CN104877065B - The big organic reversible thermochromic microcapsules of long lifespan aberration and preparation method - Google Patents
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Abstract
The present invention discloses the big organic reversible thermochromic microcapsules of long lifespan aberration and preparation method.Organic reversible thermochromic microcapsule wall material is polymerized by the acrylate of percentage by weight 30~95% or/and methacrylate, the divinyl of percentage by weight 5~70% and/or multi-vinyl monomer mixture, the acrylic acid of percentage by weight 0~10% and/or methacrylic acid mixture, core is by colour former 3,3 pairs of (4 diformazan aminophenyl) the 6 dimethylamino phthalides, the dihydroxydiphenylsulisomers of developer 4,4 ' and constituted selected from a kind of solvent in 1 dodecanol, 1 tetradecanol, 1 hexadecanol, 1 octadecanol；Its preparation method is then made up of monomer pre-polymerization by suspension polymerisation, and the organic reversible thermochromic microcapsules for obtaining have the advantages that long lifespan aberration is big, will not release formaldehyde, without bisphenol-A, using safer.
Description
Technical field
The present invention relates to organic reversible thermochromic microcapsules and preparation method, acrylate-based wall material is related specifically to
Organic reversible thermochromic microcapsules and preparation method, belong to field of fine chemical.
Background technology
Organic Reversible Thermochromic Materials refer to a kind of when temperature is higher or lower than specified temp, and color can become
The functional material of change, and have memory function, can Reusability.Organic Reversible Thermochromic Materials one based on electron exchange mechanism
As be made up of colour former, developer, solvent, colour former determine off-color material system color, shade is mainly by developer
Determine, solvent borne material plays a part of to adjust variable color system discoloring temperature.
Due to electronq donor class dyestuff composition organic reversible thermochromic compound it is bright in luster, change colour it is sensitive,
Price is less than liquid crystal material, thus has obtained necessarily should in fabrics printing and dyeing, printing-ink, false proof, thermally indicating material, coating
With, but its major defect is that, when there is color change, solvent therein can be changed into liquid or from liquid change solid from solid,
It is thus easily affected by environment, when running into strong acid, discoloration invertibity can be lost, when running into highly basic, highly basic can be with faintly acid developer
Reaction, can also lose discoloration invertibity, may be dissolved in some organic solvents, thus require organic reversible thermochromic
Compound is kept apart with use environment, and a kind of method kept apart is exactly to use macromolecular material by organic reversible thermochromic
Material is wrapped up, and obtains the microcapsules containing organic Reversible Thermochromic Materials, and this preparation process is also referred to as microencapsulation,
Organic reversible thermochromic compound in microcapsules is referred to as core, the macromolecular material that core is wrapped up referred to as wall material,
It is required that wall material energy strong alkali-acid resistance and organic solvent, not degradable, wall material is transparent, and absorptance is low, can prevent to organic reversible
Keen and vividness the influence of thermochromic material discoloration.
The document for preparing organic reversible thermochromic microcapsules is a lot, but wall material species is few, Chinese patent
CN102477290 discloses a kind of thermo-sensitive discoloration material microcapsule and preparation method thereof, and wall material raw material is melamine resin prepolymer,
Wall material disclosed in Chinese patent CN102807853 is SMA and Lauxite prepolymer shape
Into containment wall system, although preferably, but its translucency is poor, causes Lauxite and honey for Lauxite honey and melamine resin sealing
Polyimide resin makees organic Reversible Thermochromic Materials microcapsules of wall material, aberration during color change occurs small；Due to Lauxite or
Melamine resin and thermochromism compound there is a problem of incompatible, cause organic reversible thermochromic microcapsules in experience temperature
Discoloration can be quickly lost after change, service life is short；Other either Lauxite or melamine resin, are using process
Might have Form aldehyde release out, and formaldehyde is generally acknowledged carcinogen；Other common wall materials have gelatin, although the printing opacity of gelatin
Property be better than Lauxite, melamine resin, but limited by gelatin properties, its less stable, easily degraded.It is existing based on electronics
Organic reversible thermochromic compound of gain and loss mechanism, is used mostly bisphenol-A and makees developer, and bisphenol-A is incretion interferent,
Accumulation can produce serious environment and ecological problem in nature and environment.
Therefore it is an object of the present invention to provide a kind of big color change in other words of aberration is obvious, thermochromic properties are steady
Fixed long lifespan in other words, without bisphenol-A, will not release formaldehyde organic reversible thermochromic microcapsules, it is of the invention another
Purpose is to provide the method for preparing organic reversible thermochromic microcapsules.
The content of the invention
To overcome above-mentioned the deficiencies in the prior art, it is micro- that the present invention discloses a kind of big organic reversible thermochromic of long lifespan aberration
Capsule and preparation method thereof.
The big organic reversible thermochromic microcapsules of long lifespan aberration, are made up of the wall material of core and parcel core, therein
Core be containing leuco dye, developer, solvent organic reversible thermochromic compound, wall material is aggregated by monomer mixture
After obtain, constitute wall material mixture be：
Monomer first：The acrylate of percentage by weight 30~95% or/and methacrylate,
Monomer second：The divinyl of percentage by weight 5~70% and/or multi-vinyl monomer mixture,
Monomer third：The acrylic acid of percentage by weight 0~10% and/or methacrylic acid,
Organic reversible thermochromic microcapsules absorbance is more than 0.4, and organic reversible thermochromic microcapsules can at least experience
360 thermal cycle experiments, its absorbance dough softening is less than 30%；
The preferred methyl acrylate of monomer first, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate；
The preferred divinylbenzene of monomer second, GDMA, pentaerythritol triacrylate, trimethylolpropane tris propylene
Acid esters, diethylene glycol diacrylate, TEGDMA, dimethacrylate, new penta 2
Alcohol dimethylacrylate.
Double (4- diformazans the aminophenyl) -6- dimethylamino phthalides of the colour former of organic reversible thermochromic compound preferably 3,3-
(No. CAS：1552-42-7, crystal violet lactone)), developer preferably 4,4 '-dihydroxydiphenylsulisomer (No. CAS：80-09-1, bis-phenol
S), one kind in solvent selection DODECANOL, 1-, 1- tetradecanols, 1- hexadecanols, 1- octadecanols.
It is double (4- diformazans aminophenyl) -6- dimethylaminos phthalides of 3,3- in organic reversible thermochromic compound, developer, molten
The weight ratio preferably 1 of agent: (1~6): (50~250).
Organic reversible thermochromic compound core weight and monomer mixture weight and the ratio between preferably 1: (0.8~2.4).
Organic reversible thermochromic Microcapsules Size is at 40~600 microns.
The big organic reversible thermochromic microcapsule preparation method of long lifespan aberration comprises the following steps：
A) oil-soluble initiator pre-polymerization is added in monomer first or monomer first and the mixture of monomer third,
B) organic reversible thermochromic compound is added after pre-polymerization,
C) monomer second is added, it is dispersed into emulsion oil-in-water in the aqueous solution containing dispersant,
D) carry out Raolical polymerizable, filtration washing it is dry organic reversible thermochromic microcapsules.
Initiator preferred azodiisobutyronitrile when preparing organic reversible thermochromic microcapsules, initiator amount accounts for monomer first
Percentage by weight preferably 0.5~2%, 60~70 DEG C of pre-polymerization temperature, 30 minutes pre-polymerization time.
Dispersant preferred polyvinyl alcohol when preparing organic reversible thermochromic microcapsules, the concentration of polyvinyl alcohol water solution is excellent
Select 0.1%~0.8%.
Compared with prior art, the beneficial effects of the invention are as follows the long lifespan of organic Thermoreversibly discoloration microcapsules, aberration
Greatly, formaldehydeless release, without bisphenol-A, using safer.
Brief description of the drawings
Fig. 1 is the absorbance before and after comparative example 1, embodiment 1, the sample thermal cycle experiment of embodiment 2 before and after thermal cycle experiment
Curve.
Specific embodiment
To further understand the present invention, the preferred embodiment of the invention is described with reference to embodiment, but should
Work as understanding, these descriptions are simply to further illustrate the features and advantages of the present invention, rather than the limit to the claims in the present invention
System.
The big organic reversible thermochromic microcapsules of long lifespan aberration, including the wall material of core and parcel core is constituted, and it is special
Levy be core therein be containing leuco dye, developer, solvent organic reversible thermochromic compound, wall material is by monomer
Obtained after mixture is aggregated, constituting the mixture of wall material is：
Monomer first：The acrylate of percentage by weight 30~95% or/and methacrylate,
Monomer second：The divinyl of percentage by weight 5~70% and/or multi-vinyl monomer mixture,
Monomer third：The acrylic acid of percentage by weight 0~10% and/or methacrylic acid,
Organic reversible thermochromic microcapsules absorbance is more than 0.4, and organic reversible thermochromic microcapsules can at least experience
360 thermal cycle experiments, its absorbance dough softening is less than 30%；
Double (4- diformazans aminophenyl) -6- Dimethylaminobenzenes of colour former preferably 3,3- in organic reversible thermochromic compound
Phthalein, developer preferably 4,4 '-dihydroxydiphenylsulisomer, the preferred DODECANOL, 1- of solvent, 1- tetradecanols, 1- hexadecanols, 1- ten
Eight alkanols.
3,3- double (4- diformazans aminophenyl) -6- dimethylaminos phthalide, developer, the weight ratios preferably 1 of solvent: (1~6):
(50~250).
Organic reversible thermochromic compound core weight and monomer mixture weight and the ratio between preferably 1: (0.8~2.4).
Organic reversible thermochromic compound Microcapsules Size is at 40~400 microns.
Polyacrylate, polymethacrylates based polyalcohol are colourless and with good translucency, weatherability and resistance to old
The characteristics such as the property changed protrusion, thus be the excellent material for preparing thermochromism microcapsule wall material.
Acrylate or/and methacrylate in monomer first are selected from methyl acrylate, ethyl acrylate, acrylic acid fourth
Ester, 2- hydroxyethylmethacry,ates, tert-butyl acrylate, methyl methacrylate, Isobutyl methacrylate, acrylic acid benzyl
Ester, hydroxy propyl methacrylate, cyclohexyl methacrylate, preferably methyl acrylate, ethyl acrylate, butyl acrylate, first
Base acrylic acid, methyl methacrylate, the percentage by weight of monomer first is 30~95%.
Experiment finds that the homopolymers that only monomer first is formed cannot prepare thermochromism microcapsules, and monomer second is diethyl
Alkenyl or multi-vinyl monomer, monomer first can form microcapsules with the copolymer of monomer second, and monomer second is selected from divinylbenzene, two
Methacrylic acid glycol ester, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, diethylene glycol diacrylate
Ester, TEGDMA, dimethacrylate, neopentylglycol dimethacrylate, Isosorbide-5-Nitrae-
Butanediol diacrylate, 1,5-PD diacrylate, 1,6- hexanediyl esters, the propylene of 1,10- decanediols two
Acid esters, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, the preferred divinylbenzene of monomer second, dimethyl propylene
Olefin(e) acid glycol ester, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate, three
Ethylene glycol dimethacrylate, dimethacrylate, neopentylglycol dimethacrylate.Experiment discovery,
When monomer second percentage by weight is less than 5%, it is impossible to form microcapsules, and when monomer second is excessive, especially many vinyl esters
When class monomer is excessive, there is significant difference, selection monomer second percentage by weight 5~70% in thermochromism microcapsules color.
The addition of monomer third can improve the solvent resistance of microcapsules, but add at most organic micro- glue of reversible thermochromic
The discoloration invertibity of capsule can be affected, and percentage by weight is 0~10%.
Organic Reversible Thermochromic Materials based on electron exchange mechanism are typically made up of colour former, developer, solvent, hair
Toner determines the color of off-color material system, and shade is mainly determined that solvent borne material plays regulation discoloration member by developer
It is the effect of discoloring temperature.Double (4- diformazans the aminophenyl) -6- Dimethylaminobenzenes of the colour former of thermochromism compound preferably 3,3-
Phthalein, developer preferably 4,4 '-dihydroxydiphenylsulisomer, solvent selection DODECANOL, 1-, 1- tetradecanols, 1- hexadecanols, 1- ten
One kind in eight alkanols.
Three class materials preferably must be held in certain proportion scope in organic reversible thermochromic compound, could show obvious
Color change, when ratio is unreasonable, the thermochromic properties of compound can be affected, or color change very little, seriously
When even can lose invertibity, 3,3- double (4- diformazans aminophenyl) -6- dimethylaminos phthalide, developer, the weight of solvent are than excellent
Select 1: (1~6): (50~250).
Be related to the change of color and color certainly during thermochromic material use, in Ci hai by two colors it
Between difference be defined as aberration.Color includes tone, 3 features of saturation degree and brightness, and aberration is this comprehensive difference.Color
Difference typically has two kinds of method for expressing：One kind leans on subjective sensation, and aberration is divided into several grades, standard scale is made, as relative
Compare foundation；Another colour photometer is determined, by manually calculate or instrument the given data of display are compared automatically.It is international
Upper conventional NBS (NBS) aberration unit.3,3- double (4- diformazans aminophenyl) -6- dimethylamino phthalide compounds exist
Less than blueness is shown in the range of solvent temperature, during higher than solvent melting temperature, display white is right in thermochromic material research
Aberration description using it is more be the color that is given by subjective sensation, such as blue difference typically with it is dark blue, blue, sky blue,
Light blue, micro- indigo plant etc. word is represented, it is clear that very inaccurate；Using the ultraviolet-uisible spectrophotometer with integrating sphere, using unrestrained
Method for reflection, can exactly measure absorbance of the powdered substance in different wavelength range, and the general analysis all purpose instrument in Beijing has
The ultraviolet-uisible spectrophotometer of the TU-1901 of limit responsible company production, integrating sphere model is IS19-1.Shimadzu UV-3600,
The silent winged ultraviolet-visible spectrophotometers of Evolution 600 of thermofisher scientific matches and annex can complete this
A little properties are determined, and the specific operating method for determining described in product description to be defined.
During organic Reversible Thermochromic Materials use, require that organic Reversible Thermochromic Materials can undergo naturally
Temperature change repeatedly and chromatic aberration less, that is, require that organic reversible thermochromic microcapsules have relatively good heat endurance,
Therefore organic Reversible Thermochromic Materials are heated to more than discoloring temperature, and cooling down is allowed to anti-to below discoloring temperature
This thermal cycle is experienced again, when less than solvent melting temperature, 3,3- double (4- diformazans aminophenyl) -6- dimethylamino phthalide conducts
The aobvious blueness of the reversible thermochromic compound of colour former, to double (4- diformazans the aminophenyl) -6- dimethylamino phthalides of 3,3- as hair
The ultraviolet-visible spectrometry of the thermochromic material compound of toner finds that compound is maximum in the absorbance of 610nm, when super
When crossing solvent melting temperature, compound goes to zero in the absorbance of 610nm, visually observed under natural light it is white, therefore can
Using by 610nm absorbances as double (4- diformazans the aminophenyl) -6- dimethylaminos phthalides of 3,3- for developer compound and microcapsules
Change the color of product and measuring for color change, absorbance is bigger, show blue deeper, also illustrate that organic reversible thermochromic is micro-
Aberration is bigger before and after capsule discoloration, and the micro- glue of organic reversible thermochromic can be more accurately measured using 610nm absorbances and change
The color change of capsule, it is desirable to which organic reversible thermochromic microcapsules absorbance in itself is the bigger the better；Not experiencing thermal cycle reality
The organic reversible thermochromic microcapsules tested are referred to as former state, and compared with the absorbance of former state, in experience, temperature change causes repeatedly
During color change, it is desirable to which microcapsules are the smaller the better in the absorbance change of 610nm, that is, mean that microcapsules have the longer use longevity
Life, also implies that the front and rear bigger aberration of microcapsules discoloration, also there is more preferable thermal cycling stability, is quantitative measurement thermochromism
Color change size before and after microcapsules experience thermal cycle experiment, defines the absorbance dough softening to have after experience n times thermal cycle experiment
The percentage of the ratio between the difference and former state absorbance of the absorbance of machine reversible thermochromic microcapsules absorbance and former state, wherein for
The thermochromism microcapsules of Lauxite wall material N=240 times, for monomer first, monomer second, the polymer of monomer third having for wall material
For machine thermochromism microcapsules, N=360 times.
Thermal cycle experiment method is as follows：The Thermoreversibly discoloration microcapsules of certain mass are put into rub oral examination tube, by it
It is positioned in heat circulating system, temperature is circulated between less than 3 degrees Celsius of solvent fusing point and higher than 3 degrees Celsius of solvent fusing point to be handed over
Replace, sample is taken out every certain times of thermal cycle.Measured using dual-beam ultraviolet-uisible spectrophotometer and its integrating sphere accessory
Sample absorbance changes.
The acid-fast alkali-proof performance test methods of organic reversible thermochromic microcapsules：Weigh 4 parts respectively with electronic balance
The organic reversible thermochromic microcapsules of 0.02g, are placed in rub oral examination tube, are separately added into 2.00 grams of 0.10mol/L hydrochloric acid
Solution, 0.10mol/L acetic acid solutions, 0.10mol/L sodium hydroxide solutions and 0.10mol/L triethanolamine solutions, use grinding port plug
Sealing, places 24h at room temperature, microcapsules is taken out and is dried, comparative example 1, embodiment 1, the organic reversible thermotropic of embodiment 2
Color microcapsules still have Reversible thermochromic energy.0.02 gram of organic reversible thermochromic compound is dissolved in 2.00 grams
0.10mol/L aqueous hydrochloric acid solutions, 0.10mol/L acetic acid aqueous solutions, 0.10mol/L sodium hydrate aqueous solutions and 0.10mol/L tri-
Aqueous ethanolamine, and solution is colourless.
Solvent resistance method of testing：Weigh 7 parts of organic reversible thermochromic microcapsules of 0.02g respectively with assay balance,
Be placed in rub oral examination tube, be separately added into 2.00g toluene, benzene, dichloromethane, chloroform, normal heptane, ethyl acetate and
Petroleum ether, is sealed with grinding port plug, and 24h is placed at room temperature, microcapsules is taken out and is dried, and observes organic micro- glue of reversible thermochromic
Whether capsule has reversible color performance.0.02 gram of organic reversible thermochromic compound be dissolved in 2.00 grams of 2.00g toluene, benzene,
In dichloromethane, chloroform, normal heptane, ethyl acetate and petroleum ether, and solution is colourless.
Size distribution is sieved using standard sub-sieve and obtained.
The big organic reversible thermochromic microcapsule preparation method of aberration long of receiving the order comprises the following steps：
A) oil-soluble initiator pre-polymerization is added in monomer first or monomer first and the mixture of monomer third,
B) organic reversible thermochromic compound is added after pre-polymerization,
C) monomer second is added, it is dispersed into emulsion oil-in-water in the aqueous solution containing dispersant,
D) carry out Raolical polymerizable, filtration washing it is dry organic reversible thermochromic microcapsules.
The preferred azodiisobutyronitrile of initiator, initiator amount accounts for the percentage by weight preferably 0.5~2% of monomer first, in advance
Poly- temperature between 60 DEG C~70 DEG C, 30 minutes pre-polymerization time.
Acrylate and/or methacrylate intramolecular contain carbon-carbon double bond, and the group tool being connected with unsaturated bond
There is larger polarity, thus easily carry out Raolical polymerizable, for Raolical polymerizable, from monomer to polymer
Chain initiation, chain growth, chain termination three phases are experienced, after radical initiation reaction, chain rapid development is carried out, during extension polymerization
Between, simply increase the conversion ratio of monomer, and polymer molecular weight does not change, colour former 4,4 '-dihydroxydiphenylsulisomer contains
There is phenolic hydroxyl group, for the radical polymerization of vinyl monomer, aldehydes matter is common polymerization inhibitor, when organic reversible thermic
When discoloration compound selection aldehydes matter makees developer, due to the influence of the inhibition of aldehydes matter, monomer polymerization speed is bright
It is aobvious to reduce.
For monomer first or monomer first and monomer third, pre-polymerization temperature between 30 DEG C~80 DEG C, according to experimental result,
Initiator amount in preferred scope, between preferably 60 DEG C~70 DEG C of pre-polymerization temperature, during 30 minutes pre-polymerization time, the pre-polymerization for obtaining
Liquid adds core and monomer second easily to disperse, and pre-polymerization overlong time, pre-polymerization fluid viscosity is excessive, it is impossible to prepare the micro- glue of thermochromism
Capsule.
Initiator amount is big, and the free radical of generation is more, and polymer molecular weight tendency diminishes, and initiator amount is small, then be polymerized
Slow, preferred initiator amount accounts for the percentage by weight of monomer first 0.01~10%, preferably 0.1~4%, more preferably
0.5~2%.
Polymerization is divided into polymerisation in bulk, suspension polymerisation, polymerisation in solution and emulsion polymerization.Particle obtained by emulsion polymerization
Very little, generally less than 1 micron, product is difficult to separate, for the microencapsulation of reversible thermochromic compound, polymerisation in bulk
And polymerisation in solution cannot meet requirement naturally, suspension polymerisation turns into prefered method.Suspension polymerisation is by strong stirring and is dividing
In the presence of powder, monomer is scattered in medium in microballon form the polymerization for carrying out is triggered by oil-soluble initiator, suspended
In polymerization system, water is continuous phase, and monomer is dispersed phase, and monomer is insoluble or poorly soluble in water, and initiator is dissolved only in monomer, suspends poly-
, each microballon equivalent to one small body just the same with polymerisation in bulk is closed, mainly considers how to avoid in suspension polymerisation
Adhesion problems in polymer forming process, because adhesion often leads to radiating difficulty, or even can produce implode, cause and are polymerized
Cheng Buneng is smoothed out, and the effective ways that dispersant is adhesion problems in avoiding polymerization process, dispersant are added in continuous phase
It is divided into two classes, a class is the inorganic matter for being insoluble in water, such as calcium carbonate, magnesia, talcum powder, barium carbonate, calcium sulfate, diatomite
Deng, its effect be mechanical isolation act on；Another kind of is water miscible macromolecule, such as polyvinyl alcohol, gum arabic, polypropylene
Acid and salt, styrene-maleic anhydride copolymer, starch, gelatin, hydroxymethyl cellulose, the polyethylene pyrrole of polymethylacrylic acid
Pyrrolidone etc., its effect is absorption in droplet surface, formation layer protecting film；Using inorganic dispersant, in subsequent processes
The optical property of middle influence polymer, thus selection uses water soluble polymer, with gum arabic in water soluble polymer
When powder is dispersant, peptizaiton is poor, usually lumps, it is impossible to form microcapsules, and selection uses the polyvinyl alcohol of partial alcoholysis,
The polyvinyl alcohol degree of polymerization preferably 1000~3000, the still more preferably alcoholysis degree preferably 80~95% of polyvinyl alcohol, polyethylene
The alcohol degree of polymerization 1500~1900, the alcoholysis degree 85~90% of polyvinyl alcohol.The selection of polyvinyl alcohol consumption accounts for water phase weight
0.01%~5%, preferably 0.05%~2%, more preferably 0.1%~0.5%.
Specific embodiment of the invention is illustrated with preferred embodiment below.
Embodiment 1,10.0 grams of refined methyl methacrylate (MMA) is weighed with electronic balance in there-necked flask,
0.10 gram of initiator azodiisobutyronitrile (AIBN) is added, the pre-polymerization 30min under 65 DEG C of water bath conditions adds organic reversible thermic
10.0 grams of compound of discoloration, adds 1.00 grams of divinylbenzene (DVB), and organic reversible thermochromic compound proportioning is 3,3- double
(4- diformazans aminophenyl) -6- dimethylamino phthalides: 4,4 '-dihydroxydiphenylsulisomer: the proportioning of 1- hexadecanols takes 1: 3: 150, will
Mixture adds 200 gram weight percent concentrations in 0.3% polyvinyl alcohol (PVA) aqueous solution, to be cut using high-shear emulsion machine
Emulsification 3min is cut, 75 DEG C are then heated to, continues to react 3h, then be warming up to 85 DEG C of reaction 1h.By product washing and filtering, dry
Microcapsule product powder.
Embodiment 2,10.0 grams of refined methyl methacrylate (MMA) and methacrylic acid are weighed with electronic balance
(MAA) 0.20 gram in there-necked flask, add initiator azodiisobutyronitrile 0.10 gram of (AIBN), it is pre- under 65 DEG C of water bath conditions
Poly- 30min, adds 10.0 grams of thermochromism compound, adds 1.50 grams of divinylbenzene, and organic reversible thermochromic compound is matched somebody with somebody
Than being double (4- diformazans aminophenyl) -6- dimethylamino phthalides of 3,3-: 4,4 '-dihydroxydiphenylsulisomer: the proportioning of 1- hexadecanols takes 1
: 3: 150,200 gram weight percent concentrations are fed the mixture into 0.3% polyvinyl alcohol (PVA) aqueous solution, to use high shear
Mulser emulsification pretreatment 3min, then heats to 75 DEG C, continues to react 3h, then be warming up to 85 DEG C of reaction 1h.Product is washed
Filter, dries to obtain microcapsule product powder.
Comparative example 1, the organic reversible thermochromic microcapsules for preparing Lauxite wall material, by a certain amount of discoloration compound
In the Lauxite pre-polymerization liquid that addition is prepared, treat that organic reversible thermochromic compound is completely melt, using Arabic containing 4%
The aqueous solution of natural gum as water phase, 10 grams of core weight, the weight of urea and formaldehyde and 10 grams in pre-polymerization liquid, thermochromism compounding
Thing proportioning is double (4- diformazans aminophenyl) -6- dimethylamino phthalides of 3,3-: 4,4 '-dihydroxydiphenylsulisomer: 1- hexadecanols are matched somebody with somebody
Than taking 1: 3: 150, using high-shearing dispersion emulsifying machine emulsification pretreatment 3min after, be slowly added dropwise dilute acetic acid solutions regulation solution ph
4.2, by product washing and filtering, dry to obtain microcapsule product powder.
The thermochromism compound microscapsule powder that embodiment 1, embodiment 2 and comparative example 1 are obtained carries out absorbance survey
It is fixed, using the ultraviolet-uisible spectrophotometer with integrating sphere, it is measured according to instrument specification operating method, obtain extinction
Degree, its numerical value is respectively 1.262,0.875,0.265.
By after 360 thermal cycle experiments, embodiment 1, embodiment 2 and comparative example 1 being obtained by 240 thermal cycle experiments
To thermochromism microcapsules according to thermal cycle experiment method test obtaining absorbance, its numerical value is respectively 1.222,
0.672nd, 0.152, defined according to the absorbance dough softening and calculated, its dough softening is respectively 3.20%, 23.2%, 42.6%.
Fig. 1 is the absorbance of microcapsules microcapsules sample as former state and after thermal cycle experiment 360 times in embodiment 1, embodiment 2
Curve, microcapsules as former state and after thermal cycle experiment 240 times also list in Fig. 1 by the absorbance curve of sample in comparative example 1.
Comparative example 1, embodiment 1, organic reversible thermochromic microcapsules solvent-resistance test result of embodiment 2 are listed in table 1,
" √ " is represented by after solvent-resistance test, organic reversible thermochromic microcapsules still have reversible thermochromic ability in table 1,
"×" is represented by after solvent-resistance test, organic reversible thermochromic microcapsules lose reversible thermochromic ability.
Table 1,
40~600 microns of particle size distribution, embodiment 1, the granularity of embodiment 2 are concentrated and are dispersed in 80~300 microns.
Embodiment 3, embodiment 4 and comparative example 2 are listed to the experimental data and measurement result of comparative example 5 in table 1, are implemented
The remainder data and implementation of example 3 and comparative example 2 are with embodiment 1；The remainder data and embodiment party of embodiment 4 and comparative example 3
Method is with embodiment 2；
With the difference in comparative example 1 it is that core weight is 10 grams, urea in pre-polymerization liquid in comparative example 4 and comparative example 5
Increase to 20 grams, 30 grams with the weight sum of formaldehyde, remainder data and implementation are with comparative example 1.
Table 2,
Embodiment 3, the granularity of embodiment 4 are concentrated and are dispersed in 60~300 microns.
Claims (5)
1. the big organic reversible thermochromic microcapsules of long lifespan aberration, are made up of the wall material of core and parcel core, and its feature exists
In core be containing leuco dye, developer, solvent organic reversible thermochromic compound, wall material is by monomer mixture through poly-
Obtained after conjunction, constituting the monomer of wall material is：Monomer first：The acrylate of percentage by weight 30~95% or/and methacrylate,
Monomer second：The divinyl of percentage by weight 5~70% and/or multi-vinyl monomer mixture, monomer third：Percentage by weight 0~
10% acrylic acid and/or methacrylic acid, leuco dye are 3,3- double（4- diformazan aminophenyls）- 6- dimethylamino phthalides, developer
It is 4,4'- dihydroxydiphenylsulisomers, in solvent selection DODECANOL, 1-, 1- tetradecanols, 1- hexadecanols, 1- octadecanols one
Kind;Organic reversible thermochromic microcapsules absorbance is more than 0.4, and organic reversible thermochromic microcapsules can at least experience 360 times
Thermal cycle experiment, its absorbance dough softening is less than 30%.
2. big organic reversible thermochromic microcapsules of long lifespan aberration according to claim 1, it is characterised in that monomer first
It is preferred that methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate；The preferred divinylbenzene of monomer second, diformazan
Base acrylic acid glycol ester, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate
Ester, TEGDMA, dimethacrylate, neopentylglycol dimethacrylate.
3. big organic reversible thermochromic microcapsules of long lifespan aberration according to claim 1, it is characterised in that You Jike
3,3- is double in inverse thermochromism compound（4- diformazan aminophenyls）- 6- dimethylaminos phthalide, developer, the weight of solvent are than preferred
1∶（1~6）∶（50~250）.
4. big organic reversible thermochromic microcapsules of long lifespan aberration according to claim 1, it is characterised in that You Jike
Inverse thermochromism compound core weight and monomer mixture weight and the ratio between preferably 1:（0.8~2.4）.
5. big organic reversible thermochromic microcapsules of long lifespan aberration according to claim 1, it is characterised in that You Jike
Inverse thermochromism Microcapsules Size is at 40~600 microns.
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| CN109293821B (en) * | 2018-09-30 | 2020-06-09 | 江南大学 | Dye-doped liquid crystal microcapsule material and preparation method thereof |
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| CN112892429B (en) * | 2021-01-25 | 2022-07-08 | 唐山开滦化工科技有限公司 | Reversible thermochromic thermal expansion microcapsule and preparation method and application thereof |
| CN115703893A (en) * | 2021-08-13 | 2023-02-17 | 江苏双星彩塑新材料股份有限公司 | Preparation method of thermochromic polyester film |
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