde, makes stable S/O
1/ W/O
2double emulsion; The volume ratio of described cyclohexane and Span80 is 20: 1; The mol ratio of described glutaraldehyde and polyvinyl alcohol is 1: 2～2.5; Described S/O
1emulsion and decentralized photo (O in/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
2at water oil interface, there is condensation reaction in double emulsion; After 2～3 hours, carry out suction filtration, washing and dry, then obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
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 the application of inorganic reversible heat-sensible thermally indicating material in ink, coating and the exploitation of novel thermally indicating material provide method.
It is easy to control that the inventive method has particle diameter, and experiment condition is gentle, clad ratio high.Prepared complex microsphere mechanical strength is high, environmental suitability is strong, and temperature indicating is functional, stable, reproducible.
The specific embodiment
Now the invention will be further described in conjunction with the embodiments:
Embodiment 1: it is 0.5gml that the silicon-based mesoporous microballoon of 0.3gMCM-41 is joined to 15ml concentration
-1coCl
2in the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying, makes reversible heat-sensible temperature indicating microballoon (S).The silicon-based mesoporous microballoon of MCM-41 and CoCl
2amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, according to volume ratio, join at 1: 20 in 5ml cyclohexane, make oil phase (O
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, make stable S/O
1emulsion.Configuration concentration is the polyvinyl alcohol water solution of 0.8% (g/g), with concentrated hydrochloric acid, regulates acidity, makes pH be less than 2.1m1Tween80 is joined in this polyvinyl alcohol water solution of 20ml, make water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20.In water, (W) splashes into the prepared S/O of step (c)
1emulsion, makes stable S/O
1emulsion in/W.Measure 4.0mlSpan80, join in 80ml cyclohexane, make decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under 1200r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1emulsion in/W, finally adds crosslinking agent glutaraldehyde, makes 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/W
2) amount ratio be 1: 3.2 (volume ratio).S/O
1/ W/O
2there is condensation reaction at water oil interface in double emulsion, after 3 hours, suction filtration, washing, dry, obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
After measured, 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.Heating and cooling are measured for 60 times afterwards repeatedly, 41 ° of C of discoloring temperature, variable color time 210s, secondary color time 330s.Soak 24 hours in methyl alcohol, ethanol, acetone, toluene, oxolane, acetic acid (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent after, 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 to 10ml concentration
-1coCl
2in the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying, makes reversible heat-sensible temperature indicating microballoon (S).The silicon-based mesoporous microballoon of MCM-41 and CoCl
2amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, according to volume ratio, join at 1: 20 in 5ml cyclohexane, make oil phase (O
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, make stable S/O
1emulsion.Configuration concentration is the polyvinyl alcohol water solution of 0.9% (g/g), with concentrated hydrochloric acid, regulates acidity, makes pH be less than 2.1m1Tween80 is joined in this polyvinyl alcohol water solution of 20ml, make water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20.In water, (W) splashes into the prepared S/O of step (c)
1emulsion, makes stable S/O
1emulsion in/W.Measure 4.0mlSpan80, join in 80ml cyclohexane, make decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under 1200r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1emulsion in/W, finally adds crosslinking agent glutaraldehyde, makes 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/W
2) amount ratio be 1: 3.2 (volume ratio).S/O
1/ W/O
2there is condensation reaction at water oil interface in double emulsion, after 2 hours, suction filtration, washing, dry, obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
After measured, 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.Heating and cooling are measured for 60 times afterwards repeatedly, 41 ° of C of discoloring temperature, variable color time 260s, secondary color time 360s.Soak 24 hours in methyl alcohol, ethanol, acetone, toluene, oxolane, acetic acid (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent after, 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 to 10ml concentration
-1coCl
2in the aqueous solution, adsorb after 1 hour, centrifugal, vacuum drying, makes reversible heat-sensible temperature indicating microballoon (S).The silicon-based mesoporous microballoon of MCM-41 and CoCl
2amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, according to volume ratio, join at 1: 20 in 5ml cyclohexane, make oil phase (O
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, make stable S/O
1emulsion.Configuration concentration is the polyvinyl alcohol water solution of 0.8% (g/g), with concentrated hydrochloric acid, regulates acidity, makes pH be less than 2.1ml Tween80 is joined in this polyvinyl alcohol water solution of 25ml, make water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 25.In water, (W) splashes into the prepared S/O of step (c)
1emulsion, makes stable S/O
1emulsion in/W.Measure 4.5mlSpan80, join in 90ml cyclohexane, make decentralized photo (O
2), the amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under 1400r/min stirring action, in decentralized photo, splash into the prepared S/O of step (e)
1emulsion in/W, finally adds crosslinking agent glutaraldehyde, makes 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/W
2) amount ratio be 1: 3 (volume ratio).S/O
1/ W/O
2there is condensation reaction at water oil interface in double emulsion, after 3 hours, suction filtration, washing, dry, obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
After measured, 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.Heating and cooling are measured for 60 times afterwards repeatedly, 41 ° of C of discoloring temperature, variable color time 230s, secondary color time 340s.Soak 24 hours in methyl alcohol, ethanol, acetone, toluene, oxolane, acetic acid (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent after, 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 to 15ml concentration
-1coCl
2in the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying, makes reversible heat-sensible temperature indicating microballoon (S).The silicon-based mesoporous microballoon of MCM-41 and CoCl
2amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, according to volume ratio, join at 1: 20 in 5ml cyclohexane, make oil phase (O
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, make stable S/O
1emulsion.Configuration concentration is the polyvinyl alcohol water solution of 1.0% (g/g), with concentrated hydrochloric acid, regulates acidity, makes pH be less than 2.1ml Tween80 is joined in this polyvinyl alcohol water solution of 20ml, make water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 20.In water, (W) splashes into the prepared S/O of step (c)
1emulsion, makes stable S/O
1emulsion in/W.Measure 5.0mlSpan80, join in 100ml cyclohexane, make decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under 1400r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1emulsion in/W, finally adds crosslinking agent glutaraldehyde, makes 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/W
2) amount ratio be 1: 4 (volume ratio).S/O
1/ W/O
2there is condensation reaction at water oil interface in double emulsion, after 3 hours, suction filtration, washing, dry, obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
After measured, 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.Heating and cooling are measured for 60 times afterwards repeatedly, 41 ° of C of discoloring temperature, variable color time 300s, secondary color time 380s.Soak 24 hours in methyl alcohol, ethanol, acetone, toluene, oxolane, acetic acid (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent after, 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 to 20ml concentration
-1coCl
2in the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying, makes reversible heat-sensible temperature indicating microballoon (S).The silicon-based mesoporous microballoon of MCM-41 and CoCl
2amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, according to volume ratio, join at 1: 20 in 5ml cyclohexane, make oil phase (O
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, make stable S/O
1emulsion.Configuration concentration is the polyvinyl alcohol water solution of 1.0% (g/g), with concentrated hydrochloric acid, regulates acidity, makes pH be less than 2.1m1Tween80 is joined in this polyvinyl alcohol water solution of 25ml, make water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 25.In water, (W) splashes into the prepared S/O of step (c)
1emulsion, makes stable S/O
1emulsion in/W.Measure 5.0mlSpan80, join in 100ml cyclohexane, make decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under 1500r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1emulsion in/W, finally adds crosslinking agent glutaraldehyde, makes 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/W
2) amount ratio be 1: 3.4 (volume ratio).S/O
1/ W/O
2there is condensation reaction at water oil interface in double emulsion, after 3 hours, suction filtration, washing, dry, obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
After measured, 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.Heating and cooling are measured for 60 times afterwards repeatedly, 41 ° of C of discoloring temperature, variable color time 250s, secondary color time 330s.Soak 24 hours in methyl alcohol, ethanol, acetone, toluene, oxolane, acetic acid (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent after, 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 to 15ml concentration
-1coCl
2in the aqueous solution, adsorb after 2 hours, centrifugal, vacuum drying, makes reversible heat-sensible temperature indicating microballoon (S).The silicon-based mesoporous microballoon of MCM-41 and CoCl
2amount ratio be 1: 25 (mass ratio).Get emulsifying agent Span800.25ml, according to volume ratio, join at 1: 20 in 5ml cyclohexane, make oil phase (O
1).Get the prepared reversible heat-sensible temperature indicating microballoon (S) of step (a) and join oil phase (O
1) in, make stable S/O
1emulsion.Configuration concentration is the polyvinyl alcohol water solution of 0.9% (g/g), with concentrated hydrochloric acid, regulates acidity, makes pH be less than 2.1m1Tween80 is joined in this polyvinyl alcohol water solution of 25ml, make water (W), the volume ratio of emulsifying agent Tween80 and polyvinyl alcohol water solution is 1: 25.In water, (W) splashes into the prepared S/O of step (c)
1emulsion, makes stable S/O
1emulsion in/W.Measure 4.5mlSpan80, join in 90ml cyclohexane, make decentralized photo (O
2).The amount ratio of cyclohexane and Span80 is 20: 1 (volume ratio); Under 1300r/min stirring action, to decentralized photo (O
2) in splash into the prepared S/O of step (e)
1emulsion in/W, finally adds crosslinking agent glutaraldehyde, makes 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/W
2) amount ratio be 1: 3 (volume ratio).S/O
1/ W/O
2there is condensation reaction at water oil interface in double emulsion, after 3 hours, suction filtration, washing, dry, obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
After measured, 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.Heating and cooling are measured for 60 times afterwards repeatedly, 41 ° of C of discoloring temperature, variable color time 220s, secondary color time 360s.Soak 24 hours in methyl alcohol, ethanol, acetone, toluene, oxolane, acetic acid (10%), hydrochloric acid (5%) and NaOH (2%) equal solvent after, measure, 41 ° of C of discoloring temperature, the variable color time remains on 230s ± 10s, secondary color time 370s ± 10s.
Claims (1)
1. a preparation method for hud typed reversible heat-sensible temperature indicating complex microsphere, is characterized in that step is as follows:
Step 1: it is 0.5gmL that the silicon-based mesoporous microballoon of MCM-41 is joined to concentration
-1coCl
2in the aqueous solution, adsorb after 1～2 hour, carry out centrifugally, vacuum drying, makes reversible heat-sensible temperature indicating microballoon (S); The silicon-based mesoporous microballoon of described MCM-41 and CoCl
2mass ratio be 1:25;
Step 2: by emulsifying agent Span80, join in cyclohexane according to volume ratio 1:20, make oil phase (O
1);
Step 3: reversible heat-sensible temperature indicating microballoon (S) is joined to oil phase (O
1) in, make stable S/O
1emulsion;
Step 4: by emulsifying agent Tween80, join in polyvinyl alcohol water solution, make water (W); The volume ratio of described emulsifying agent Tween80 and polyvinyl alcohol water solution is 1:20～25; Described polyvinyl alcohol water solution concentration is 0.8%～1.0% (g/g), with concentrated hydrochloric acid, regulates acidity, makes pH be less than 2;
Step 5: splash into the prepared S/O of step 3 in water (W)
1emulsion, makes stable S/O
1emulsion in/W;
Step 6: emulsifying agent Span80 is joined and makes decentralized photo (O in 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/W, finally adds crosslinking agent glutaraldehyde, makes stable S/O
1/ W/O
2double emulsion; The volume ratio of described cyclohexane and Span80 is 20:1; The mol ratio of described glutaraldehyde and polyvinyl alcohol is 1:2～2.5; Described S/O
1emulsion and decentralized photo (O in/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
2at water oil interface, there is condensation reaction in double emulsion; After 2～3 hours, carry out suction filtration, washing and dry, then obtain hud typed reversible heat-sensible temperature indicating complex microsphere.
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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 |
-
2012
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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 |
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