CN105949384B - A kind of preparation method and application of temperature sensing color changing optical material - Google Patents
A kind of preparation method and application of temperature sensing color changing optical material Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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- C—CHEMISTRY; METALLURGY
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The present invention provides a kind of preparation method and application of temperature sensing color changing optical material, prepares the nanoparticle with nucleocapsid with emulsion polymerization, the nanoparticle of nucleocapsid includes core and shell, and Shell Materials include viscoelastic body；The nanoparticle of preparation is coated in substrate with rubbing method and is processed into composite optical film, is temperature sensing color changing optical material.Change nanoparticle shell chemical composition by adding in heat sensitization monomer, realize response of the temperature sensing color changing optical material to any critical-temperature in the range of 0 90 DEG C, in critical-temperature, the refractive index of Shell Materials can vary widely, so as to cause the change of integral color, the temperature sensing color changing optical material of the present invention adds the corresponding color shifting properties of excellent temperature, has relatively broad application prospect in furnishing fields, field of product packaging, anti-counterfeit field and sensor indicator, energy saving solar film, photoprotection etc..
Description
Technical field
The present invention relates to technical field of material, and in particular to a kind of preparation method of temperature sensing color changing optical material and should
With.
Background technology
Temperature sensing color changing material has reversible irreversible two kinds from reversible irreversibly division at present, has from metachromatic principle division
Chemical reaction discoloration and phase transformation change colour two kinds.Chemical principle temperature sensing color changing material mainly includes iodide, the network of heavy metal
Object and loop coil class in organic material, dianthracene ketone, Synthesis of diaminodiphenyl etc. are closed, these materials pass through temperature sensitive
Selfoxidation-reduction reaction complete electron transfer change self color.The material of phase transformation class mainly includes the oxide of vanadium metal
And liquid crystal etc., the variation of energy band is realized by the variation of crystal structure, and then changes optical characteristics.React class materials synthesis work
Skill is simply at low cost, but use temperature range is narrow, and pollution is big, and color change is not notable；The characteristics of phase transformation class material is to temperature
High sensitivity is spent, but color gamut is narrow, color changeable effect is unstable, sensitive to chemical substance.
Photonic crystal is a kind of novel optical material.Different from electron transfer chemical optics material and phase-change type optical material
Material, the optical characteristics of photonic crystal is the selective reflecting by internal nanostructure to light, i.e., complete and incomplete photon
What forbidden band was realized.The opal stone of nature is a kind of natural photon crystal material, and silica or other inorganics are received
Meter Wei Qiu by complicated long-term geologic process in opal stone internal arrangement into the solid matter or other structures of rule so that naturally
Opal stone has magnificent color representation and is treasured by people.It is inspired by natural opal stone structure, from last century the eighties
Since people synthesized a variety of artificial photonic crystals, wherein polymer opal stone luminescent crystal material is exactly wherein special
It is a kind of.
Technical principle used in polymer opal stone photon crystal material is to be existed by the polymer nano-microspheres of nucleocapsid
Three dimensions dense accumulation permutation and combination forms certain regular lattice structure, disordered structure or regular mixed with irregular structure
It closes and incident ray is selectively reflected into specific wave band and angle by Bragg diffraction principle.Polymer photon crystal
Production prepares that the technical difficulty that is related to is higher, and polymer photon crystal has a potential quality to temperature respective change, however at present this
The research of aspect seldom relates to.Polymer photon crystal is because material is all polymer, and the refractive index of most polymers
It is not it is obvious that therefore temperature sensitive polymer photon crystal prepares difficulty higher with the different caused variations of temperature.
The patent of invention of Application No. CN201310135432.9 discloses a kind of temperature sensing color changing insulating moulding coating, by following heavy
Measure the color stuffing of percentage composition 32%~52%, 2%~10% slurrying solvent, 1%~12% pulping agents, 30%~
50% filming emulsion, 1%~8% temperature-sensitive reversible color material, 1%~11.5% paint auxiliary agent and 0%~10%
Paint solvent be made, achieve the purpose that temperature sensing color changing, high temperature reflective insulation, low temperature heat absorption, have good energy-saving effect with
Decorative effect, but the technical solution of the invention is not directed to nanoparticle, colour change function does not possess to 0-90 DEG C of scope yet
The response of interior any critical-temperature.
The content of the invention
In order to overcome more than problems of the prior art, the present invention discloses a kind of preparation of temperature sensing color changing optical material
Method and application prepare the nanoparticle with nucleocapsid with emulsion polymerization, and the nanoparticle of nucleocapsid includes core
Layer and shell, Shell Materials include viscoelastic body；The nanoparticle of preparation is coated in substrate with rubbing method and is processed into again
Condensation material optical thin film is temperature sensing color changing optical material.By the change to nanoparticle shell chemical composition, one is such as added in
Determine the heat sensitization monomer of mass fraction, realize sound of the temperature sensing color changing optical material to any critical-temperature in the range of 0-90 DEG C
Should, in critical-temperature, the refractive index of Shell Materials can vary widely, and cause the change of integral color, and of the invention is temperature sensitive
Color-change optical material adds on the basis of the functions such as the excellent changeable colors along with angle of raw material, strain discoloration, color change with voltage are retained
The corresponding color shifting properties of excellent temperature, in furnishing fields, field of product packaging, anti-counterfeit field and sensor indicator, energy saving
Solar film, photoprotection etc. have relatively broad application prospect.
The core microballoon material of the nanoparticle of nucleocapsid, which is generally but is not limited only to polystyrene, silica etc., to be had
Machine or inorganic material, the shell of nanoparticle are generally but are not limited only to the elastomers such as polyethyl acrylate or viscoelastic body polymer
Material.The size of nanoparticle is generally 100-1000 nanometers, and the size dispersity of same nanoparticle is generally below 5%.
Nanoparticle is prepared by emulsion polymerization, and dried nanoparticle is formed after addition organic solvent or specific monomer sticky to be had
The mixture of certain fluidity coated on basement membrane, forms elastic film, using roll-in and subsequent technique by UV photocurings
Improve optical property.Prepared optical material since internal nanostructure characteristic causes color constantly to change in different angle,
The variation that strain causes nanostructured lattice variations thus reflected light wave band occurs can occur under outer signals stimulation simultaneously, into
And cause the variation of material appearance color.
The present invention provides a kind of preparation method of temperature sensing color changing optical material, including preparing nanoparticle, including：
Step (1)：The nanoparticle with nucleocapsid is prepared with emulsion polymerization, the nanoparticle of nucleocapsid includes
Core and shell, Shell Materials include polymer viscoelastic body；
Step (2)：The nanoparticle of preparation is coated in substrate with rubbing method and is processed into composite optical film, i.e.,
For temperature sensing color changing optical material.
Preferably, the weight percentage that the core accounts for the nuclear shell structure nano microballoon is 30-55%.
Any of the above-described scheme is preferably, and the weight percentage that the shell accounts for the nuclear shell structure nano microballoon is
30%-60%.
Any of the above-described scheme is preferably, and is attached between the shell and core by interlayer, and interlayer accounts for described
The weight percentage of nuclear shell structure nano microballoon is 5-20%.
Any of the above-described scheme is preferably, and core includes core material and crosslinking agent.
Any of the above-described scheme is preferably, and core material layer includes polystyrene, silica, poly-methyl methacrylate
At least one of ester, ferroso-ferric oxide, phenylethylamine, tin indium oxide, arsenic trioxide.When core layer uses polystyrene,
In order to increase hardness, therefore crosslinking agent can be added in, if being added without crosslinking agent, polystyrene more softness is can to deform
's.Under normal circumstances be harder polystyrene.
Any of the above-described scheme is preferably, and the Shell Materials include polyethyl acrylate, dimethyl silicone polymer, poly- third
In two fat of olefin(e) acid second, polymethyl methacrylate, polyurethane, polystyrene, heat sensitization monomer, acrylic compounds and rubber
One or more.
Any of the above-described scheme is preferably, and core includes polystyrene and crosslinking agent, and interlayer includes polyethyl acrylate
And polyallylmethacrylate, shell include polyethyl acrylate and heat sensitization monomer.Polyallylmethacrylate is by first
It is obtained after base allyl acrylate monomer polymerization.Polyethyl acrylate obtains after being polymerize by acrylic acid ethyl ester monomer.
Any of the above-described scheme is preferably, and crosslinking agent accounts for the 1%-20% of core weight.
Any of the above-described scheme is preferably, and crosslinking agent accounts for the 10% of core weight.
Any of the above-described scheme is preferably, and heat sensitization monomer accounts for the 1%-85% of shell weight.
Any of the above-described scheme is preferably, and heat sensitization monomer accounts for the 30-60% of shell weight.
Any of the above-described scheme is preferably, the polystyrene and crosslinking agent of core layer：The polyethyl acrylate in interlayer and
Polyallylmethacrylate：The polyethyl acrylate of shell and weight ratio=32.5 of heat sensitization monomer:11.2:56.3.
Any of the above-described scheme is preferably, and the polystyrene and crosslinking agent of core account for nuclear shell structure nano microspheres quality
20-45%.
Any of the above-described scheme is preferably, and the polyethyl acrylate and polyallylmethacrylate in interlayer account for nucleocapsid knot
The 5-20% of structure nanoparticle quality.
Any of the above-described scheme is preferably, and the polyethyl acrylate and heat sensitization monomer of shell account for nuclear shell structure nano microballoon
The 30-60% of quality.
Any of the above-described scheme is preferably, and crosslinking agent is 1,3-BDO diacrylate (BDDA) or divinylbenzene
(DVB)。
Any of the above-described scheme is preferably, the heat sensitization monomer for oligosaccharide glycol propylene acid methyl esters (ethylene glycol
Unit changes between 2 and 9), n-isopropyl acrylamide, dimethylaminoethyl methacrylate or N, N- dimethyl allene
At least one of amide.
Any of the above-described scheme is preferably, and the nanoparticle with nucleocapsid, specific method are prepared with emulsion polymerization
Comprise the following steps：
Step (a)：The preparation of core layer：The preparation of core layer：Core material, crosslinking agent, main initiator and auxiliary are drawn
Agent is sent out in 60-90 DEG C of mixing, adjusting pH value to 7-8 reacts 30 minutes；
Step (b)：The preparation in interlayer：Buffer layer material with the drop speed of 7-21ml/min is added in again, and adds in emulsification
Agent is reacted 20 minutes；
Step (c)：The preparation of shell：Shell Materials and heat sensitization monomer with the drop speed of 8-27ml/min are added in, and are added
Enter adjustable refractive index material, when reaction 1 is small, nanoparticle is obtained after demulsification, drying.
Any of the above-described scheme is preferably, and the main initiator is sodium peroxydisulfate (Na2S2O8)。
Any of the above-described scheme is preferably, and the co initiator is sodium pyrosulfite (Na2S2O5)。
Any of the above-described scheme is preferably, and the emulsifier is disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt (Dowfax2A1).
Any of the above-described scheme is preferably, and the adjustable refractive index material is TFMA.
Any of the above-described scheme is preferably, and the nanoparticle of preparation is coated in substrate by the step (2) with rubbing method
Composite optical film is processed into, specific preparation method includes：
Step (a)：The nanoparticle that step 1 synthesizes is formed into sticky stabilization after addition organic solvent or specific monomer
Mixture applies mixture on basement membrane, covered with protective film on basement membrane；
Step (b)：It is put into UV solidification cases, is taken out after curing；
Step (c)：Make its upper and lower surface smooth the basement membrane microstress roller extruding of taking-up, then sheared by concussion to obtain the final product
To composite optical film.
Any of the above-described scheme is preferably, and organic solvent or specific monomer include BDDA, ethyl alcohol or oligosaccharide ethylene glycol third
E pioic acid methyl ester.
Any of the above-described scheme is preferably, and basement membrane is PET basement membranes in the step (a).
Any of the above-described scheme is preferably, and hardening time is three minutes in UV solidification cases in the step (b), ultraviolet wavelength
Scope is 200-350nm.
Invention additionally discloses a kind of temperature sensing color changing optical material prepared using the above method in base camp tent, architectural appearance
Or built-in, packaging material, electronic equipment appearance material, automobile appearance material, dress material, sporting goods material, building decoration
Application in terms of material, currency security strip material, brand material, pattern anti-fake material.
The present invention provides a kind of preparation method and application of temperature sensing color changing optical material, and being prepared with emulsion polymerization has core
The nanoparticle of shell structure, the nanoparticle of nucleocapsid include core and shell, and Shell Materials include viscoelastic body；With painting
The nanoparticle of preparation is coated in substrate and is processed into composite optical film by cloth method, is temperature sensing color changing optical material.
Change nanoparticle shell chemical composition by adding in heat sensitization monomer, such as oligosaccharide glycol propylene acid methyl esters (oligo
(ethylene glycol)-methacrylate), H2C=C (CH3) CO (OCH2CH2)nO(CH3), and by adjusting ethylene glycol
Number in oligosaccharide glycol propylene acid methyl esters (oligo (ethylene glycol)-methacrylate), realizes
Response of the temperature sensing color changing optical material to any critical-temperature in the range of 0-90 DEG C, in critical-temperature, the refractive index of Shell Materials
It can vary widely, so as to cause the change of integral color, temperature sensing color changing optical material of the invention is excellent in reservation raw material
On the basis of the functions such as good changeable colors along with angle, strain discoloration, color change with voltage, the corresponding color shifting properties of excellent temperature are added,
Furnishing fields, field of product packaging, anti-counterfeit field and sensor indicator, energy saving solar film, photoprotection etc. have more
It is widely applied prospect.
Description of the drawings
Fig. 1, material coating are light-cured into membrane process；
Fig. 2, nuclear shell structure nano microballoon prepare composite optical film；
Composite optical film prepared by Fig. 3, nuclear shell structure nano microballoon is with angle discoloration schematic diagram；
Composite optical film prepared by Fig. 4, nuclear shell structure nano microballoon is with color change mirror-reflection spectrum example；
The application of composite optical film prepared by Fig. 5, nuclear shell structure nano microballoon on military camouflage tent；
The application of composite optical film prepared by Fig. 6, nuclear shell structure nano microballoon in architectural appearance；
The application that composite optical film prepared by Fig. 7, nuclear shell structure nano microballoon is loaded onto inside；
The composite optical film that Fig. 8 is prepared for nuclear shell structure nano microballoon uses schematic diagram；
Fig. 9 is 7.1 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 10 is 7.2 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 11 is 7.2 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 12 is 7.3 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 13 is 7.4 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 14 is 7.5 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 15 is 7.5 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 16 is 7.6 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 17 is 7.6 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
Figure 18 is 7.6 application examples of composite optical film prepared by nuclear shell structure nano microballoon；
7.7 application examples of composite optical film prepared by Figure 19 nuclear shell structure nanos microballoon；
Figure 20 is 7.8 application examples of composite optical film prepared by nuclear shell structure nano microballoon.
Specific embodiment
In order to be best understood from technical scheme and advantage, below by way of specific embodiment, and with reference to attached drawing pair
The present invention is described further.
The present invention, which provides a kind of preparation method of temperature sensing color changing optical material, to be included：
Step (1)：The nanoparticle with nucleocapsid is prepared with emulsion polymerization, the nanoparticle of nucleocapsid includes
Core, interlayer and shell containing heat sensitization monomer in Shell Materials, are attached between shell and core by interlayer；
Step (2)：The nanoparticle of preparation is coated in substrate with rubbing method and is processed into composite optical film.
Core material uses organic or inorganic material, such as polystyrene or silica.Shell uses polymer viscoelastic body
Material such as polyethyl acrylate.Core includes polystyrene and crosslinking agent, and interlayer includes EA monomers and ALMA monomers.Shell bag
Include EA monomers and heat sensitization monomer.Polystyrene and crosslinking agent：EA monomers and ALMA monomers：EA monomers and heat sensitization monomer are most
Good weight ratio is=32.5:11.2:56.3..
Heat sensitization monomer is oligosaccharide glycol propylene acid methyl esters, and the unit of ethylene glycol can change between 2 and 9.Heat
It can also be n-isopropyl acrylamide, dimethylaminoethyl methacrylate, N, N- dimethacrylamide to be sensitized monomer
In any one.
Step (1)：The nanoparticle with nucleocapsid is prepared with emulsion polymerization, is received with 320nm sized core-shell structures
Exemplified by meter Wei Qiu, following steps are specifically included：
Step (a)：The preparation of core layer：2.6 grams of SDS (as emulsifier, a nanometer seed grain being made to be uniformly dispersed) are premixed,
2800 grams of deionized waters, 36 grams of polystyrene monomers, 4 grams of crosslinking agents enter reaction kettle, and crosslinking agent accounts for the 1%- of core layer weight
20%, 0.72 gram of main initiator and 5.18 grams of co initiators are then added in, argon gas protection is heated to 75 DEG C, core layer
Weight percentage is 30-50%；2.3 grams of SDS are added in 10ml speed per minute after 20 minutes, adjust pH value to 7-8,
2.2 grams of emulsifiers, 900 grams of deionized waters, 700 grams of polystyrene monomers, 70 grams of crosslinking agents；0.25 gram is added in after 30 minutes
Na2S2O8With the mixed solution of 5 grams of deionized water compositions；
Step (b)：The preparation in interlayer is attached between shell and core layer by the monomer crosslinked interlayers of EA, in
The weight percentage of interbed is 5-20%：0.5 gram of SDS, 2.1 grams of emulsifications are added in speed per minute 14ml after 15 minutes
Agent, 320g deionized waters, 250 grams of EA monomers and 30 grams of ALMA monomer ALMA monomers interlayers；
Step (c)：The preparation of shell, the weight percentage of shell is 30%-60%：It is per minute with 18ml after twenty minutes
Speed add in 4 grams of SDS, adjust pH value to 7-8,1600 grams of deionized waters, 250 grams of EA monomers, 750 grams of heat sensitization monomers (heat
Sensitization monomer accounts for the 1%-60% of shell weight), 350 grams of IBMA (Tg conditioning agents) and 100 grams of adjustable refractive index materials.Heat
Sensitization monomer can float in the mass fraction of Shell Materials between 1%-60%.
Wherein, heat sensitization monomer can use oligosaccharide glycol propylene acid methyl esters (oligo (ethylene glycol)-
Methacrylate, chemical formula H2C=C (CH3) CO (OCH2CH2)nO(CH3)) or N-isopropylacrylamide (N-
N-isopropylacrylamide) either N-isopropylmethacrylamide. (N- isopropyl acrylamides) or
Dimethylaminoethylmethacrylate (dimethylaminoethyl methacrylate) or N-, N-
Any one in dimethylacrylamide (N, N- dimethacrylamide).
Step (d)：Demulsification filtering is carried out after when completion of dropwise addition 1 is small and is dried to obtain nanoparticle agglomerate precursor.It will obtain
Nanoparticle agglomerate precursor and 32% mass fraction crosslinking agent and 2% mass fraction Benzophenon be mixed
Form sticky stabilized mixture.
Wherein main initiator is Na2S2O8, co initiator Na2S2O5, emulsifier Dowfax2A1, crosslinking agent is
BDDA。
The heat sensitization monomer that the present invention uses is oligosaccharide glycol propylene acid methyl esters, and by adjusting ethylene glycol oligomeric
The number of sugared glycol propylene acid methyl esters (oligo (ethylene glycol)-methacrylate) realizes critical-temperature
Adjustment, i.e., unit changes between 2 and 9, and critical-temperature can change between 0 and 90 degree Celsius.Here the list of ethylene glycol
Position refers to this functional group of ethylene glycol in oligosaccharide glycol propylene acid methyl esters (oligo (ethylene
Glycol)-methacrylate) number in chemical formula, adjust critical-temperature, oligosaccharide ethylene glycol by adjusting the number
Methyl acrylate (oligo (ethylene glycol)-methacrylate) concrete structure formula is：
N=2-9 in formula.
Such as n=2, chemical formula is
As n=4, chemical formula is
As n=6, chemical formula is
The specific preparation of step (2), composite optical film：
Step (a)：On the mixture coating basement membrane that step 1 is synthesized, covered with protective film on basement membrane；
Step (b)：It is put into UV solidification cases, is taken out after curing；
Step (c)：Make its upper and lower surface smooth the basement membrane microstress roller extruding of taking-up, be then by concussion shearing
Obtain composite optical film.
Embodiment 1
Exemplified by synthesizing 320nm sized core-shell structure nano microballoons, preparation method is illustrated
The first step：The preparation of the nanoparticle of nucleocapsid：
Step (a)：The preparation of core layer：Using 10 liters of reaction kettles with blender, argon gas protection is heated to 60 and takes the photograph the first step
Family name's degree premixes 2.6 grams of SDS (SDS makes a nanometer seed grain be uniformly dispersed as emulsifier), and 2800 grams of deionized waters, 36 grams poly-
Styrene monomer, 4 grams of BDDA (polystyrene is crosslinked by 1,3-BDO diacrylate, crosslinking agent, increases hardness and strength)
Enter reaction kettle, then reaction kettle mixing speed 250rpm adds in 0.72 gram of Na2S2O5(sodium pyrosulfite, co initiator increase
Efficiency of initiation) and 5.18 grams of Na2S2O8(main initiator, make monomer polymerization)；
2.3 grams of SDS (dodecyl sodium sulfate) are added in 10ml speed per minute after 20 minutes, 4 grams of NaOH (are adjusted anti-
The pH value answered is smoothed out polymerisation to alkalescent), 2.2 grams of Dowfax2A1 (disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt,
The preferable emulsifying dispersant of effect), 900 grams of deionized waters, 700 grams of polystyrene monomers, 70 grams of BDDA.It is added in after 30 minutes
0.25 gram of Na2S2O8(this is the initiator added, and is smoothed out the polymerization in interlayer) and the mixing of 5 grams of deionized water compositions
Solution；
Step (b)：The preparation in interlayer：0.5 gram of SDS is added in 14ml speed per minute after 15 minutes, 2.1 grams
250 grams of ethylacrylate (EA) monomers (ethyl acrylate) of Dowfax2A1,320g deionized water and 30 grams of ALMA monomers
(allyl methacrylate)；
Step (c)：The preparation of shell：2 grams of SDS, 2 grams of KOH (adjustment pH are added in speed per minute 18ml after twenty minutes
Value), 1600 grams of deionized waters, 250 grams of EA monomers, 750 grams of oligosaccharide glycol propylene acid methyl esters (oligo (ethylene
Glycol)-methacrylate) in be Unit two ethylene glycol, 350 grams of i-butyl methacrylate (IBMA) (first
Base isobutyl acrylate is Tg conditioning agents, and temperature sensitive monomer can adjust the critical transition temperature of material by the content of addition),
42 grams of hydroxyethylmethacrylate (HEMA：Thermal cross-linking agent is used when material needs heat cross-linking, also may be used
To be not added with) and 100 gram 2, (TFMA adjusts the additive of Refractive Index of Material to 2,2-trifluoroethyl acrylate, can
To increase the comparison of Refractive Index of Material, make the intensity of reflected light higher of material).
Step (d)：Demulsification filtering is carried out after when completion of dropwise addition 1 is small and is dried to obtain nanoparticle agglomerate precursor.It will obtain
Nanoparticle and the butanediol acrylate (BDDA) of 32% mass fraction and mass fraction 2%
Benzophenone (benzophenone, UV cross-linked evocating agents) mixings form sticky stabilized mixture.
Second step：The specific preparation of composite optical film：
Step (a)：By the mixture of synthesis as shown in Figure 1, being coated in PET or other bases using scraper or other instruments
On film, other layer protecting film is covered above；
Step (b)：It is put into UV solidification cases, is taken out after three minutes.
Step (c)：Make upper and lower surface smooth by microstress roll-in the basement membrane of taking-up, it is then regular by concussion shearing
Change process makes the queueing discipline of nanoparticle obtain more preferably optical property, and prepared material is in 0 degree Celsius of critical-temperature
With apparent colour change function.
As shown in Figure 1, it is light-cured into membrane process for nanoparticle coating；Fig. 1 a, by sticky slurry scraper or other
Instrument is coated uniformly on PET basement membranes；Fig. 1 b, affix surface protection film simultaneously are compacted become the three-decker being close to, three-layered node
Structure is as illustrated in figure 1 c；Film is put into UV curing ovens afterwards, as shown in Figure 1 d；It is taken out after three minutes thin after being cured
Film, such as Fig. 1 e and Fig. 1 f.
Fig. 2 nuclear shell structure nano microballoons prepare composite optical film.Since nanoparticle shell and core layer be not by
Same material preparation, shell use elastomeric polymer materials such as polyethyl acrylate, and viscoelastic shell is in subsequent technique
Softer filler forms continuous phase medium into the gap of ball and ball.The height changes in contrast of microballoon and medium refraction index, film
Structure can be formal or trans.
Fig. 3 is the composite optical film of nuclear shell structure nano microballoon preparation with angle discoloration schematic diagram.
Composite optical film prepared by Fig. 4 nuclear shell structure nanos microballoon with color change mirror-reflection spectrum example,
R is reflectivity, and direction indicated by arrows constantly changes with the color of incident angle change material in figure.It is optical reflection and thoroughly
The a certain wavelength specular reflectivity 40% for comparing visible-range is penetrated, the transmittance of the same band is less than 15%, reflection peak and thoroughly
The half-wave width of paddy is penetrated as 20-50nm, the reflection peak of material constantly changes with the variation of angle, is highest in positive incident reflection
Reflection wavelength, reflection peak shifts when incidence angle increases.
Embodiment 2
Exemplified by synthesizing 320nm sized core-shell structure nano microballoons
The first step：The preparation of the nanoparticle of nucleocapsid：
Step (a)：The preparation of core layer：Using 10 liters of reaction kettles with blender, argon gas protection is heated to 75 and takes the photograph the first step
Family name's degree premixes 2.6 grams of SDS, 2800 grams of deionized waters, 36 grams of polystyrene monomers, 4 grams of BDDA (1,3-BDO diacrylates
Ester) enter reaction kettle, then reaction kettle mixing speed 250rpm adds in 0.72 gram of Na2S2O5(sodium pyrosulfite) and 5.18 grams
Na2S2O8；
2.3 grams of SDS (dodecyl sodium sulfate) are added in 10ml speed per minute after 20 minutes, 4 grams of NaOH (adjust pH
Value is to 7.5), 2.2 grams of Dowfax2A1 (disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt), 900 grams of deionized waters, 700 grams of polystyrene
Monomer, 70 grams of BDDA.0.25 gram of Na is added in after 30 minutes2S2O8With the mixed solution of 5 grams of deionized water compositions；
Step (b)：The preparation in interlayer：0.5 gram of SDS is added in 14ml speed per minute after 15 minutes, 2.1 grams
250 grams of ethylacrylate (EA) monomers (ethyl acrylate) of Dowfax2A1,320g deionized water and 30 grams of ALMA monomers
(allyl methacrylate)；
Step (c)：The preparation of shell：4 grams of SDS, 2 grams of NaOH, 1600 are added in speed per minute 18ml after twenty minutes
Gram deionized water, 250 grams of EA monomers, 750 grams of N-isopropylacrylamide (n-isopropyl acrylamide), 350 grams of IBMA
(IBMA is as Tg conditioning agents), 42 grams of HEMA (HEMA, hydroxyethyl methacrylate is as thermal cross-linking agent) and 100 gram 2,2,
2-trifluoroethyl acrylate (TFMA, acrylic acid 2,2,2- trifluoro ethyl esters are as adjustable refractive index material).
Step (d)：Demulsification filtering is carried out after when completion of dropwise addition 1 is small and is dried to obtain nanoparticle agglomerate precursor.It will obtain
Nanoparticle and the butanediol acrylate (BDDA) of 32% mass fraction and mass fraction 2%
Benzophenon (benzophenone, UV cross-linked evocating agents) mixings form sticky stabilized mixture.
Second step：The specific preparation of composite optical film：
Step (a)：By the mixture of synthesis as shown in Figure 1, being coated in PET or other bases using scraper or other instruments
On film, other layer protecting film is covered above；
Step (b)：It is put into UV solidification cases, is taken out after three minutes.
Step (c)：Make upper and lower surface smooth by microstress roll-in the basement membrane of taking-up, it is then regular by concussion shearing
Change process makes the queueing discipline of nanoparticle obtain more preferably optical property, and prepared material is in 0 degree Celsius of critical-temperature
With apparent colour change function.
Embodiment 3
Exemplified by synthesizing 320nm sized core-shell structure nano microballoons
The first step：The preparation of the nanoparticle of nucleocapsid：
Step (a)：The preparation of core layer：The first step is used using 10 liters of reaction kettles with blender, and argon gas protection is heated to
80 degrees Celsius, 2.6 grams of SDS are premixed, 2800 grams of deionized waters, 36 grams of polystyrene monomers, 4 grams of DVB enter reaction kettle, and reaction kettle stirs
Speed 250rpm is mixed, then adds in 0.72 gram of Na2S2O5(sodium pyrosulfite) and 5.18 grams of Na2S2O8；
2.3 grams of SDS (dodecyl sodium sulfate) are added in 10ml speed per minute after 20 minutes, 4 grams of NaOH adjust pH
It is worth to 7.8,2.2 grams of Dowfax2A1 (disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt), 900 grams of deionized waters, 700 grams of polystyrene
Monomer, 70 grams of DVB.0.25 gram of Na is added in after 30 minutes2S2O8With the mixed solution of 5 grams of deionized water compositions；
Step (b)：The preparation in interlayer：0.5 gram of SDS is added in 14ml speed per minute after 15 minutes, 2.1 grams
250 grams of ethylacrylate (EA) monomers (ethyl acrylate) of Dowfax2A1,320g deionized water and 30 grams of ALMA monomers
(allyl methacrylate)；
Step (c)：The preparation of shell：5 grams of SDS, 2 grams of NaOH, 1600 are added in speed per minute 18ml after twenty minutes
Gram deionized water, 250 grams of EA monomers, 750 grams of dimethylaminoethylmethacrylate (dimethylaminoethyl acrylate methyl base ammonia
Base ethyl ester, 350 grams of i-butyl methacrylate (IBMA), IBMA is as Tg conditioning agents), 42 grams
hydroxyethylmethacrylate(HEMA)：HEMA is as thermal cross-linking agent, and 100 gram 2,2,2-
Trifluoroethyl acrylate (TFMA), TFMA is as adjustable refractive index material.
Step (d)：Demulsification filtering is carried out after when completion of dropwise addition 1 is small and is dried to obtain nanoparticle agglomerate precursor.It will obtain
Nanoparticle and 32% mass fraction DVB and mass fraction 2% Benzophenon (benzophenone UV crosslinking trigger
Agent) be mixed form sticky stabilized mixture.
Second step：The specific preparation of composite optical film：
Step (a)：By the mixture of synthesis as shown in Figure 1, being coated in PET or other bases using scraper or other instruments
On film, other layer protecting film is covered above；
Step (b)：It is put into UV solidification cases, is taken out after three minutes.
Step (c)：Make upper and lower surface smooth by microstress roll-in the basement membrane of taking-up, it is then regular by concussion shearing
Change process makes the queueing discipline of nanoparticle obtain more preferably optical property, and prepared material is in 0 degree Celsius of critical-temperature
With apparent colour change function.
Embodiment 4
Exemplified by synthesizing 320nm sized core-shell structure nano microballoons
The first step：The preparation of the nanoparticle of nucleocapsid：
Step (a)：The preparation of core layer：Using 10 liters of reaction kettles with blender, argon gas protection is heated to 90 and takes the photograph the first step
Family name's degree, 2.6 grams of SDS of premix, 2800 grams of deionized waters, 36 grams of polystyrene monomers, 4 grams of DVB enter reaction kettle, reaction kettle stirring speed
250rpm is spent, then adds in 0.72 gram of Na2S2O5And 5.18 grams of Na2S2O8；
2.3 grams of SDS (dodecyl sodium sulfate) are added in 10ml speed per minute after 20 minutes, 4 grams of NaOH adjust pH
It is worth to 8.0,2.2 grams of Dowfax2A1 (disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt), 900 grams of deionized waters, 700 grams of polystyrene
Monomer, 70 grams of DVB.0.25 gram of Na is added in after 30 minutes2S2O8With the mixed solution of 5 grams of deionized water compositions；
Step (b)：The preparation in interlayer：0.5 gram of SDS is added in 14ml speed per minute after 15 minutes, 2.1 grams
250 grams of ethylacrylate (EA) monomers (ethyl acrylate) of Dowfax2A1,320g deionized water and 30 grams of ALMA monomers
(allyl methacrylate)；
Step (c)：The preparation of shell：6 grams of SDS, 2 grams of NaOH, 1600 are added in speed per minute 18ml after twenty minutes
Gram deionized water, 250 grams of EA monomers, 750 grams of N-, N-dimethylacrylamide (N,N-DMAA), 350 grams
I-butyl methacrylate (IBMA), IBMA is as Tg conditioning agents), 42 grams of hydroxyethylmethacrylate
(HEMA)：HEMA makees as thermal cross-linking agent, and 100 gram 2,2,2-trifluoroethyl acrylate (TFMA), TFMA
For adjustable refractive index material.
Step (d)：Demulsification filtering is carried out after when completion of dropwise addition 1 is small and is dried to obtain nanoparticle agglomerate precursor.It will obtain
Nanoparticle and 32% mass fraction DVB and mass fraction 2% Benzophenon (benzophenone UV crosslinking trigger
Agent) be mixed form sticky stabilized mixture.
Second step：The specific preparation of composite optical film：
Step (a)：By the mixture of synthesis as shown in Figure 1, being coated in PET or other bases using scraper or other instruments
On film, other layer protecting film is covered above；
Step (b)：It is put into UV solidification cases, is taken out after three minutes.
Step (c)：Make upper and lower surface smooth by microstress roll-in the basement membrane of taking-up, it is then regular by concussion shearing
Change process makes the queueing discipline of nanoparticle obtain more preferably optical property, and prepared material is in 0 degree Celsius of critical-temperature
With apparent colour change function.
Embodiment 5：
The application example of composite optical film prepared by nuclear shell structure nano microballoon：
5.1. the composite optical film that prepared by nuclear shell structure nanos microballoon as shown in Figure 5 is on military camouflage tent
The application in face, 1 is the fluffy face of tent in figure, is used in the case where four support feets 2 are fixed.It it is prepared by nuclear shell structure nano microballoon
Composite optical film is fitted tightly on the fluffy face of cloth cover or plastic cover base material, and the critical-temperature of material is adjusted to 40 and takes the photograph
Family name's degree, material is green in forest or meadow thermal environment, but since temperature drastically raises in tropical desert Environment, material
Material discoloration is yellow, is adapted to ambient color.
5.2. the composite optical film that prepared by nuclear shell structure nanos microballoon as shown in Figure 6 answering in architectural appearance
With.By way of pad pasting, composite optical film can be adhered directly to building 4 grade of 3 outer surfaces and glass curtain wall
Smooth finish surface, composite optical film appearance color changes when temperature change, and the color of building is caused to exist
Different variations are generated when morning, noon, evening.
5.3. the application that the composite optical film that prepared by nuclear shell structure nanos microballoon as shown in Figure 7 is loaded onto inside.It is logical
Crossing the mode composite optical film of pad pasting can be adhered directly at interior of building door and window 5 and door and window peripheral region 6,
Composite optical film appearance color changes when temperature change, causes door and window 5 and door and window peripheral region 6
Color in the morning, noon, evening when generate different variations.
Embodiment 6：
Completed optical thin-film material prepared by the present invention generally has two layers of protective film up and down, takes the circumstances into consideration to take off when in use
The exposure of optical material is directly attached on application target surface as shown in Figure 8 by wherein any one surface protective film.Specifically should
It is to take the protective film (P) of material (O) one side off with mode, is then attached on the surface substrate by cleaning treatment (S), this
According to the surface roughness of base material during a, adhesive can alternatively be used.
Embodiment 7：
The application example of composite optical film prepared by nuclear shell structure nano microballoon：
7.1 packaging materials as shown in Figure 9.Fig. 9 is application of the temperature sensing color changing optical material in terms of product packaging material,
By taking medicine packing box as an example.After the protective film of this material one side is removed, exposed optical material (O) surface has due to itself
High viscosity directly can press or be attached to product packing box (B) surface, appearance such as (OB) after fitting.
7.2 electromagnetic induction as shown in Figure 10 and Figure 11.Figure 10 is compound as the electrochromism of flexible electrode material using water
Materials optical film applicating example.Film (O) is attached to one layer of VHB polymeric substrates (V), VHB polymeric substrates (V) up and down
There is the flexible electrode (W) that deionized water is done on two sides, and the flexible electrode (W) of lower floor is placed in vessel (P), makees in extra electric field
The light projected with lower light source is collected the variation of spectral signal after above device is penetrated by spectrometer.
Figure 11 illustrates for no attaching type application of electrode.After composite material film (O) is embedded in stent coil (R), then put
It puts between the two poles of the earth of high-tension apparatus (E), the variation of voltage (V) causes composite material film strain discoloration.
Application of the 7.3 temperature sensing color changing optical materials as shown in figure 12 in terms of electronic equipment appearance.Figure 12 temperature sensing color changing light
Learn applicating example of the material as the wearable electronic appearance by taking iwatch as an example.Temperature sensing color changing optical material is glued with film
For attached or band form as wrist strap (B) or the appearance material of dial plate (R) or display screen (D), visual effect is preferable, increases
Ornamental value.
7.4 automobile appearances as shown in fig. 13 that.Figure 13 is applicating example of the temperature sensing color changing optical material on automobile appearance.
Temperature sensing color changing optical thin film can be used for vehicle body (B) and vehicle window (W) pad pasting, and film is directed or through viscose and is attached to vehicle
Body or glass surface, outside apply PET or other materials protective layer, can realize the personalized repacking of vehicle body and vehicle window color.
Temperature sensing color changing optical material is attached on automobile to change with angle different colours, and visual effect is preferable, adds ornamental value.
7.5 mechanically deform as shown in Figure 14 and Figure 15.
Figure 14 causes temperature sensing color changing optical material discoloration applicating example for mechanically deform.Undeformed composite optical is thin
Film (O) has homogeneous stretching discoloration property in the case where not there is any additional structure, now the convex print with certain pattern
Template (S), which is pressed on film, realizes pattern transfer.The rough patterning of film surface causes under identical stress not
Different with the strain of position, weaker position should become larger and thicker position should become smaller, when film is through Tensile not
Strain difference with position causes color that different variations occurs.Effect same can be certain thickness by being added on film
Other one layer or the realization of a few layer films.
Figure 15 causes temperature sensing color changing optical material discoloration applicating example for mechanically deform.Undeformed polymer composites
Optical thin film (O) has homogeneous stretching discoloration property, now using UV lamp (L) by the shade (M) of opening selectively according to
The some characteristic areas of material surface are penetrated, are made using the photocrosslinking agent added in material illuminated partial cross-linked.Cross-linked areas material
The Young's modulus of material is much higher than the Young's modulus of uncrosslinked region material, so strains and is focusing more on when material is stretched
Uncrosslinked region, crosslinked region then strain relatively small, the field color that should become larger changes relatively uncrosslinked region
Bigger.Required security pattern can be radiated at material surface in advance by this method, material face when not having mechanically deform
Color is homogeneous, and pattern is stealthy, when material is subjected to mechanically deform since the different pattern of different zones deflection displays.
Application of the 7.6 temperature sensing color changing optical materials in the equipment such as pressure sensor or pressure indicator.
Figure 16 is color change of the composite optical film after not pressurizeing and pressurizeing, and material heaves two-way drawing after pressurization
It stretches, color is caused to become blueness from green.
Figure 17 is temperature sensing color changing optical material as pressure indicator schematic diagram.Temperature sensing color changing optical material (O) is enclosed in pressure
Power room (C) sensing opening (left side), to (right side) after gas pressurized in balancing gate pit, the stretching of material bulging causes color to change.
Figure 18 does pressure applied to football surface for temperature sensing color changing optical material and indicates material schematic diagram.Temperature sensing color changing optics
Material (O) is adhered to football (B) surface (left side), after football inflation (right side) material tension-thining cause color change,
This process can take a turn for the worse when air pressure inside reduces.
7.7 temperature sensing color changing optical material is in the application at anti-fake aspect.
Figure 19 is applicating example of the temperature sensing color changing optical material on currency (C) as anti-counterfeiting code band (O).For different goods
Coin base material, this material can be cut to band and are directly attached on currency base material use as anti-counterfeiting code.
Figure 20 is temperature sensing color changing optical material as trade mark or security pattern applicating example.Except by temperature sensing color changing optics material
Material is directly attached on base material outside use, can on material film (OS) various patterns of coining or it is compound one or more layers not
Material (OP) with sized microspheres preparation realizes more complicated antiforge function so as to form different pattern.
It should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；Although
The present invention is described in detail with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：It is still
It can modify to the technical solution recorded in foregoing embodiments and either which part or all technical characteristic are carried out
Equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is not made to depart from various embodiments of the present invention technical side
The scope of case.
Claims (26)
1. a kind of preparation method of temperature sensing color changing optical material, including preparing nanoparticle, which is characterized in that specifically include following
Step：
Step（1）：The nanoparticle with nucleocapsid is prepared with emulsion polymerization, the nanoparticle of nucleocapsid includes core
And shell, Shell Materials include polymer viscoelastic body；
Step（2）：The nanoparticle of preparation is coated in substrate with rubbing method and is processed into composite optical film, is temperature
Quick color-change optical material；Step（2）The nanoparticle of preparation is coated in substrate with rubbing method and is processed into composite optical
Film, specific preparation method include：
Step（a）：Step (1) synthesis nanoparticle is formed into the mixed of sticky stabilization after addition organic solvent or specific monomer
Object is closed, mixture is applied on basement membrane, covered with protective film on basement membrane；
Step（b）：It is put into UV solidification cases, is taken out after curing；
Step（c）：Make its upper and lower surface smooth the basement membrane microstress roller extruding of taking-up, then obtained by concussion shearing
Composite optical film.
2. the preparation method of temperature sensing color changing optical material as described in claim 1, it is characterised in that：The core accounts for the core
The weight percentage of shell structural nano microballoon is 30-55%.
3. the preparation method of temperature sensing color changing optical material as described in claim 1, it is characterised in that：The shell accounts for the core
The weight percentage of shell structural nano microballoon is 30%-60%.
4. the preparation method of temperature sensing color changing optical material as described in claim 1, it is characterised in that：The shell and core it
Between be attached by interlayer, interlayer account for the nuclear shell structure nano microballoon weight percentage be 5-20%.
5. the preparation method of temperature sensing color changing optical material as described in claim 1, it is characterised in that：The core includes core
Material and crosslinking agent.
6. the preparation method of temperature sensing color changing optical material as claimed in claim 5, it is characterised in that：The core material includes
At least one in polystyrene, silica, polymethyl methacrylate, ferroso-ferric oxide, tin indium oxide, arsenic trioxide
Kind.
7. the preparation method of temperature sensing color changing optical material as described in claim 1, it is characterised in that：Shell Materials include poly- third
In olefin(e) acid ethyl ester, dimethyl silicone polymer, polymethyl methacrylate, polyurethane, polystyrene, heat sensitization monomer and rubber
It is one or more of.
8. the preparation method of temperature sensing color changing optical material as claimed in claim 4, it is characterised in that：The core includes polyphenyl
Ethylene and crosslinking agent, interlayer include polyethyl acrylate and polyallylmethacrylate, and shell includes polyethyl acrylate
With heat sensitization monomer.
9. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：The crosslinking agent accounts for core
The 1%-20% of weight.
10. the preparation method of temperature sensing color changing optical material as claimed in claim 9, it is characterised in that：The crosslinking agent accounts for core
The 10% of heart weight.
11. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：The heat sensitization monomer
Account for the 1%-85% of shell weight.
12. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：The heat sensitization monomer
Account for the 30-60% of shell weight.
13. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：The polystyrene of core
And crosslinking agent：The polyethyl acrylate and polyallylmethacrylate in interlayer：The polyethyl acrylate of shell and heat sensitization
Weight ratio=32.5 of monomer:11.2:56.3.
14. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：The polystyrene of core
The 20-45% of nuclear shell structure nano microspheres quality is accounted for crosslinking agent.
15. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：The polypropylene in interlayer
Acetoacetic ester and polyallylmethacrylate account for the 5-20% of nuclear shell structure nano microspheres quality.
16. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：The polyacrylic acid of shell
Ethyl ester and heat sensitization monomer account for the 30-60% of nuclear shell structure nano microspheres quality.
17. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：Crosslinking agent is 1,3- fourths
Omega-diol diacrylate or divinylbenzene.
18. the preparation method of temperature sensing color changing optical material as claimed in claim 8, it is characterised in that：The heat sensitization monomer
For oligosaccharide glycol propylene acid methyl esters, n-isopropyl acrylamide, dimethylaminoethyl methacrylate or N, N- diformazan
At least one of base acrylamide.
19. the preparation method of temperature sensing color changing optical material as described in claim 1, it is characterised in that：With emulsion polymerization legal system
The standby nanoparticle with nucleocapsid, specific method comprise the following steps：
Step（a）：The preparation of core layer：Core material, crosslinking agent, main initiator and co initiator are mixed at 60-90 DEG C,
PH values are adjusted to 7-8, are reacted 30 minutes；
Step（b）：The preparation in interlayer：Buffer layer material with the drop speed of 7-21ml/min is added in again, and adds in emulsifier, instead
It answers 20 minutes；
Step（c）：The preparation of shell：Shell Materials and heat sensitization monomer with the drop speed of 8-27ml/min are added in, and add in folding
It penetrates rate and adjusts material, when reaction 1 is small, nanoparticle is obtained after demulsification, drying.
20. the preparation method of temperature sensing color changing optical material as claimed in claim 19, it is characterised in that：The main initiator is
Sodium peroxydisulfate.
21. the preparation method of temperature sensing color changing optical material as claimed in claim 19, it is characterised in that：The co initiator
For sodium pyrosulfite.
22. the preparation method of temperature sensing color changing optical material as claimed in claim 19, it is characterised in that：The emulsifier is ten
Dialkyl diphenyl ether disulfonic acid sodium salt.
23. the preparation method of temperature sensing color changing optical material as claimed in claim 19, it is characterised in that：The adjustable refractive index
Material is TFMA.
24. the preparation method of temperature sensing color changing optical material as described in claim 1, it is characterised in that：The step（a）Middle base
Film is PET basement membranes.
25. the preparation method of temperature sensing color changing optical material as described in claim 1, it is characterised in that：The step（b）Middle UV
Hardening time is three minutes in solidification case, UV wavelength range 200-350nm.
26. temperature sensing color changing optical material prepared by the method as described in above-mentioned any one claim is in base camp tent, building
Appearance or built-in, packaging material, electronic equipment appearance material, automobile appearance material, dress material, sporting goods material, building
Application in terms of ornament materials, currency security strip material, brand material, pattern anti-fake material.
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| CN106938742B (en) * | 2017-03-13 | 2019-02-12 | 电子科技大学中山学院 | A kind of simple Cold Chain Logistics dispensing device |
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| CN108165254B (en) * | 2017-12-25 | 2021-04-09 | 苏州善恩纳米功能材料科技有限公司 | Metastable state temperature-sensitive color-changing material |
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| CN112625289B (en) * | 2020-12-16 | 2021-10-26 | 华南理工大学 | Polyacrylic acid-based structural color elastomer and preparation method and application thereof |
| CN112876622A (en) * | 2021-01-08 | 2021-06-01 | 复旦大学 | Intelligent monitoring label for vaccine cold chain transportation and preparation method thereof |
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