CN101665677A - Thermosensitive chromotropic material and manufacturing method and application thereof - Google Patents
Thermosensitive chromotropic material and manufacturing method and application thereof Download PDFInfo
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- CN101665677A CN101665677A CN 200910034527 CN200910034527A CN101665677A CN 101665677 A CN101665677 A CN 101665677A CN 200910034527 CN200910034527 CN 200910034527 CN 200910034527 A CN200910034527 A CN 200910034527A CN 101665677 A CN101665677 A CN 101665677A
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Images
Abstract
The invention provides a chromotropic material using material phase transition control chromotropic reaction for realizing irreversible thermosensitive discoloration, and a manufacturing method and anapplication thereof, which is characterized in that a temperature-sensitive function and a chromotropic function are separated and respectively born by two materials, and the functions of the two materials are coordinated through designing a solidified carrier material structure with a specific melting point, realizing low temperature irreversible thermosensitive discoloration, enlarging the optional range of chromotropic temperature and chromotropic modes, and satisfying the different demands of practical application. The concrete method comprises the following steps: dissolving one of reactants of a chromotropic reaction into a material with the specific melting point by using the solid-liquid phase transition process of the material, solidifying into powder or grains, and then mixing with the other reactant of the chromotropic reaction to manufacture the irreversible thermosensitive chromotropic material. The invention has the principle that when the temperature of the mixture increases to be above a solidification point, the material dissolved with the chromotropic reactant is melted, and the reactant is released to react with the other reactant through contact to generate products with different colors.
Description
Technical field
The present invention relates to a kind of material and method for making and purposes of utilizing material phase transformation control metachromasia to realize irreversible heat-sensitive variable colour, belong to heat-sensitive variable colour smart material and structure field.
Background technology
Thermosensitive chromotropic material is a class intelligent material that can manifest different colours in response to temperature variation, be widely used in fields such as industry, medical treatment, false proof, clothes and daily decoration, as make thermo-paint, heat-sensitive colour-changing ink, extraordinary variable color paper, display material, allochroic clothes, variable color toy etc., have potential economic benefit and social benefit.
Thermosensitive chromotropic material is divided into reversible heat-sensible off-color material and irreversible thermosensitive chromotropic material.The reversible heat-sensible off-color material mainly contains three major types, is respectively mineral-type, organic class and liquid crystal type thermosensitive chromotropic material.The camouflage paint of mineral-type reversible heat-sensible off-color material is the iodide that contain Ag, Cu, Hg etc., complex compound, double salt etc. mostly, and the hexamethylenetetramine mixture that is formed by cobalt salt and nickel salt, as Ag
2HgI
4, HgI
2, CuHgI
4, CoCl
22C
5H
12N
410H
2O etc.Be characterized in that synthesis technique is simple, cost is low, but that its shortcoming is a temperature limit is narrow, toxicity is big, and aberration is little, has limited its application.The kind of organic class reversible heat-sensible off-color material is more, and volution class, dianthracene ketone, Schiff bases, glimmering hydro carbons, Synthesis of diaminodiphenyl can be as the pigment of organic thermosensitive chromotropic material.Organic reversible heat-sensible off-color material is often by electron donor, electron acceptor, conditioning agent, sensitizing agent and other solvent composition.Because of temperature variation produces the transfer transport phenomenon, absorb in the electronic transfer process or the light of the certain wavelength of radiation between electron donor and the electron acceptor, apparently colorific variation.The advantage of liquid crystal type thermosensitive chromotropic material is that variable color is highly sensitive, and in most cases temperature variation less than 1 ℃ change in color will take place, and selects for use different liquid crystal materials to realize variable color in very wide temperature range.Liquid crystal is between the intermediate state thing between solid-state and the liquid state mutually, and the mechanism that produces variable color also is because variation has taken place the state of material.Its shortcoming is the price height, to the chemical substance sensitivity, and the color changeable effect instability, overall discoloration is not as dyestuff.
The research of irreversible thermosensitive chromotropic material has also obtained extensive studies.At present, in the irreversible thermosensitive chromotropic material on the market, adopt single-material to bear temperature sensitive and two functions of colour-change more, caused the control of discoloring temperature and variable color mode relatively poor.Simultaneously, the temperature sensitive scope of most of products concentrates on the high-temperature zone, utilize some materials fusing back change in color to develop a series of temperature sensitive scopes at 60 ℃ to the 400 ℃ thermosensitive chromotropic materials that do not wait as Raychem company, the controlled thermosensitive chromotropic material product of low temperature is less relatively.
A potential application of the irreversible thermosensitive chromotropic material of low temperature is to be used for indicating some stability whether the highstrung product of temperature is surpassed the temperature of setting in storage or transportation.For example, the intelligent label that utilizes the irreversible thermosensitive chromotropic material of low temperature to make, can pass through change in color, accurately various vaccines (how between 2 ℃～8 ℃) that need low-temperature storage of indication and biological activity sample etc. whether store or transportation in lost efficacy or inactivation because surpass design temperature, thereby the safe in utilization and effect of assurance medicine or biological activity sample.In order to realize the industrial applications of this intelligent label, need the cheap irreversible thermo-sensitive material of low temperature, and low-cost label preparing technology, and do not need the production line of product is carried out big change when using this intelligent label.
At the demand of this intelligent label to the irreversible thermo-sensitive material of low temperature, doctor Rougeau of France Universit é de-Savoie etc. has synthesized the diacetylene compounds that series has irreversible heat-sensitive variable colour function, and corresponding alcohols, glycols, ester derivative.These compounds can manifest irreversible heat-sensitive variable colour characteristic in-50 ℃～70 ℃ temperature range, discoloring temperature depends on the chain length and the deriveding group of compound, but there is certain degree of difficulty in the accurate control of discoloring temperature.
Summary of the invention
The objective of the invention is to overcome the irreversible thermosensitive chromotropic material of traditional low temperature owing to integrate temperature sensitive function and colour change function, the shortcoming that causes the optional scope of discoloring temperature and variable color mode to be restricted, temperature sensitive function and colour change function are separated, bear by two kinds of materials, by designing intelligentized material structure, coordinate the function of two kinds of materials, realize the irreversible heat-sensitive variable colour of low temperature, widen the scope of discoloring temperature and variable color mode, satisfy the different demands of practical application.
First purpose of the present invention is achieved through the following technical solutions:
A kind of thermosensitive chromotropic material, comprising reacts to each other, and first reactant and second reactant of variable color take place, it is characterized in that: a kind of dissolving cured in the outer package carrier of specific fusing point in described first reactant or second reactant, another kind of reactant mixes with arbitrary proportion with solid state powder or granular carrier, and wherein said carrier has chemistry respectively with first, second reactant and contacts inertia.
First purpose of the present invention can also be achieved through the following technical solutions:
A kind of thermosensitive chromotropic material, comprising reacts to each other, and first reactant and second reactant of variable color take place, it is characterized in that: a kind of in described first reactant or second reactant for having the solid state powder or the particle of specific fusing point, have chemistry contact inertia with respect to another kind of reactant when solid-state, and mix with arbitrary proportion with another kind of reactant.
First purpose of the present invention can be achieved through the following technical solutions again:
A kind of thermosensitive chromotropic material, comprising reacts to each other, and first reactant, second reactant and the 3rd reactant of variable color take place, it is characterized in that: a kind of dissolving cured in having the outer package carrier of first fusing point in described three kinds of reactants, and a kind of in described in addition two kinds of reactants for having the solid state powder or the particle of second fusing point, have chemistry with respect to other reactant and carrier when solid-state and contact inertia, two kinds of reactants of described carrier and other mix with arbitrary proportion; Described first fusing point is higher than second fusing point or first fusing point is lower than second fusing point.
Further, three close technical schemes of above-mentioned a kind of thermosensitive chromotropic material, wherein solid state powder or particulate surface are formed with protective layer.
Second purpose of the present invention is achieved through the following technical solutions:
A kind of method for making of thermosensitive chromotropic material, its characterization step comprises: I, one of metachromatic reactant is dissolved in the carrier with specific fusing point; II, the carrier that will be dissolved with reactant are solidified into powder or particle; III, be lower than under the temperature environment of specific fusing point, solid state powder or particle and another kind of reactant are being mixed into thermosensitive chromotropic material with arbitrary proportion.
Further, the method for making of above-mentioned a kind of thermosensitive chromotropic material, the kind of wherein said carrier is distinguished mutually by specific fusing point own and chemistry contact inertia, or is same kind of time-like, by changing the specific fusing point of solute concentration modulation itself.
Second purpose of the present invention can also be achieved through the following technical solutions:
A kind of method for making of thermosensitive chromotropic material, its characterization step comprises: I, one of metachromatic reactant is solidified into powder or particle; II, be lower than under the temperature environment of specific fusing point, solid state powder or particle and another kind of reactant are being mixed into thermosensitive chromotropic material with arbitrary proportion.
Further; two close technical schemes of above-mentioned a kind of thermosensitive chromotropic material method for making; wherein said be solidified into pulverize after powder or particulate method comprise direct condensation cured, spray congealing solidifies; or be configured to the protective layer of emulsion form with tensio-active agent; solidify in process of cooling with interior phase emulsified particle, separate again.
Further, on be solidified in powder or the particulate method, by change forming the thickness of protective layer, the diffusion process after the regulation and control reactant discharges realizes the kinetics regulation and control to the variable color process.
A kind of tinting pigment, be meant ink, printing ink or coating, be used to make thermo-paint, heat-sensitive colour-changing ink, variable color paper, display material etc., it is characterized in that: described tinting pigment is made by each described thermosensitive chromotropic material in the claim 1 to 3, needing under the differing temps to be used for the occasion of heat-sensitive variable colour.
The outstanding substantive distinguishing features and the obvious improvement of a kind of thermosensitive chromotropic material of the present invention and method for making and purposes is mainly reflected in:
The present invention separates temperature sensitive function and colour change function, bear by two kinds of different materials respectively, work in coordination with the function of two kinds of materials again by an intelligence structure, widened the range of choice of discoloring temperature and variable color mode, can be suitable for different application demands, effectively reduce material cost.Discoloring temperature can be by the definite and adjusting of material of selecting to have specific fusing point or solidification value, being used to dissolve one of metachromasia thing, and the variable color mode then can arbitrarily be adjusted by selecting different metachromasias.
In addition, by using different materials or designing the dynamic process that different material structures is modulated heat-sensitive variable colour, enable the thermolability dynamic process that fully reflection is instructed to product.
Description of drawings
Below in conjunction with specific embodiment and accompanying drawing thereof innovation essence of the present invention is described in further detail:
Fig. 1 is a kind of metachromatic model synoptic diagram that the embodiment of the invention is selected;
Fig. 2 is the effect synoptic diagram of the irreversible thermosensitive chromotropic material of low temperature when being lower than discoloring temperature of embodiment of the invention preparation;
Fig. 3 is the effect synoptic diagram when being higher than discoloring temperature embodiment illustrated in fig. 2.
Embodiment
The invention provides a kind of novel thermosensitive material that utilizes material phase transformation control metachromasia realization arbitrary temp scope inside irreversible heat-sensitive variable colour and preparation method thereof.Its principle of design is: temperature sensitive function and colour change function are separated, bear by two kinds of materials, by designing intelligentized material structure, coordinate the function of two kinds of materials, realize the irreversible heat-sensitive variable colour of low temperature, widen the optional scope of discoloring temperature and variable color mode, satisfy the different demands of practical application.
This kind thermosensitive chromotropic material can be realized a metachromasia or the repeatedly metachromasia under condition of different temperatures according to the difference of constitutional features.Its representative constitutional features can be understood as:
A kind of thermosensitive chromotropic material, comprising reacts to each other, and first reactant and second reactant of variable color take place, a kind of dissolving cured in the outer package carrier of specific fusing point in wherein said first reactant or second reactant, another kind of reactant mixes with arbitrary proportion with solid state powder or granular carrier, and wherein said carrier has chemistry respectively with first, second reactant and contacts inertia.
Another kind of thermosensitive chromotropic material, comprising reacts to each other, and first reactant and second reactant of variable color take place, a kind of in wherein said first reactant or second reactant for having the solid state powder or the particle of specific fusing point, have chemistry contact inertia with respect to another kind of reactant when solid-state, and mix with arbitrary proportion with another kind of reactant.
Another thermosensitive chromotropic material, comprising reacts to each other, and first reactant, second reactant and the 3rd reactant of variable color take place, a kind of dissolving cured in having the outer package carrier of first fusing point in wherein said three kinds of reactants, and a kind of in described in addition two kinds of reactants for having the solid state powder or the particle of second fusing point, have chemistry with respect to other reactant and carrier when solid-state and contact inertia, two kinds of reactants of described carrier and other mix with arbitrary proportion; Described first fusing point both can be higher than second fusing point (in addition two kinds of reactants take place earlier after the metachromasias again with carrier in reactant generation metachromasia), (reactant in the carrier is prior to a kind of reactant generation metachromasia also can first fusing point to be lower than second fusing point, and after temperature continues to raise, continue and another kind of reactant generation metachromasia).
As the optimization of said structure technical scheme, wherein solid state powder or particulate surface can also form a water lactous protective layer.
From the preparation method, according to different material structures, there is subtle difference in its preparation process, but has consistence in general.Its characterization step comprises in detail: I, one of metachromatic reactant is dissolved in the carrier with specific fusing point; II, the carrier that will be dissolved with reactant are solidified into powder or particle; III, be lower than under the temperature environment of specific fusing point, solid state powder or particle and another kind of reactant are being mixed into thermosensitive chromotropic material with arbitrary proportion;
Perhaps comprise: I, one of metachromatic reactant is solidified into powder or particle; II, be lower than under the temperature environment of specific fusing point, solid state powder or particle and another kind of reactant are being mixed into thermosensitive chromotropic material with arbitrary proportion.
Be solidified in the above-mentioned method for making powder or particulate method comprise after the direct condensation cured pulverize, spray congealing solidifies, or is configured to the protective layer of emulsion form with tensio-active agent, solidifies separation again with interior phase emulsified particle in process of cooling; And by changing the thickness that forms protective layer, the diffusion process after the regulation and control reactant discharges realizes the kinetics regulation and control to the variable color process.
The preparation that thermosensitive chromotropic material of the present invention is concrete and practice step and be:
(1) select suitable metachromasia: require stable, the nontoxic or toxicity of selected metachromatic reactant to be not enough to constitute harm, electrochromic substance chemical property that the reaction back generates and colour stable, nontoxic or toxicity are not enough to constitute and endanger.
(2) select suitable temperature sensitive functional materials: select the material (solvent) of a suitable fusing point, what can dissolve metachromatic reactant in right amount forms sosoloid in the lump.Require colourless, stable, the nontoxic or toxicity of this material to be not enough to constitute harm.The melting point values of this material and fused temperature range depend on demands of applications.After the temperature-sensitive material fusion, the velocity of diffusion that is dissolved in metachromasia thing wherein can be regulated and control by appropriate means.
The preparation method of sosoloid is dissolved into the metachromasia thing in the selected solvent, and the condensation cured of directly lowering the temperature is then made powder again, and the method for also available use spray congealing is solidified.Last again with suitable chemical reagent protection powder, directly contact with another reactant to avoid powder surface.
Another sosoloid preparation method be select one with the immiscible solvent of selecting of solvent, utilize tensio-active agent to make emulsion.Require selected solvent low as far as possible, and its fusing point is lower than the fusing point of the solvent of dissolving metachromasia thing to the solubleness of metachromasia thing.Use suitable tensio-active agent that two kinds of solvents (having dissolved certain density metachromasia thing in wherein a kind of solvent) are made emulsion then, and dissolved the interior phase of the solvent formation emulsion of metachromasia thing.With this emulsion cooling, phase condensation cured in making generates the particle that the surface has coated the layer of surface promoting agent, filters at last, and cryopreservation is stand-by.The promoting agent that is adsorbed on the surface can prevent the direct contact of two kinds of reactants in the metachromasia.
(3) select metachromatic another reactant of another volatile dissolution with solvents, simultaneously powder or the particle can dissolved destruction step (2) do not made of this solvent.Utilize an amount of metachromatic another reactant of this dissolution with solvents, and cooling stores.Powder or the particle thorough mixing made from step (2) utilizes appropriate means that solvent evaporates is removed at low temperatures, makes that dissolved metachromasia thing is attached to powder or the particle surface that step (2) is made in this solvent.
(4) the structure mixture of step 3 being made is made ink or printing ink with proper formula, is used for the printing of intelligent label.
Provide an example that application of the present invention is described below.
A lot of vaccines and biological activity sample etc. need at low temperatures, and (between 2 ℃～8 ℃) store or transportation.By making intelligent label, can borrow change in color caution product whether to lose efficacy or inactivation, thereby guarantee the safe in utilization and effect of medicine or biological activity sample because in storage or transportation, surpass design temperature.At the demand of this intelligent label, utilize the irreversible thermosensitive chromotropic material of method design preparation low temperature of the present invention.
As shown in Figure 1, select adjacent phenanthroline A and ferrous sulfate B reaction to generate red ferrous complex C as metachromasia.Adjacent phenanthroline A is colourless in the reactant, and ferrous sulfate B is light yellow, and the complex compound C that reaction generates is red, can be used for the inefficacy or the inactivation caution of vaccine or active sample.
Between 2 ℃～8 ℃, select n-nonanoic acid based on the temperature range of the storage of a lot of vaccines and transportation as the temperature sensitive functional materials.The fusing point of n-nonanoic acid is 15 ℃, dissolve an amount of adjacent phenanthroline after, its fusing point drops to about 9 ℃～10 ℃.At about 2 ℃ refrigerator cold-storage, the n-nonanoic acid that is dissolved with adjacent phenanthroline solidifies with this solution, again under this temperature with the adjacent phenanthroline of refrigerated-n-nonanoic acid sosoloid grind into powder.On the other hand, an amount of ferrous sulfate is dissolved in the water, gets a certain amount of this drips of solution and be added on the filter paper, air-dry or oven dry refrigerates this filter paper again in about 2 ℃ refrigerator.
Being lower than adjacent phenanthroline-(T＜specific fusing point) below the n-nonanoic acid Solid solution fusing point, this solid-solution powder is added on the filter paper that contains ferrous sulfate, filter paper variable color (as shown in Figure 2) is not seen in refrigeration for a long time under this temperature again.The filter paper that will contain ferrous sulfate and adjacent phenanthroline-n-nonanoic acid Solid solution powder is transferred to (T＞specific fusing point) under the room temperature, solid dissolves rapidly, adjacent phenanthroline wherein and ferrous sulfate reaction, the very fast complex compound (as shown in Figure 3) that generates redness illustrates that this intelligent material system has good temperature sensitive discoloration.
As seen, innovation part of the present invention is temperature sensitive function and colour change function are separated, and is born by two kinds of different materials respectively, works in coordination with the function of two kinds of materials again by an intelligence structure, realize the irreversible heat-sensitive variable colour of low temperature, widen the optional scope of discoloring temperature and variable color mode.
In addition, by using different materials or designing the dynamic process that different material structures is modulated heat-sensitive variable colour, enable the thermolability dynamic process that fully reflection is instructed to product.
Claims (10)
1. thermosensitive chromotropic material, comprising reacts to each other, and first reactant and second reactant of variable color take place, it is characterized in that: a kind of dissolving cured in the outer package carrier of specific fusing point in described first reactant or second reactant, another kind of reactant mixes with arbitrary proportion with solid state powder or granular carrier, and wherein said carrier has chemistry respectively with first, second reactant and contacts inertia.
2. thermosensitive chromotropic material, comprising reacts to each other, and first reactant and second reactant of variable color take place, it is characterized in that: a kind of in described first reactant or second reactant for having the solid state powder or the particle of specific fusing point, have chemistry contact inertia with respect to another kind of reactant when solid-state, and mix with arbitrary proportion with another kind of reactant.
3. thermosensitive chromotropic material, comprising reacts to each other, and first reactant, second reactant and the 3rd reactant of variable color take place, it is characterized in that: a kind of dissolving cured in having the outer package carrier of first fusing point in described three kinds of reactants, and a kind of in described in addition two kinds of reactants for having the solid state powder or the particle of second fusing point, have chemistry with respect to other reactant and carrier when solid-state and contact inertia, two kinds of reactants of described carrier and other mix with arbitrary proportion; Described first fusing point is higher than second fusing point or first fusing point is lower than second fusing point.
4. according to each described a kind of thermosensitive chromotropic material in the claim 1 to 3, it is characterized in that: described solid state powder or particulate surface are formed with protective layer.
5. the method for making of the described a kind of thermosensitive chromotropic material of claim 1, its characterization step comprises:
I, one of metachromatic reactant is dissolved in the carrier with specific fusing point;
II, the carrier that will be dissolved with reactant are solidified into powder or particle;
III, be lower than under the temperature environment of specific fusing point, solid state powder or particle and another kind of reactant are being mixed into thermosensitive chromotropic material with arbitrary proportion.
6. the method for making of a kind of thermosensitive chromotropic material according to claim 5 is characterized in that: the kind of described carrier is distinguished mutually by specific fusing point itself and chemistry contact inertia, or be same kind of time-like, by the specific fusing point of change solute concentration modulation itself.
7. the method for making of the described a kind of thermosensitive chromotropic material of claim 2, its characterization step comprises:
I, one of metachromatic reactant is solidified into powder or particle;
II, be lower than under the temperature environment of specific fusing point, solid state powder or particle and another kind of reactant are being mixed into thermosensitive chromotropic material with arbitrary proportion.
8. according to the method for making of claim 5 or 7 described a kind of thermosensitive chromotropic materials; it is characterized in that: described be solidified into pulverize after powder or particulate method comprise direct condensation cured, spray congealing solidifies; or be configured to the protective layer of emulsion form with tensio-active agent; solidify in process of cooling with interior phase emulsified particle, separate again.
9. the law enforcement of a kind of thermosensitive chromotropic material according to claim 8 is characterized in that: by changing the thickness that forms protective layer, the diffusion process after the regulation and control reactant discharges realizes the kinetics regulation and control to the variable color process.
10. a tinting pigment is meant ink, printing ink or coating, it is characterized in that: described tinting pigment is made by each described thermosensitive chromotropic material in the claim 1 to 3, needing under the differing temps to be used for the occasion of heat-sensitive variable colour.
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