CN116515020A - Schiff base/methyl methacrylate composite material and preparation method and application thereof - Google Patents
Schiff base/methyl methacrylate composite material and preparation method and application thereof Download PDFInfo
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- CN116515020A CN116515020A CN202310484712.4A CN202310484712A CN116515020A CN 116515020 A CN116515020 A CN 116515020A CN 202310484712 A CN202310484712 A CN 202310484712A CN 116515020 A CN116515020 A CN 116515020A
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- methyl methacrylate
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000002262 Schiff base Substances 0.000 title claims abstract description 59
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000767 polyaniline Polymers 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 25
- 239000000376 reactant Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 238000013500 data storage Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000638 stimulation Effects 0.000 abstract description 10
- 238000000862 absorption spectrum Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 6
- QMBQNYROFAQYMV-UHFFFAOYSA-N NC1=CC=CC=C1.C(C)(C)(C)C1=C(C(C=O)=CC(=C1)C(C)(C)C)O Chemical compound NC1=CC=CC=C1.C(C)(C)(C)C1=C(C(C=O)=CC(=C1)C(C)(C)C)O QMBQNYROFAQYMV-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 aromatic Schiff base Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a Schiff base/methyl methacrylate composite material, a preparation method and application thereof, wherein the preparation method of the Schiff base/methyl methacrylate composite material comprises the following steps: and mixing the Schiff base, methyl methacrylate and an initiator, and heating and cooling to obtain the Schiff base/methyl methacrylate composite material, wherein the Schiff base comprises 3, 5-di-tert-butyl salicylaldehyde polyaniline. Therefore, the preparation method is simple, and the obtained Schiff base/methyl methacrylate composite material is colorless and transparent, can be rapidly colored under the stimulation of ultraviolet light, can be rapidly recovered under the stimulation of visible light, and has good photochromic performance.
Description
Technical Field
The application relates to the technical field of organic photochromism and high molecular polymers, in particular to a Schiff base/methyl methacrylate composite material, a preparation method and application thereof.
Background
Salicylaldehyde aniline is an aromatic Schiff base, and the molecules have excellent photochromic performance, have application potential in the fields of optical information storage, anti-counterfeiting, spinning, wearing equipment and the like, and are of great interest to scientific researchers. Salicylaldehyde aniline and its derivatives have very good anti-fatigue ability, and the life of the photochromic form in the crystalline state can reach hundreds of days. The simplest and most prevalent photochromic cycle of salicylaldehyde anilines and derivatives thereof is assumed as follows. After the initial enol (trans-enol) tautomer is excited, ultra-fast Excited State Intramolecular Proton Transfer (ESIPT) occurs, and an excited state ketone tautomer (cis-ketone or zwitterionic form thereof) is formed, and strong Stokes shift fluorescence bands are shown. Having a reaction volume of photoinduced isomerization in a confining medium large enough is one way to increase the photochromic ability of salicylaldehyde aniline derivatives. Therefore, 3, 5-di-tert-butyl salicylaldehyde aniline with di-tert-butyl introduced into the structure has more stable photochromic capability. In many application fields such as optical films, color-changing glasses, transparent displays and the like, the materials are required to be colorless and transparent, but the 3, 5-di-tert-butyl salicylaldehyde aniline powder is dark and opaque, which prevents the Schiff base from being widely applied to the aspect of photochromism. The present application aims to propose a method for preparing a schiff base/methyl methacrylate composite material, so as to solve the above problems.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent.
In one aspect of the present invention, a method of preparing a schiff base/methyl methacrylate composite is presented, the method comprising: and mixing the Schiff base, methyl methacrylate and an initiator, and heating and cooling to obtain the Schiff base/methyl methacrylate composite material, wherein the Schiff base comprises 3, 5-di-tert-butyl salicylaldehyde polyaniline. Therefore, the preparation method is simple, and the obtained Schiff base/methyl methacrylate composite material is colorless and transparent, can be rapidly colored under the stimulation of ultraviolet light, can be rapidly recovered under the stimulation of visible light, and has good photochromic performance.
According to some embodiments of the invention, the method further comprises uniformly mixing the schiff base and the methyl methacrylate to obtain a first mixture; mixing the first mixture with the initiator to obtain a second mixture, and heating and cooling the second mixture to obtain the Schiff base/methyl methacrylate composite material.
According to some embodiments of the invention, the mass ratio of the 3, 5-di-tert-butyl salicylaldehyde polyaniline to the methyl methacrylate is: 1:100000-1:1000.
According to some embodiments of the invention, the mass ratio of the 3, 5-di-tert-butyl salicylaldehyde polyaniline to the methyl methacrylate is: 1:50000-1:1000.
According to some embodiments of the invention, the mass ratio of the initiator to the methyl methacrylate is: 1:1000-1:100.
According to some embodiments of the invention, the method comprises: subjecting the second mixture to a first heat treatment to obtain a first reactant; cooling the first reactant and placing the cooled first reactant in a mold; the cooled first reactant is subjected to a second heating treatment and cooled to obtain a second reactant; and carrying out third heat treatment on the second reactant, and cooling to obtain the Schiff base/methyl methacrylate composite material, wherein the temperature of the third heat treatment is higher than that of the first heat treatment, and the temperature of the first heat treatment is higher than that of the second heat treatment.
According to some embodiments of the invention, the method satisfies at least one of the following conditions: the temperature of the first heating treatment is 80-95 ℃; the temperature of the second heating treatment is 40-60 ℃; the temperature of the third heating treatment is 90-120 ℃.
According to some embodiments of the invention, the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, and benzoyl peroxide.
In another aspect of the present invention, a Schiff base/methyl methacrylate composite is provided, which is prepared by the method described above. Therefore, the Schiff base/methyl methacrylate composite material is colorless and transparent, can be rapidly colored under ultraviolet light stimulation, and can be rapidly recovered under visible light stimulation, and has good photochromic performance.
In yet another aspect of the present invention, there is provided the use of the foregoing schiff base/methyl methacrylate composite, including at least one of the transparent display field, the battery field, the wearable device field, and the three-dimensional data storage field. Therefore, when the Schiff base/methyl methacrylate composite material is applied to related devices in the fields, the good photochromic performance and the fatigue resistance of the Schiff base/methyl methacrylate composite material can be exerted.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a schematic flow diagram of a process for preparing a Schiff base/methyl methacrylate composite according to one embodiment of the present invention.
Fig. 2 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 1.
Fig. 3 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 2.
Fig. 4 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 3.
Fig. 5 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 4.
Fig. 6 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 5.
Fig. 7 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 6.
Fig. 8 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 7.
Fig. 9 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 8.
Fig. 10 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 9.
Fig. 11 shows the absorption spectra and photographs before and after photochromism of the composite material prepared in example 10.
FIG. 12 shows absorption spectra and photographs before and after photochromic of pure polymethyl methacrylate prepared in comparative example 1.
FIG. 13 shows photographs before and after photochromic of 3, 5-di-t-butylsalicylaldehyde polyaniline prepared in comparative example 2.
Detailed Description
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In one aspect of the present invention, a method of preparing a schiff base/methyl methacrylate composite is presented, comprising: and mixing the Schiff base, methyl methacrylate and an initiator, and heating and cooling to obtain the Schiff base/methyl methacrylate composite material, wherein the Schiff base comprises 3, 5-di-tert-butyl salicylaldehyde polyaniline. Specifically, the initiator polymerizes methyl methacrylate, and the Schiff base is randomly dispersed in the polymerized methyl methacrylate. Therefore, the preparation method is simple, and the obtained Schiff base/methyl methacrylate composite material is colorless and transparent, can be rapidly colored under the stimulation of ultraviolet light, can be rapidly recovered under the stimulation of visible light, and has good photochromic performance.
According to some embodiments of the invention, the method further comprises: uniformly mixing the 3, 5-di-tert-butyl salicylaldehyde polyaniline and the methyl methacrylate to obtain a first mixture; mixing the first mixture with the initiator to obtain a second mixture, and heating and cooling the second mixture to obtain the Schiff base/methyl methacrylate composite material. Therefore, 3, 5-di-tert-butyl salicylaldehyde polyaniline and methacrylic acid are firstly mixed and then an initiator is added, and in the process of polymerizing methyl methacrylate, the 3, 5-di-tert-butyl salicylaldehyde aniline can be further wrapped in the polymerized methyl methacrylate so as to improve the photochromic performance of Schiff base/methyl methacrylate.
According to some embodiments of the invention, the mass ratio of the 3, 5-di-tert-butyl salicylaldehyde polyaniline to the methyl methacrylate is: 1:100000-1:1000. Specifically, the mass ratio of the 3, 5-di-tert-butyl salicylaldehyde polyaniline to the methyl methacrylate can be 1:90000-1:2000, 1:80000-1:3000, 1:70000-1:4000, 1:60000-1:5000, 1:50000-1:6000, 1:40000-1:7000, 1:30000-1:8000, 1:20000-1:9000 and the like. If the content of the 3, 5-di-tert-butyl salicylaldehyde polyaniline is excessive, the color of the Schiff base/methyl methacrylate composite material can be influenced to a certain extent, so that the color of the Schiff base/methyl methacrylate composite material is deepened and even is yellowing; if the content of 3, 5-di-tert-butyl salicylaldehyde polyaniline is too small, the photochromic effect of the Schiff base/methyl methacrylate composite material can be affected to a certain extent.
According to some embodiments of the invention, the mass ratio of the 3, 5-di-tert-butyl salicylaldehyde polyaniline to the methyl methacrylate is: 1:50000-1:1000. For example, the mass ratio of the 3, 5-di-tert-butyl salicylaldehyde polyaniline to the methyl methacrylate may be 1:40000-1:2000, 1:30000-1:3000, 1:20000-1:4000, 1:10000-1:5000, 1:9000-1:6000, 1:8000-1:7000, etc.
According to some embodiments of the invention, the mass ratio of the initiator to the methyl methacrylate is: 1:1000-1:100. For example, the mass ratio of the initiator to the methyl methacrylate may be between 1:900 and 1:200, 1:800 and 1:300, 1:700 and 1:400, 1:600 and 1:500. If the content of the initiator is too small, the polymerization rate of methyl methacrylate is reduced to some extent; if the content of the initiator is too large, the polymerization intensity of methyl methacrylate is increased to some extent, and the explosion polymerization is caused.
According to some embodiments of the invention, the method of preparing a schiff base/methyl methacrylate composite may further comprise: subjecting the second mixture to a first heat treatment to obtain a first reactant; cooling the first reactant and placing the cooled first reactant in a mold; the cooled first reactant is subjected to a second heating treatment and cooled to obtain a second reactant; and carrying out third heat treatment on the second reactant, and cooling to obtain the Schiff base/methyl methacrylate composite material, wherein the temperature of the third heat treatment is higher than that of the first heat treatment, and the temperature of the first heat treatment is higher than that of the second heat treatment. Therefore, the second mixture is heated in a sectionalized way to control the speed of the polymerization reaction, prevent the explosion polymerization in the polymerization process and improve the photochromic performance of the Schiff base/methyl methacrylate composite material.
The following describes in detail the various steps of the present invention, and with reference to fig. 1, a method of preparing a schiff base/methyl methacrylate composite may comprise:
s100: mixing 3, 5-di-tert-butyl salicylaldehyde aniline, methyl methacrylate and initiator
Specifically, in this step, the 3, 5-di-tert-butyl salicylaldehyde polyaniline and the methyl methacrylate are uniformly mixed to obtain a first mixture, and then the first mixture is mixed with an initiator to obtain a second mixture.
S200: subjecting the second mixture to a first heat treatment to obtain a first reactant
Specifically, in this step, the temperature of the first heat treatment may be 80 to 95 ℃. For example, the temperature may be 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, or the like. According to some embodiments of the present invention, the heating means is not particularly limited, and the second mixture may be heated in a water bath, and the methyl methacrylate is polymerized during the heating process, and the polymerization reaction proceeds more slowly due to the lower heating temperature. The time of the first heating treatment is not particularly limited, and one skilled in the art can control the heating treatment according to actual needs. Specifically, for the present application, the first heat treatment may be ended when the progress of the polymerization reaction proceeds to about 15% to 25%.
S300: cooling the first reactant
Specifically, in this step, the temperature of the cooled first reactant is not particularly limited, and for example, the first reactant may be cooled to 30 to 40 ℃ and poured into a mold.
S400: performing a second heating treatment on the cooled first reactant to obtain a second reactant
Specifically, in this step, the temperature of the second heat treatment is 40℃to 60℃and may be, for example, 42℃44℃46℃48℃50℃52℃54℃56℃58 ℃. According to some embodiments of the present invention, the manner of the second heat treatment is not particularly limited, and the first reactant may be heated in a water bath, during which the polymerization of methyl methacrylate continues. The time of the second heating treatment is not particularly limited, and one skilled in the art can control the second heating treatment according to actual needs. Specifically, the time of the second heat treatment may be 10 to 40 hours, for example, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, or the like.
S500: the second mixture is subjected to a third heating treatment and cooled to obtain a Schiff base/methyl methacrylate composite material
Specifically, in this step, the temperature of the third heat treatment may be 90℃to 120℃and, for example, may be 95℃100℃105℃110℃115℃or the like. Thus, the methyl methacrylate is completely polymerized to obtain the solid Schiff base/methyl methacrylate composite material, and the solid Schiff base/methyl methacrylate composite material is slowly cooled to room temperature and then is demoulded.
In another aspect of the present invention, a Schiff base/methyl methacrylate composite is provided, which is prepared by the method described above. Therefore, the Schiff base/methyl methacrylate composite material is colorless and transparent, can be rapidly colored under ultraviolet light stimulation, and can be rapidly recovered under visible light stimulation, and has good photochromic performance.
In yet another aspect of the present invention, there is provided the use of the foregoing schiff base/methyl methacrylate composite, including at least one of the transparent display field, the battery field, the wearable device field, and the three-dimensional data storage field. Therefore, when the Schiff base/methyl methacrylate composite material is applied to related devices in the fields, the good photochromic performance and the fatigue resistance of the Schiff base/methyl methacrylate composite material can be exerted.
According to some embodiments of the present invention, schiff base/methyl methacrylate composites may be used in transparent displays, solar cells, organic light emitting diodes, three-dimensional data storage, optical films, color changing glasses, wearable devices, and the like.
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
3, 5-di-tert-butyl salicylaldehyde aniline and methyl methacrylate are uniformly mixed according to the mass ratio of 1:10000, 0.4% benzoyl peroxide is added based on the total mass of the methyl methacrylate, the mixture is prepolymerized in a water bath at 85 ℃ until the raw material liquid is glycerol viscosity, the raw material liquid is cooled to 30 ℃, the mixture is poured into a mould, the mould is placed in a water bath at 50 ℃ for heat preservation for 10 hours, finally high-temperature polymerization is carried out for 1 hour at 100 ℃, the mixture is slowly cooled to room temperature, and the Schiff base/methyl methacrylate composite material can be obtained after demoulding.
After 365nm ultraviolet light irradiates for 5 seconds, the composite material absorbs visible light in the range of 400-550 nm, changes from colorless to orange, and recovers after visible light irradiation, as shown in figure 2.
Example 2
The specific preparation process is the same as in example 1, except that the mass ratio of 3, 5-di-tert-butylsalicylaldehyde polyaniline to methyl methacrylate is 1:50000.
After 365nm ultraviolet light irradiates for 5 seconds, the composite material absorbs visible light in the range of 400-550 nm, changes from colorless to orange, and recovers after visible light irradiation, as shown in figure 3.
Example 3
The specific preparation process was the same as in example 1, except that the mass ratio of 3, 5-di-tert-butylsalicylaldehyde polyaniline to methyl methacrylate was 1:90000.
After 365nm ultraviolet light irradiates for 5 seconds, the composite material absorbs visible light in the range of 400-550 nm, changes from colorless to orange, and recovers after visible light irradiation, as shown in fig. 4.
Example 4
The specific preparation process is the same as in example 1, except that the mass ratio of 3, 5-di-tert-butylsalicylaldehyde polyaniline to methyl methacrylate is 1:1100.
After 365nm ultraviolet light irradiates for 5 seconds, the composite material absorbs visible light in the range of 400-550 nm, changes from colorless to orange, and recovers after visible light irradiation, as shown in fig. 5.
Example 5
The specific preparation process is the same as in example 1, except that the mass ratio of 3, 5-di-tert-butylsalicylaldehyde polyaniline to methyl methacrylate is 1:200000.
After the composite material is irradiated by 365nm ultraviolet light for 5 seconds, as shown in fig. 6, the composite material weakly absorbs visible light in the range of 400-550 nm, and is changed from colorless to pale yellow. The photochromic phenomenon is not obvious and is mainly caused by the fact that the doping amount of 3, 5-di-tert-butyl salicylaldehyde polyaniline is too small.
Example 6
The specific preparation process is the same as in example 1, except that the mass ratio of 3, 5-di-tert-butylsalicylaldehyde polyaniline to methyl methacrylate is 1:500.
After the composite material is irradiated by 365nm ultraviolet light for 5 seconds, as shown in fig. 7, the absorption peak of 400-550 nm is not obvious, and the color is too deep, mainly caused by that the ultraviolet light cannot penetrate due to excessive doping amount of 3, 5-di-tert-butyl salicylaldehyde polyaniline.
Example 7
The specific preparation was the same as in example 1, except that 0.9% of benzoyl peroxide was added based on the total mass of methyl methacrylate.
The composite material has uniform and transparent appearance, absorbs visible light in the range of 400-550 nm after 365nm ultraviolet light irradiation for 5 seconds, changes from colorless to orange, and recovers after visible light irradiation, as shown in fig. 8.
Example 8
The specific preparation was the same as in example 1, except that 0.12% of benzoyl peroxide was added based on the total mass of methyl methacrylate.
The composite material was uniform and transparent in appearance, absorbing visible light in the range of 400-550 nm after 5s irradiation with 365nm ultraviolet light, changing from colorless to orange, and recovering after visible light irradiation, as shown in fig. 9.
Example 9
The specific preparation was the same as in example 1, except that 0.08% benzoyl peroxide was added based on the total mass of methyl methacrylate, and the heat-insulating time in a water bath at 50℃was prolonged to 45 hours.
As shown in fig. 10, the composite material has uniform and transparent appearance and can be photochromic, but the polymerization time process is too long, and the production efficiency is affected.
Example 10
The specific preparation was the same as in example 1, except that 1.5% of benzoyl peroxide was added based on the total mass of methyl methacrylate.
The composite is unevenly transparent due to the intense exotherm of the polymerization process. However, the block was still photochromic after 5s irradiation with 365nm ultraviolet light, as shown in FIG. 11.
Comparative example 1
Adding 0.4% benzoyl peroxide into methyl methacrylate, pre-polymerizing in 85 ℃ water bath until the raw material liquid is glycerol viscosity, cooling the raw material liquid to 30 ℃, pouring the raw material liquid into a mold, placing the mold in 50 ℃ water bath for heat preservation for 10 hours, finally performing high-temperature polymerization for 1 hour at 100 ℃, slowly cooling to room temperature, and demolding to obtain pure polymethyl methacrylate.
Polymethyl methacrylate did not change at all after 5s irradiation with 365nm uv light as shown in fig. 12.
Comparative example 2
3, 5-Di-tert-Butylsalicylaldehyde (0.47 g,2 mmol) and aniline (0.28 g,2 mmol) were mixed in 20mL absolute ethanol, heated to reflux at 78℃and reacted for 4h with stirring; after the reaction is finished, removing the solvent by rotary evaporation to obtain a crude product, and recrystallizing with absolute ethyl alcohol to obtain the 3, 5-di-tert-butyl salicylaldehyde polyaniline.
The 3, 5-di-t-butylsalicylaldehyde polyaniline powder changed from yellow to orange after 5s of irradiation with 365nm ultraviolet light and recovered after irradiation with visible light, as shown in fig. 13.
The testing method comprises the following steps:
ultraviolet-visible absorption spectrum: the baseline was scanned over 300-700 nm using a 1cm thick clear block of pure PMMA as a standard sample. The samples to be tested are cut, polished and polished to a thickness of 1cm, and ultraviolet-visible absorption spectrum data are respectively tested before and after 365nm ultraviolet light is irradiated for 5 seconds, wherein the testing temperature is 15 ℃.
In the present invention, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A method of making a schiff base/methyl methacrylate composite comprising:
and mixing the Schiff base, methyl methacrylate and an initiator, and heating and cooling to obtain the Schiff base/methyl methacrylate composite material, wherein the Schiff base comprises 3, 5-di-tert-butyl salicylaldehyde polyaniline.
2. The method as recited in claim 1, further comprising: uniformly mixing the 3, 5-di-tert-butyl salicylaldehyde polyaniline and the methyl methacrylate to obtain a first mixture;
mixing the first mixture with the initiator to obtain a second mixture, and heating and cooling the second mixture to obtain the Schiff base/methyl methacrylate composite material.
3. The method according to claim 1 or 2, wherein the mass ratio of the 3, 5-di-tert-butyl salicylaldehyde polyaniline to the methyl methacrylate is: 1:100000-1:1000.
4. A method according to claim 3, wherein the mass ratio of 3, 5-di-tert-butylsalicylaldehyde polyaniline to methyl methacrylate is: 1:50000-1:1000.
5. The method according to claim 1, wherein the mass ratio of the initiator to the methyl methacrylate is: 1:1000-1:100.
6. The method according to claim 2, characterized by comprising:
subjecting the second mixture to a first heat treatment to obtain a first reactant;
cooling the first reactant and placing the cooled first reactant in a mold;
the cooled first reactant is subjected to a second heating treatment and cooled to obtain a second reactant;
and carrying out third heat treatment on the second reactant, and cooling to obtain the Schiff base/methyl methacrylate composite material, wherein the temperature of the third heat treatment is higher than that of the first heat treatment, and the temperature of the first heat treatment is higher than that of the second heat treatment.
7. The method of claim 6, wherein at least one of the following conditions is satisfied:
the temperature of the first heating treatment is 80-95 ℃;
the temperature of the second heating treatment is 40-60 ℃;
the temperature of the third heating treatment is 90-120 ℃.
8. The method of claim 1, wherein the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, and benzoyl peroxide.
9. A Schiff base/methyl methacrylate composite material, characterized in that it is prepared by the method according to any one of claims 1 to 8.
10. Use of a schiff base/methyl methacrylate composite according to claim 9, comprising at least one of the fields of transparent displays, batteries, wearable devices and three-dimensional data storage.
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| CN112812210A (en) * | 2021-01-21 | 2021-05-18 | 福建师范大学 | Thermal polymerization process of PQ/PMMA photopolymer material, PQ/PMMA photopolymer material and holographic optical disk thereof |
| US20220220235A1 (en) * | 2019-12-27 | 2022-07-14 | Hoya Lens Thailand Ltd. | Polymerizable composition for optical article and optical article |
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| US20220220235A1 (en) * | 2019-12-27 | 2022-07-14 | Hoya Lens Thailand Ltd. | Polymerizable composition for optical article and optical article |
| CN112812210A (en) * | 2021-01-21 | 2021-05-18 | 福建师范大学 | Thermal polymerization process of PQ/PMMA photopolymer material, PQ/PMMA photopolymer material and holographic optical disk thereof |
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