CN110746327A - A kind of azobenzene-graphene composite material and its application in color-changing encryption and secrecy - Google Patents
A kind of azobenzene-graphene composite material and its application in color-changing encryption and secrecy Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000002360 preparation method Methods 0.000 claims abstract description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 33
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 19
- GBWNQBBVSVGAAL-UHFFFAOYSA-N 5-aminobenzene-1,3-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1 GBWNQBBVSVGAAL-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 235000010288 sodium nitrite Nutrition 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 238000002845 discoloration Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000012954 diazonium Substances 0.000 claims description 5
- 150000001989 diazonium salts Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WNRGWPVJGDABME-UHFFFAOYSA-N 3,5-Dimethoxyaniline Chemical compound COC1=CC(N)=CC(OC)=C1 WNRGWPVJGDABME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 239000000049 pigment Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 230000000638 stimulation Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 8
- 239000011232 storage material Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- -1 Polypropylene Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- TYHQAMJTELNECQ-UHFFFAOYSA-N 3,5-dimethoxy-n-phenylaniline Chemical compound COC1=CC(OC)=CC(NC=2C=CC=CC=2)=C1 TYHQAMJTELNECQ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000005266 side chain polymer Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/46—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
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- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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Abstract
本发明公开一种偶氮苯—石墨烯复合材料及其在变色加密保密中的应用，偶氮苯分子以共价键的方式接枝到石墨烯表面，每20～40个碳原子接枝一个偶氮苯分子；首先偶氮苯分子的制备；然后还原氧化石墨烯预处理；进行偶氮苯分子石墨烯复合材料的制备；最后进行偶氮苯石墨烯材料与热致变色颜料的结合，得到最终的加密保密材料。通过紫外光照射偶氮苯石墨烯材料充热和对其进行加热刺激放热，完成加密保密的过程，为加密保密行业提供了一种新的思路与方法。
The invention discloses an azobenzene-graphene composite material and its application in color-changing encryption and secrecy. Azobenzene molecules are grafted to the graphene surface in the form of covalent bonds, and each 20-40 carbon atoms are grafted one Azobenzene molecule; firstly preparation of azobenzene molecule; then reduction of graphene oxide pretreatment; preparation of azobenzene molecular graphene composite material; finally, combination of azobenzene graphene material and thermochromic pigment to obtain The final encrypted confidential material. The process of encryption and confidentiality is completed by irradiating the azobenzene graphene material with ultraviolet light and heating it to stimulate heat release, which provides a new idea and method for the encryption and confidentiality industry.
Description
技术领域technical field
本发明属于功能复合材料领域，更加具体地说，涉及一种偶氮苯石墨烯材料与变色浆料一体的加密保密材料及制备方法，其在太阳能利用和加密解密方面具有重要的应用前景。The invention belongs to the field of functional composite materials, and more particularly relates to an encryption and security material and a preparation method integrating an azobenzene graphene material and a color-changing slurry, which have important application prospects in solar energy utilization and encryption and decryption.
背景技术Background technique
随着我国科学技术的发展，各行各业的竞争日趋激烈。并且在国际上，我国的影响力也越来越大，国与国之间的竞争进入到白热化阶段。在这种情况下，信息的安全显得尤为重要。各个企业，各个国家的信息安全保密工作形势十分严峻，泄密事件一旦发生，造成的损失会十分惨重。因此发展一种新的加密保密的方式与材料是十分有必要的。太阳能作为一种可再生能源受到了诸多的关注。它具有很多其他能源不具备的优势，例如其能量多，利用开发无污染，不受地理环境的影响等。通过恰当的技术与材料，太阳能可以被利用到各个领域。偶氮苯分子是一种光响应分子，具有顺反异构的特性。在紫外光的照射下，反式结构通过吸收光子能量会转变为顺式结构，之后在加热或可见光照射等外界刺激下可将吸收的能量转变为热能释放出来，从而转变回反式结构，以石墨烯为模板可增加偶氮苯分子间的相互作用力，大大提高其能量密度。目前大多数研究集中在提升材料能量密度这个方面，在其他方面涉及的较少。With the development of science and technology in our country, the competition in all walks of life is becoming increasingly fierce. And in the international arena, my country's influence is also growing, and the competition between countries has entered a white-hot stage. In this case, the security of information is particularly important. The information security and confidentiality work situation of various enterprises and countries is very serious. Once a leak occurs, the loss will be very heavy. Therefore, it is very necessary to develop a new encryption method and material. Solar energy has received a lot of attention as a renewable energy source. It has many advantages that other energy sources do not have, such as more energy, pollution-free utilization and development, and no impact on the geographical environment. With the right technology and materials, solar energy can be utilized in various fields. Azobenzene molecule is a light-responsive molecule with cis-trans isomerism. Under the irradiation of ultraviolet light, the trans structure will be converted into a cis structure by absorbing photon energy, and then the absorbed energy can be converted into heat energy and released under external stimuli such as heating or visible light irradiation, thereby converting back to the trans structure. Graphene as a template can increase the interaction force between azobenzene molecules and greatly improve its energy density. At present, most of the research focuses on improving the energy density of materials, and involves less in other aspects.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术的不足，提供一种偶氮苯—石墨烯复合材料及其在变色加密保密中的应用，即研究一种能够将太阳能转化成热能，从而达到保密加密效果的一种复合材料，以及基于复合材料的加密保密体系。热致变色颜料的特点是在环境温度达到特定温度时，会改变自身颜色。将偶氮苯石墨烯材料与热致变色颜料结合，利用偶氮苯石墨烯材料放出的热与变色浆料能够改变颜色的特性，得到一种新型的加密保密体系。The object of the present invention is to overcome the deficiencies in the prior art, provide a kind of azobenzene-graphene composite material and its application in color-changing encryption and confidentiality, that is to study a kind of solar energy can be converted into thermal energy, thereby achieving the effect of encryption encryption A composite material, and an encryption security system based on the composite material. Thermochromic pigments are characterized by changing their color when the ambient temperature reaches a certain temperature. The azobenzene graphene material is combined with the thermochromic pigment, and the heat and discoloration slurry released by the azobenzene graphene material can be used to change the characteristics of the color, and a new type of encryption and security system is obtained.
本发明的技术目的通过下述技术方案予以实现：The technical purpose of the present invention is achieved through the following technical solutions:
偶氮苯—石墨烯复合材料，将杂环偶氮分子以共价键接枝到石墨烯表面。Azobenzene-graphene composite material, the heterocyclic azo molecules are covalently grafted to the graphene surface.
在本发明的技术方案中，石墨烯可采用氧化石墨烯还原得到石墨烯(即还原氧化石墨烯)，以使组成石墨烯的苯环结构出现破损结构，致密的六元环(苯环)结构出现某个碳原子的缺失，形成空位，为杂环偶氮苯的接枝提供反应位点(与杂环偶氮苯分子的羟基OH、氨基NH2等官能团进行反应)，达到每20～50个碳原子接枝一个杂环偶氮苯分子，优选每20～30个碳原子接枝一个偶氮苯分子。In the technical scheme of the present invention, graphene can be reduced by graphene oxide to obtain graphene (that is, reduced graphene oxide), so that the benzene ring structure of graphene has a damaged structure, and the dense six-membered ring (benzene ring) structure A certain carbon atom is missing, forming a vacancy, providing a reaction site for the grafting of heterocyclic azobenzene (reacting with functional groups such as hydroxyl OH and amino NH 2 of the heterocyclic azobenzene molecule), reaching every 20-50 Each carbon atom is grafted to one heterocyclic azobenzene molecule, preferably every 20-30 carbon atoms is grafted to one azobenzene molecule.
杂环偶氮苯分子为偶氮苯—石墨烯复合材料提供具有储能功能的基团，具有分子式之一所示的结构：The heterocyclic azobenzene molecule provides a group with energy storage function for the azobenzene-graphene composite material, and has the structure shown in one of the molecular formulas:
偶氮苯—石墨烯复合材料，将上述杂环偶氮苯分子键接到石墨烯表面，具体来说，具有如下分子式之一所示的结构Azobenzene-graphene composite material, the above-mentioned heterocyclic azobenzene molecule is bonded to the graphene surface, specifically, has the structure shown in one of the following molecular formulas
上述偶氮苯分子和偶氮苯—石墨烯复合材料的制备详见如下中国专利：一种可用于太阳能储热的偶氮苯分子及其制备方法、2015105747896；一种三枝偶氮苯/石墨烯复合储能材料及制备方法、2016103482626；一种双枝偶氮苯/石墨烯储能材料及其制备方法、2016103770977；一类用于太阳能热存储的邻位含吸电基团的偶氮苯衍生物及其制备方法、2016108934776；一种线性双枝偶氮苯/石墨烯复合材料及制备方法和应用、2017101510787；偶氮苯—石墨烯复合材料在制备防冰材料中的应用、2017102679190；基于偶氮苯的氟化衍生物及其制备方法、2017103180599；一种交替双层偶氮苯/石墨烯复合储能材料及制备方法、2017108331434；一种杂环偶氮苯/石墨烯太阳能储热材料及制备方法、2017108331345；一种双接枝偶氮苯/石墨烯复合储能材料及制备方法、 2017108337093；三枝偶氮苯分子及其制备方法、2017109547309；一种偶氮苯侧链聚合物储能材料及制备方法、2018107923063；一种双接枝杂环偶氮苯石墨烯储能材料及制备方法、2018108058460；一种含偶氮苯/碳杂化材料的热感氟碳功能涂料及制备方法、 2016100671683。The preparation of the above-mentioned azobenzene molecule and azobenzene-graphene composite material is detailed in the following Chinese patents: A kind of azobenzene molecule that can be used for solar heat storage and preparation method thereof, 2015105747896; A three-branched azobenzene/graphene Composite energy storage material and preparation method, 2016103482626; A double-branched azobenzene/graphene energy storage material and preparation method thereof, 2016103770977; A class of azobenzene derivatives containing ortho-position electricity-absorbing groups for solar thermal storage Compound and preparation method thereof, 2016108934776; A linear double-branched azobenzene/graphene composite material, preparation method and application thereof, 2017101510787; Application of azobenzene-graphene composite material in the preparation of anti-icing materials, 2017102679190; Fluorinated derivatives of azobenzene and preparation method thereof, 2017103180599; A kind of alternating double-layer azobenzene/graphene composite energy storage material and preparation method, 2017108331434; A heterocyclic azobenzene/graphene solar energy heat storage material and Preparation method, 2017108331345; A double-grafted azobenzene/graphene composite energy storage material and preparation method, 2017108337093; Tri-branched azobenzene molecule and preparation method thereof, 2017109547309; An azobenzene side chain polymer energy storage material And preparation method, 2018107923063; A double-grafted heterocyclic azobenzene graphene energy storage material and preparation method, 2018108058460; A thermally sensitive fluorocarbon functional coating containing azobenzene/carbon hybrid material and preparation method, 2016100671683 .
以如下偶氮苯分子和相应的偶氮苯—石墨烯复合材料为例，简要说明其制备过程Taking the following azobenzene molecules and the corresponding azobenzene-graphene composites as examples, the preparation process is briefly described
偶氮苯分子的制备：将5-氨基-1,3-苯二磺酸和氢氧化钠均匀分散在去离子水中，加入亚硝酸钠水溶液，搅拌反应形成重氮盐溶液；将重氮盐溶液滴加到盐酸中冰浴下反应，加入3,5-二甲氧基苯胺并在惰性保护气体氛围下继续反应，以得到偶氮苯分子。Preparation of azobenzene molecule: 5-amino-1,3-benzenedisulfonic acid and sodium hydroxide are uniformly dispersed in deionized water, sodium nitrite aqueous solution is added, and the reaction is stirred to form a diazonium salt solution; Add dropwise to hydrochloric acid and react under ice bath, add 3,5-dimethoxyaniline and continue the reaction under inert protective gas atmosphere to obtain azobenzene molecule.
5-氨基-1,3-苯二磺酸用量为20～30摩尔份，每一摩尔份为1mmol。The dosage of 5-amino-1,3-benzenedisulfonic acid is 20-30 mole parts, and each mole part is 1 mmol.
5-氨基-1,3-苯二磺酸和氢氧化钠的摩尔比为1：1。The molar ratio of 5-amino-1,3-benzenedisulfonic acid and sodium hydroxide was 1:1.
5-氨基-1,3-苯二磺酸和亚硝酸钠的摩尔比为1：(1—1.5)。The molar ratio of 5-amino-1,3-benzenedisulfonic acid and sodium nitrite is 1:(1-1.5).
5-氨基-1,3-苯二磺酸和盐酸中氯化氢的摩尔比为1：(3—5)，盐酸的浓度为1mol/L。The molar ratio of hydrogen chloride in 5-amino-1,3-benzenedisulfonic acid and hydrochloric acid is 1:(3-5), and the concentration of hydrochloric acid is 1 mol/L.
搅拌速度为每分钟100—300转，惰性保护气体为氮气、氦气或者氩气。The stirring speed is 100-300 revolutions per minute, and the inert protective gas is nitrogen, helium or argon.
将重氮盐溶液滴加到盐酸，用时20—30min，冰浴下反应1—2小时，在惰性保护气体氛围下持续搅拌反应1—5小时，优选2—3小时。The diazonium salt solution is added dropwise to hydrochloric acid for 20-30 min, the reaction is carried out in an ice bath for 1-2 hours, and the reaction is continuously stirred under an inert protective gas atmosphere for 1-5 hours, preferably 2-3 hours.
在反应结束之后，抽滤得到粗产品，用蒸馏水多次洗涤之后，在乙醇和丙酮的混合溶液(乙醇和丙酮的体积比为1:1)中进行重结晶，得到目标的偶氮单体。After the reaction is completed, the crude product is obtained by suction filtration, washed with distilled water for many times, and then recrystallized in a mixed solution of ethanol and acetone (the volume ratio of ethanol and acetone is 1:1) to obtain the target azo monomer.
还原氧化石墨烯(RGO)处理：利用氢氧化钠将均匀分散氧化石墨烯的水溶液的pH调节至8～9，再加入硼氢化钠，在惰性保护气体下利用硼氢化钠对氧化石墨烯进行还原处理，得到还原氧化石墨烯。产物经过多次离心、抽滤，洗涤之后得到制备好的；最后利用超声使其分散在水中。具体来说：Reduced graphene oxide (RGO) treatment: the pH of the aqueous solution of uniformly dispersed graphene oxide is adjusted to 8-9 with sodium hydroxide, then sodium borohydride is added, and the graphene oxide is reduced with sodium borohydride under an inert protective gas treatment to obtain reduced graphene oxide. The product is prepared by centrifugation, suction filtration, and washing for many times; finally, it is dispersed in water by ultrasonic wave. Specifically:
在反应过程中采用搅拌，以使其均匀分散和反应，搅拌速度为每分钟100—300转，惰性保护气体为氮气、氦气或者氩气。During the reaction, stirring is used to make it evenly dispersed and reacted, the stirring speed is 100-300 revolutions per minute, and the inert protective gas is nitrogen, helium or argon.
在进行反应时，在80～90℃下反应1—5小时，优选2～3小时。When the reaction is carried out, the reaction is carried out at 80 to 90° C. for 1 to 5 hours, preferably 2 to 3 hours.
硼氢化钠的浓度为10-30mg/ml(硼氢化钠质量，mg/水体积，ml)，相对于氧化石墨烯，硼氢化钠用量为过量，以使氧化石墨烯充分还原。The concentration of sodium borohydride is 10-30 mg/ml (mass of sodium borohydride, mg/volume of water, ml), and the amount of sodium borohydride is excessive relative to graphene oxide to fully reduce graphene oxide.
偶氮苯—石墨烯复合材料的制备方法：将偶氮苯分子和亚硝酸钠均匀分散在去离子水中，在冰浴条件下滴加到盐酸中进行反应，得到含有偶氮苯的水溶液；在冰浴条件下将含有偶氮苯的水溶液滴加到分散有还原氧化石墨烯的水溶液中进行反应，以得到偶氮苯—石墨烯复合材料。The preparation method of azobenzene-graphene composite material: the azobenzene molecules and sodium nitrite are uniformly dispersed in deionized water, and added dropwise to hydrochloric acid under ice bath conditions for reaction to obtain an aqueous solution containing azobenzene; Under ice bath conditions, the aqueous solution containing azobenzene is added dropwise to the aqueous solution dispersed with reduced graphene oxide for reaction to obtain the azobenzene-graphene composite material.
偶氮苯分子和亚硝酸钠为等摩尔比，在冰浴条件下反应1—5小时，优选1—2小时，得到含有偶氮苯的水溶液，盐酸浓度为1M，盐酸和去离子水的用量为等体积比。Azobenzene molecule and sodium nitrite are in an equimolar ratio, react under ice bath conditions for 1-5 hours, preferably 1-2 hours, to obtain an aqueous solution containing azobenzene, the concentration of hydrochloric acid is 1M, the consumption of hydrochloric acid and deionized water is an equal volume ratio.
偶氮苯分子用量为1—5摩尔份，每一摩尔份为1mmol。The molecular dosage of azobenzene is 1-5 mole parts, and each mole part is 1 mmol.
将含有偶氮苯的水溶液逐滴加入均匀分散还原氧化石墨烯的水溶液，冰浴条件下反应5—10小时，优选8—10小时，然后在室温20—25摄氏度下继续反应20—50小时，优选24—48小时，以使偶氮苯以共价键方式接枝到石墨烯表面。The aqueous solution containing azobenzene is added dropwise to the aqueous solution of uniformly dispersed reduced graphene oxide, the reaction is performed under ice bath conditions for 5-10 hours, preferably 8-10 hours, and then the reaction is continued at room temperature of 20-25 degrees Celsius for 20-50 hours, It is preferably 24-48 hours, so that the azobenzene is grafted to the graphene surface in a covalent bond manner.
反应产物减压抽滤，使用去离子水、DMF洗涤3—6次，抽滤得到目标产物。The reaction product is suction filtered under reduced pressure, washed 3-6 times with deionized water and DMF, and suction filtered to obtain the target product.
在分散有还原氧化石墨烯的水溶液中，还原氧化石墨烯的用量为20—50质量份，每一质量份为1mg，优选20—30质量份，均匀分散还原氧化石墨烯的水溶液用量为50—100体积份，每一体积份为1ml，优选60—80体积份。In the aqueous solution dispersed with reduced graphene oxide, the amount of reduced graphene oxide used is 20-50 parts by mass, and each part by mass is 1 mg, preferably 20-30 parts by mass, and the amount of the aqueous solution of uniformly dispersed reduced graphene oxide is 50-50 parts by mass. 100 volume parts, each volume part is 1ml, preferably 60-80 volume parts.
偶氮苯—石墨烯复合材料顺反异构效果结构式如下：The structural formula of the cis-trans isomerization effect of the azobenzene-graphene composite material is as follows:
上述的杂环偶氮苯分子、偶氮苯—石墨烯复合材料在变色加密保密、信息存储显示中的应用。The application of the above-mentioned heterocyclic azobenzene molecule and azobenzene-graphene composite material in color-changing encryption and confidentiality, information storage and display.
将热致变色颜料和偶氮苯—石墨烯复合材料设置在信息内容区域，并使用紫外光对信息内容区域中部分偶氮苯—石墨烯复合材料进行辐照充热，其他区域遮挡住不接受任何刺激，最后对信息内容区域进行加热，加热至热致变色颜料的变色温度之下，经过辐照充热的偶氮苯—石墨烯复合材料在加热刺激下进行放热，对与之对应的信息内容区域进行加热，以达到热致变色颜料的变色温度，从而造成在信息内容区域中被紫外光照射过的区域与没有照射过的区域存在温差，造成热致变色颜料改变颜色显现出相应信息，完成加密保密的过程。Set the thermochromic pigment and azobenzene-graphene composite material in the information content area, and use ultraviolet light to irradiate and heat some azobenzene-graphene composite materials in the information content area, and block other areas and do not accept it. Any stimulation, the information content area is finally heated, heated to below the discoloration temperature of the thermochromic pigment, and the azobenzene-graphene composite material heated by irradiation will release heat under the heating stimulation, and the corresponding The information content area is heated to reach the discoloration temperature of the thermochromic pigment, resulting in a temperature difference between the area irradiated by ultraviolet light and the area not irradiated in the information content area, causing the thermochromic pigment to change color and display the corresponding information , complete the process of encryption and secrecy.
其中加热至热致变色颜料的变色温度之下5℃以内。It is heated to within 5°C below the discoloration temperature of the thermochromic pigment.
具体来说，偶氮苯石墨烯体系变色加密保密材料的制备：取30～60mg抽滤得到的偶氮苯石墨烯薄膜裁剪成规则的长方形，然后将65℃的热致变色颜料通过丝印印于聚丙烯不干胶表面。将聚丙烯薄膜粘贴在偶氮苯石墨烯复合材料的表面，根据信息内容分区域用紫外光对此材料照射3～6个小时进行充热，其他区域遮挡住不接受任何刺激。最后将此材料放置在热台上，加热到60℃，充过热的偶氮苯石墨烯复合材料会在加热刺激下进行放热，从而造成被紫外光照射过的区域与没有照射过的区域存在5℃的温差，从而使热致变色颜料改变颜色，显现出信息，完成加密保密的过程。Specifically, the preparation of the azobenzene graphene system discoloration encryption confidential material: take 30-60 mg of the azobenzene graphene film obtained by suction filtration and cut it into a regular rectangle, and then the thermochromic pigment at 65 ° C is screen-printed on the Polypropylene self-adhesive surface. The polypropylene film is pasted on the surface of the azobenzene-graphene composite material, and the material is irradiated with ultraviolet light for 3 to 6 hours according to the information content to heat the material, and other areas are blocked and do not receive any stimulation. Finally, the material is placed on a hot stage and heated to 60°C. The superheated azobenzene-graphene composite material will exotherm under heating stimulation, resulting in the existence of areas irradiated by ultraviolet light and areas that have not been irradiated. The temperature difference of 5 °C makes the thermochromic pigment change color, reveal information, and complete the process of encryption and confidentiality.
附图说明Description of drawings
图1为本发明实施例中偶氮苯分子的红外谱图。Fig. 1 is the infrared spectrogram of azobenzene molecule in the embodiment of the present invention.
图2为本发明实施例中偶氮苯—石墨烯复合材料的扫描电镜图。Fig. 2 is the scanning electron microscope picture of azobenzene-graphene composite material in the embodiment of the present invention.
图3为本发明实施例中偶氮苯—石墨烯复合材料的DSC(差式扫描量热)图。Fig. 3 is the DSC (differential scanning calorimetry) diagram of the azobenzene-graphene composite material in the embodiment of the present invention.
图4为本发明实施例中偶氮苯—石墨烯复合材料的变色加密保密材料效果示意图。FIG. 4 is a schematic diagram of the effect of the color-changing encryption and security material of the azobenzene-graphene composite material in the embodiment of the present invention.
具体实施方式Detailed ways
以如下偶氮苯分子和相应的偶氮苯—石墨烯复合材料为例，对本发明的进一步说明，而不是限制本发明的范围。The following azobenzene molecules and corresponding azobenzene-graphene composite materials are taken as examples to further illustrate the present invention, rather than limiting the scope of the present invention.
实施例1Example 1
1)偶氮苯分子的制备：取20mmol的5-氨基-1,3-苯二磺酸和等当量(即与5-氨基-1,3- 苯二磺酸等摩尔比)的氢氧化钠，溶于去离子水中，然后向其中滴加1.1当量的亚硝酸钠 (5-氨基-1,3-苯二磺酸摩尔的1.1倍)的水溶液，分散均匀后再将此溶液缓慢滴加到3当量1mol/l的盐酸(氯化氢为5-氨基-1,3-苯二磺酸摩尔的3倍)中，冰浴条件下搅拌2个小时后，加入1.2当量的3,5-二甲氧基苯胺(5-氨基-1,3-苯二磺酸摩尔的1.2倍)并在氮气保护下继续反应3个小时得到偶氮苯分子。1) the preparation of azobenzene molecule: get the sodium hydroxide of 5-amino-1,3-benzenedisulfonic acid of 20mmol and equivalent (being equimolar ratio with 5-amino-1,3-benzenedisulfonic acid) , dissolved in deionized water, and then dropwise added 1.1 equivalents of sodium nitrite (1.1 times the mole of 5-amino-1,3-benzenedisulfonic acid) aqueous solution, dispersed evenly, and then slowly added this solution dropwise to the 3 equivalents of 1 mol/l hydrochloric acid (hydrogen chloride is 3 times the mole of 5-amino-1,3-benzenedisulfonic acid), stirred for 2 hours under ice bath conditions, and then added 1.2 equivalents of 3,5-dimethoxy phenylaniline (1.2 times the mole of 5-amino-1,3-benzenedisulfonic acid) and continue to react under nitrogen protection for 3 hours to obtain azobenzene molecule.
2)还原氧化石墨烯预处理：用质量百分数为20％～25％的碳酸钠水溶液将分散氧化石墨烯的水溶液调节pH到9，在20mg/ml硼氢化钠水溶液中加入40ml的pH调好的氧化石墨烯水溶液，并在90℃下放置8小时；通过离心，过滤，蒸馏水水洗得到所需要的 RGO；然后把通过超声重新分散在水中。2) Pretreatment of reduced graphene oxide: adjust the pH of the aqueous solution of dispersed graphene oxide to 9 with an aqueous sodium carbonate solution with a mass percentage of 20% to 25%, add 40ml of pH to the 20mg/ml aqueous sodium borohydride solution and adjust The graphene oxide aqueous solution was placed at 90 °C for 8 hours; the required RGO was obtained by centrifugation, filtration, and distilled water washing; and then re-dispersed in water by ultrasound.
3)偶氮苯石墨烯复合材料的制备：取3mmol步骤1)得到的偶氮苯分子和等当量亚硝酸钠溶解在去离子水中，然后在冰浴条件下滴加到1mol/l盐酸溶液中，反应2个小时，在冰浴条件下将其滴加到30mg还原氧化石墨烯的水溶液(水体积为100ml)中，冰浴中反应10个小时，然后在室温下反应48个小时；减压抽滤，用去离子水和DMF反复洗涤多次，最后真空干燥得到目标产物偶氮苯石墨烯复合材料。3) preparation of azobenzene graphene composite material: get 3mmol step 1) azobenzene molecule that obtains and equivalent sodium nitrite are dissolved in deionized water, then dropwise in 1mol/l hydrochloric acid solution under ice bath condition , reacted for 2 hours, was added dropwise to the aqueous solution of 30mg reduced graphene oxide (water volume was 100ml) under ice bath conditions, reacted in ice bath for 10 hours, and then reacted at room temperature for 48 hours; Suction filtration, repeated washing with deionized water and DMF for several times, and finally vacuum drying to obtain the target product azobenzene-graphene composite material.
4)偶氮苯石墨烯体系变色加密保密材料的制备：取30mg步骤3)抽滤得到的偶氮苯石墨烯薄膜裁剪成规则的长方形，然后将65℃的热致变色颜料通过丝印印于聚丙烯不干胶表面。将聚丙烯薄膜粘贴在偶氮苯石墨烯复合材料的表面，根据信息内容分区域用紫外光对此材料照射6个小时进行充热，其他区域遮挡住不接受任何刺激。最后将此材料放置在热台上，加热到60℃，充过热的偶氮苯石墨烯复合材料会在加热刺激下进行放热，从而造成被紫外光照射过的区域与没有照射过的区域存在5℃的温差，从而使热致变色颜料改变颜色，显现出信息，完成加密保密的过程。4) Preparation of azobenzene graphene system discoloration encryption and confidentiality material: take 30 mg of the azobenzene graphene film obtained in step 3) by suction filtration and cut it into a regular rectangle, and then the thermochromic pigment at 65 ° C is screen-printed on the polystyrene. Acrylic self-adhesive surface. The polypropylene film was pasted on the surface of the azobenzene-graphene composite material. According to the information content, the material was irradiated with ultraviolet light for 6 hours to heat the material, and other areas were blocked and did not receive any stimulation. Finally, the material is placed on a hot stage and heated to 60°C. The superheated azobenzene-graphene composite material will exotherm under heating stimulation, resulting in the existence of areas irradiated by ultraviolet light and areas that have not been irradiated. The temperature difference of 5 °C makes the thermochromic pigment change color, reveal information, and complete the process of encryption and confidentiality.
实施例2Example 2
1)偶氮苯分子的制备：取30mmol的5-氨基-1,3-苯二磺酸和等当量的氢氧化钠，溶于去离子水中，然后向其中滴加1.5当量的亚硝酸钠溶液，分散均匀后再将此溶液缓慢滴加到5当量1mol/l的盐酸中，冰浴条件下搅拌2个小时后，加入1当量的3,5-二甲氧基苯胺并在氮气保护下继续反应2个小时得到偶氮苯分子。1) Preparation of azobenzene molecule: take 30mmol of 5-amino-1,3-benzenedisulfonic acid and equivalent sodium hydroxide, dissolve in deionized water, and then dropwise add 1.5 equivalent sodium nitrite solution to it , after uniform dispersion, the solution was slowly added dropwise to 5 equivalents of 1 mol/l hydrochloric acid. After stirring for 2 hours under ice bath conditions, 1 equivalent of 3,5-dimethoxyaniline was added and continued under nitrogen protection. After 2 hours of reaction, azobenzene molecules were obtained.
2)还原氧化石墨烯预处理：用质量百分数为20％的碳酸钠水溶液将分散氧化石墨烯的水溶液调节pH到8，在20mg/ml硼氢化钠水溶液中加入40ml的pH调好的氧化石墨烯水溶液，并在85℃下放置8小时；通过离心，过滤，蒸馏水水洗得到所需要的RGO；然后把通过超声重新分散在水中。2) Pretreatment of reduced graphene oxide: adjust the pH of the aqueous solution of dispersed graphene oxide to 8 with an aqueous solution of sodium carbonate with a mass percentage of 20%, and add 40ml of pH-adjusted graphene oxide to the 20mg/ml sodium borohydride aqueous solution Aqueous solution, and placed at 85°C for 8 hours; the desired RGO was obtained by centrifugation, filtration, and washed with distilled water; and then redispersed in water by ultrasound.
3)偶氮苯石墨烯复合材料的制备：取2mmol步骤1)得到的偶氮苯分子和等当量亚硝酸钠溶解在去离子水中，然后在冰浴条件下滴加到1mol/l盐酸溶液中，反应1个小时，在冰浴条件下将其滴加到20mg的步骤2)得到的还原氧化石墨烯的水溶液(水溶液为 60ml)中，冰浴中反应8小时，然后在室温下反应24个小时；减压抽滤，用去离子水和DMF反复洗涤多次，最后真空干燥得到目标产物偶氮苯石墨烯复合材料。3) Preparation of azobenzene-graphene composite material: take 2mmol of the azobenzene molecule obtained in step 1) and dissolve it in deionized water with equivalent sodium nitrite, then add dropwise to 1mol/l hydrochloric acid solution under ice-bath conditions , reacted for 1 hour, and added dropwise to the aqueous solution of reduced graphene oxide (60 ml) obtained in step 2) of 20 mg under ice bath conditions, reacted in ice bath for 8 hours, and then reacted at room temperature for 24 hour; suction filtration under reduced pressure, repeated washing with deionized water and DMF for several times, and finally vacuum drying to obtain the target product azobenzene-graphene composite material.
4)偶氮苯石墨烯体系变色加密保密材料的制备：取40mg步骤3)抽滤得到的偶氮苯石墨烯薄膜裁剪成规则的长方形，然后将65℃的热致变色颜料通过丝印印于聚丙烯不干胶表面。将聚丙烯薄膜粘贴在偶氮苯石墨烯复合材料的表面，根据信息内容分区域用紫外光对此材料照射6个小时进行充热，其他区域遮挡住不接受任何刺激。最后将此材料放置在热台上，加热到60℃，充过热的偶氮苯石墨烯复合材料会在加热刺激下进行放热，从而造成被紫外光照射过的区域与没有照射过的区域存在5℃的温差，从而使热致变色颜料改变颜色，显现出信息，完成加密保密的过程。4) Preparation of azobenzene graphene system discoloration encryption security material: take 40 mg of the azobenzene graphene film obtained in step 3) by suction filtration and cut it into a regular rectangle, and then the thermochromic pigment at 65 ° C is screen-printed on the polymer. Acrylic self-adhesive surface. The polypropylene film was pasted on the surface of the azobenzene-graphene composite material. According to the information content, the material was irradiated with ultraviolet light for 6 hours to heat the material, and other areas were blocked and did not receive any stimulation. Finally, the material is placed on a hot stage and heated to 60°C. The superheated azobenzene-graphene composite material will exotherm under heating stimulation, resulting in the existence of areas irradiated by ultraviolet light and areas that have not been irradiated. The temperature difference of 5 °C makes the thermochromic pigment change color, reveal information, and complete the process of encryption and confidentiality.
实施例3Example 3
1)偶氮苯分子的制备：取25mmol的5-氨基-1,3-苯二磺酸和等当量的氢氧化钠，溶于去离子水中，然后向其中滴加1.2当量的亚硝酸钠溶液，分散均匀后再将此溶液缓慢滴加到4当量1mol/l的盐酸中，冰浴条件下搅拌2小时后，加入1.2当量的3,5-二甲氧基苯胺并在氮气保护下继续反应3小时得到偶氮苯分子。1) Preparation of azobenzene molecule: take 25mmol of 5-amino-1,3-benzenedisulfonic acid and equivalent sodium hydroxide, dissolve in deionized water, and then dropwise add 1.2 equivalent sodium nitrite solution to it , and then the solution was slowly added dropwise to 4 equivalents of 1 mol/l hydrochloric acid. After stirring for 2 hours under ice bath conditions, 1.2 equivalents of 3,5-dimethoxyaniline were added and the reaction continued under nitrogen protection. Azobenzene molecules were obtained in 3 hours.
2)还原氧化石墨烯预处理：用质量百分数为25％的碳酸钠水溶液将分散氧化石墨烯的水溶液调节pH到9，在20mg/ml硼氢化钠水溶液中加入40ml的pH调好的氧化石墨烯水溶液，并在90℃下放置7小时；通过离心，过滤，蒸馏水水洗得到所需要的RGO；然后把通过超声重新分散在水中。2) Pretreatment of reduced graphene oxide: adjust the pH of the aqueous solution of dispersed graphene oxide to 9 with a sodium carbonate aqueous solution whose mass percentage is 25%, and add 40 ml of the pH-adjusted graphene oxide to the 20 mg/ml sodium borohydride aqueous solution Aqueous solution, and placed at 90 ° C for 7 hours; by centrifugation, filtration, washed with distilled water to obtain the desired RGO; and then re-dispersed in water by sonication.
3)偶氮苯石墨烯复合材料的制备：取3mmol步骤1)得到的偶氮苯分子和等当量亚硝酸钠溶解在去离子水中，然后在冰浴条件下滴加到1mol/l盐酸溶液中，反应2小时，在冰浴条件下将其滴加到30mg的步骤2)得到的还原氧化石墨烯水溶液(水体积为50ml) 中，冰浴中反应10小时，然后在室温下反应30小时；减压抽滤，用去离子水和DMF 反复洗涤多次，最后真空干燥得到目标产物偶氮苯石墨烯复合材料。3) preparation of azobenzene graphene composite material: get 3mmol step 1) azobenzene molecule that obtains and equivalent sodium nitrite are dissolved in deionized water, then dropwise in 1mol/l hydrochloric acid solution under ice bath condition , reacted for 2 hours, was added dropwise to the reduced graphene oxide aqueous solution (water volume is 50ml) obtained in step 2 of 30mg under ice bath conditions, reacted in ice bath for 10 hours, and then reacted at room temperature for 30 hours; Filter under reduced pressure, repeatedly wash with deionized water and DMF for several times, and finally vacuum dry to obtain the target product azobenzene-graphene composite material.
4)偶氮苯石墨烯体系变色加密保密材料的制备：取60mg步骤3)抽滤得到的偶氮苯石墨烯薄膜裁剪成规则的长方形，然后将65℃的热致变色颜料通过丝印印于聚丙烯不干胶表面。将聚丙烯薄膜粘贴在偶氮苯石墨烯复合材料的表面，根据信息内容分区域用紫外光对此材料照射6个小时进行充热，其他区域遮挡住不接受任何刺激。最后将此材料放置在热台上，加热到60℃，充过热的偶氮苯石墨烯复合材料会在加热刺激下进行放热，从而造成被紫外光照射过的区域与没有照射过的区域存在5℃的温差，从而使热致变色颜料改变颜色，显现出信息，完成加密保密的过程。4) Preparation of azobenzene graphene system discoloration encryption and security material: take 60 mg of the azobenzene graphene film obtained in step 3) by suction filtration and cut it into a regular rectangle, and then the thermochromic pigment at 65° C. is screen-printed on the polymer. Acrylic self-adhesive surface. The polypropylene film was pasted on the surface of the azobenzene-graphene composite material. According to the information content, the material was irradiated with ultraviolet light for 6 hours to heat the material, and other areas were blocked and did not receive any stimulation. Finally, the material is placed on a hot stage and heated to 60°C. The superheated azobenzene-graphene composite material will exotherm under heating stimulation, resulting in the existence of areas irradiated by ultraviolet light and areas that have not been irradiated. The temperature difference of 5 °C makes the thermochromic pigment change color, reveal information, and complete the process of encryption and confidentiality.
针对实施例制备的偶氮苯分子进行红外表征，如图1所示，1045cm-1和1201cm-1的吸收峰分别隶属于SO3-的对称伸缩振动峰和反对称伸缩振动峰。1272cm-1的吸收峰为 C-O的伸缩振动峰。1340cm-1的吸收峰为-N＝N-基团。1430～1602cm-1的吸收峰为苯环的特征吸收峰。甲氧基中C-H的吸收峰在2870cm-1和2940cm-1附近，3400～3500cm-1的吸收峰为-OH基团，覆盖了-NH2的吸收峰。由上述分析可知，目标偶氮苯分子被成功合成出来。对本发明实施例中偶氮苯—石墨烯复合材料进行表征，如附图2—3所示，RGO 表面存在明显的褶皱，表明偶氮苯分子已经接枝到RGO表面，而褶皱相互穿插堆叠有益于RGO间的相互作用和形成分子间的穿插结构；利用DSC(差热扫描量热)扫描出材料的放热峰，然后利用软件将放热峰进行积分得到释放出的能量，然后除以质量，计算出相应的能量密度，平均达到130—150Wh/kg。The azobenzene molecules prepared in the examples were characterized by infrared, as shown in FIG. 1 , the absorption peaks at 1045 cm -1 and 1201 cm -1 belong to the symmetric stretching vibration peak and the antisymmetric stretching vibration peak of SO 3 - respectively. The absorption peak at 1272 cm -1 is the stretching vibration peak of CO. The absorption peak at 1340 cm -1 is the -N=N- group. The absorption peak of 1430～1602cm -1 is the characteristic absorption peak of benzene ring. The absorption peaks of CH in the methoxy group are around 2870 cm -1 and 2940 cm -1 , and the absorption peaks at 3400-3500 cm -1 are -OH groups, covering the absorption peaks of -NH 2 . It can be seen from the above analysis that the target azobenzene molecule was successfully synthesized. The azobenzene-graphene composite material in the embodiment of the present invention is characterized. As shown in Figures 2-3, there are obvious folds on the surface of RGO, indicating that the azobenzene molecules have been grafted to the surface of RGO, and the interspersed and stacked folds are beneficial. The interaction between RGO and the formation of intermolecular interspersed structure; use DSC (differential scanning calorimetry) to scan the exothermic peak of the material, and then use the software to integrate the exothermic peak to obtain the released energy, and then divide by the mass , calculate the corresponding energy density, the average reaches 130-150Wh/kg.
如附图4所示，将热致变色颜料和偶氮苯—石墨烯复合材料设置在信息内容区域，并使用紫外光对信息内容区域中部分偶氮苯—石墨烯复合材料进行辐照充热，其他区域遮挡住不接受任何刺激，最后对信息内容区域进行加热，加热至热致变色颜料的变色温度之下，经过辐照充热的偶氮苯—石墨烯复合材料在加热刺激下进行放热，对与之对应的信息内容区域进行加热，以达到热致变色颜料的变色温度，从而造成在信息内容区域中被紫外光照射过的区域与没有照射过的区域存在温差，造成热致变色颜料改变颜色显现出相应信息，完成加密保密的过程。由发明内容可知，偶氮苯分子以及相关偶氮苯—石墨烯复合材料的制备有关中国专利，制备的偶氮苯分子以及相关偶氮苯—石墨烯复合材料表现出储能的性能，均可适用于如附图4所示的信息加密保密和信息显示过程。As shown in Figure 4, the thermochromic pigment and azobenzene-graphene composite material are arranged in the information content area, and part of the azobenzene-graphene composite material in the information content area is irradiated and heated by ultraviolet light , other areas are blocked and do not receive any stimulation, and finally the information content area is heated to below the discoloration temperature of the thermochromic pigment, and the azobenzene-graphene composite material heated by irradiation is released under heating stimulation. Heat, heat the corresponding information content area to reach the discoloration temperature of the thermochromic pigment, resulting in a temperature difference between the area irradiated by ultraviolet light and the area not irradiated in the information content area, resulting in thermochromic The pigment changes color to reveal the corresponding information, completing the process of encryption and confidentiality. It can be seen from the content of the invention that the preparation of azobenzene molecules and related azobenzene-graphene composite materials is related to Chinese patents, and the prepared azobenzene molecules and related azobenzene-graphene composite materials show the performance of energy storage. It is suitable for the information encryption and confidentiality and information display process as shown in FIG. 4 .
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。The present invention has been exemplarily described above. It should be noted that, without departing from the core of the present invention, any simple deformation, modification, or other equivalent replacements that can be performed by those skilled in the art without any creative effort fall into the scope of the present invention. the scope of protection of the invention.
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