CN112745825B - Preparation method of frozen reversible color-changing warning material for roads - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 90
- 230000002441 reversible effect Effects 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003094 microcapsule Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011162 core material Substances 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 20
- 229920000877 Melamine resin Polymers 0.000 claims description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229920005646 polycarboxylate Polymers 0.000 claims description 10
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical group CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical group OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 4
- 238000002845 discoloration Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 206010039203 Road traffic accident Diseases 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
- B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
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- G01K11/16—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials
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Abstract
A preparation method of a frozen reversible color-changing warning material for roads belongs to the field of road traffic safety. The reversible thermochromic material aims to solve the problems that the conventional secondary frozen road section after snow melting on a road in winter lacks obvious road area warning representation, and the conventional reversible thermochromic material can only change color freely at normal temperature and high temperature and can change color reversibly at low temperature. The preparation method comprises the following steps: 1. preparing a core material; 2. preparing a wall material; 3. the frozen reversible color-changing material microcapsule is prepared by adopting an in-situ polymerization method. The invention is used for preparing the frozen reversible color-changing warning material for the road.
Description
Technical Field
The invention belongs to the field of road traffic safety.
Background
After snow on the road is frozen in winter, the skid resistance of the road surface is rapidly reduced, the traffic safety is seriously influenced, and particularly the influence on a special road section which is easy to freeze for the second time after snow melting is serious. Because the formed dark ice is very thin, smooth and transparent, the dark ice is not easy to be found, great potential safety hazard is brought to driving, and traffic accidents are more easily caused by unobtrusive and missing road warning information, so that casualties and property loss are caused. As a safety early warning measure, the road traffic warning mark not only can psychologically mobilize the attention of a driver and passengers, but also can physiologically influence the skill response of the driver, so that the driver and the passengers can consciously or instinctively notice unsafe factors existing around and correctly and quickly react, and finally traffic accidents are reduced or avoided. Therefore, aiming at the problem that the secondary icing road section lacks obvious road area warning representation after snow melting on the road in winter, a color-changing material and technology with a frozen state sensing function and warning are necessary to be invented so as to improve the travel safety in winter, warn a driver to drive safely and provide technical reserve for the road traffic safety in winter.
At present, inorganic thermochromic materials, organic thermochromic materials and liquid crystal thermochromic materials are mainly adopted as thermochromic materials; compared with inorganic and liquid crystal reversible thermochromic materials, the organic reversible thermochromic material has the characteristics of low color change temperature, high color change sensitivity, capability of realizing free color selection and the like, and becomes the hottest reversible thermochromic material with great potential at present. The reversible organic thermochromic material mainly comprises a leuco agent (an electron donor), a color developing agent (an electron acceptor) and an organic solvent. However, the current reversible thermochromic materials can change color freely only under normal temperature and high temperature conditions, and lack materials capable of changing color reversibly under low temperature conditions, so the invention of reversible thermochromic materials under low temperature freezing conditions needs to be developed.
Disclosure of Invention
The invention provides a preparation method of a frozen reversible color-changing warning material for roads, aiming at solving the problems that the existing secondary frozen road section after snow melting of the road in winter lacks obvious road area warning representation, and the existing reversible thermochromic material can only change color freely under normal temperature and high temperature conditions and lacks material capable of changing color reversibly under low temperature conditions.
A method for preparing a frozen reversible color-changing warning material for roads comprises the following steps:
1. preparing a core material:
(1) weighing 10-90 parts of organic solvent, 1-10 parts of color developing agent and 1-5 parts of color hiding agent according to parts by weight;
the organic solvent is decanol; the color developing agent is bisphenol A; the leuco agent is crystal violet lactone;
(2) placing 10-90 parts of weighed organic solvent in a constant-temperature water bath at the temperature of 70-90 ℃ for heating, adding 1-10 parts of color developing agent and 1-5 parts of color hiding agent under the constant-temperature condition at the temperature of 70-90 ℃, stirring for 0.5-1 h at the stirring speed of 500-1500 r/min, and naturally cooling to obtain a frozen reversible thermochromic compound solution;
2. preparing a wall material:
(1) mixing melamine, urea, 30-40% by mass of formaldehyde aqueous solution and distilled water to obtain mixed solution A;
the molar ratio of the melamine to the urea is 1 (1-3); the molar ratio of the melamine to the formaldehyde in the 30-40% formaldehyde aqueous solution is 1 (6-8); the mass ratio of the melamine in the step two (1) to the distilled water in the step two (1) is 1 (3-5);
(2) adding anhydrous sodium carbonate powder into the mixed solution A until the pH value is 8-9 to obtain mixed solution B;
(3) stirring the mixed solution B until the mixed solution B is completely dissolved under the conditions that the stirring speed is 500 r/min-1500 r/min and the constant temperature is 60-80 ℃, putting the mixed solution B into ice water to cool to 35-45 ℃, and then adding distilled water to obtain a wall material solution;
the mass ratio of the melamine in the step two (1) to the distilled water in the step two (3) is 1 (20-30);
3. preparing the frozen reversible color-changing material microcapsule by adopting an in-situ polymerization method:
(1) weighing 1 to 4 parts of frozen reversible thermochromic compound solution, 3 to 10 parts of wall material solution, 0.05 to 0.2 part of polycarboxylate dispersant and 0.05 to 0.15 part of potassium hydrogen phthalate catalyst in parts by mass;
(2) adding 0.05 to 0.2 part of polycarboxylate dispersant into 1 to 4 parts of frozen reversible thermochromic compound solution, stirring for 15 to 30 minutes under the conditions that the stirring speed is 1000 to 2000r/min and the constant temperature is 60 to 80 ℃ to obtain mixed solution D, adding 3 to 10 parts of wall material solution into the mixed solution D, and stirring for 20 to 40 minutes under the conditions that the stirring speed is 1000 to 2000r/min and the constant temperature is 60 to 80 ℃ to obtain mixed solution E;
(3) regulating the pH value of the mixed solution E to be 3-4 by using glacial acetic acid with the concentration of more than 99.5%, and stirring for 20-40 min under the conditions that the stirring speed is 1000-2000 r/min and the constant temperature is 60-80 ℃ to obtain a mixed solution F;
(4) adding 0.05 to 0.15 part of potassium hydrogen phthalate catalyst into the mixed solution F, stirring for 1 to 2 hours at the stirring speed of 1000 to 2000r/min and at the constant temperature of 60 to 80 ℃, and standing for 20 to 40 minutes at the constant temperature of 60 to 80 ℃ to obtain a color-changing microcapsule suspension;
(5) and repeatedly cleaning the color-changing microcapsule suspension with distilled water, filtering out insoluble substances, and drying the insoluble substances to obtain the frozen reversible color-changing microcapsule material.
The beneficial effects of the invention are:
according to the intelligent sensing and warning requirements of the road surface in winter, a reversible color-changing compound solution is prepared under a freezing condition, and the compound solution is obviously changed into blue when the temperature is lower than 0 ℃; above 0 ℃ it turns colorless. The compound solution is prepared into the frozen reversible color-changing microcapsule powder by adopting an in-situ polymerization method, so that the frozen reversible color-changing material can still keep the original color-changing performance in the processes of temperature rise and temperature reduction, meanwhile, the wall material plays a role in protecting the core material, the durability of the reversible color-changing material is improved, and the frozen reversible color-changing warning material is better and more widely combined with road materials. The material can automatically sense the temperature of the road surface, change the color of the road in extremely severe weather, warn a driver, improve the safety of travel in winter, reduce the occurrence of traffic accidents to the maximum extent and provide guarantee for the traffic safety of the road in frozen weather.
The invention relates to a preparation method of a frozen reversible color-changing warning material for roads.
Drawings
FIG. 1 is a graph of the total color difference and the temperature change of the frozen reversible color-changing microcapsule material prepared in the first embodiment, wherein 1 is the color restoration process of the total color difference of the frozen reversible color-changing microcapsule material with the decrease of the temperature, and 2 is the color reduction process of the total color difference of the frozen reversible color-changing microcapsule material with the increase of the temperature;
FIG. 2 is a diagram of a pre-frozen material of the frozen reversible color-changing microcapsule prepared in the first example before freezing at a temperature of 5 ℃;
FIG. 3 is a diagram showing a frozen reversible color-changing microcapsule material prepared in the first example after freezing at a temperature of-8 ℃.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of a frozen reversible color-changing warning material for roads, which is completed by the following steps:
1. preparing a core material:
(1) weighing 10-90 parts of organic solvent, 1-10 parts of color developing agent and 1-5 parts of latent color agent according to the parts by weight;
the organic solvent is decanol; the color developing agent is bisphenol A; the leuco agent is crystal violet lactone;
(2) heating 10-90 parts of weighed organic solvent in a constant-temperature water bath at the temperature of 70-90 ℃, adding 1-10 parts of color developing agent and 1-5 parts of color hiding agent under the constant temperature condition of 70-90 ℃, stirring at the stirring speed of 500-1500 r/min for 0.5-1 h, and naturally cooling to obtain a frozen reversible thermochromic compound solution;
2. preparing a wall material:
(1) mixing melamine, urea, 30-40% by mass of formaldehyde aqueous solution and distilled water to obtain mixed solution A;
the molar ratio of the melamine to the urea is 1 (1-3); the molar ratio of the melamine to the formaldehyde in the 30-40% formaldehyde aqueous solution is 1 (6-8); the mass ratio of the melamine in the step two (1) to the distilled water in the step two (1) is 1 (3-5);
(2) adding anhydrous sodium carbonate powder into the mixed solution A until the pH value is 8-9 to obtain mixed solution B;
(3) stirring the mixed solution B until the mixed solution B is completely dissolved under the conditions that the stirring speed is 500-1500 r/min and the constant temperature is 60-80 ℃, putting the mixed solution B into ice water to cool to 35-45 ℃, and then adding distilled water to obtain a wall material solution;
the mass ratio of the melamine in the step two (1) to the distilled water in the step two (3) is 1 (20-30);
3. preparing the frozen reversible color-changing material microcapsule by adopting an in-situ polymerization method:
(1) weighing 1 to 4 parts of frozen reversible thermochromic compound solution, 3 to 10 parts of wall material solution, 0.05 to 0.2 part of polycarboxylate dispersant and 0.05 to 0.15 part of potassium hydrogen phthalate catalyst in parts by mass;
(2) adding 0.05 to 0.2 part of polycarboxylate dispersant into 1 to 4 parts of frozen reversible thermochromic compound solution, stirring for 15 to 30 minutes under the conditions that the stirring speed is 1000 to 2000r/min and the constant temperature is 60 to 80 ℃ to obtain mixed solution D, adding 3 to 10 parts of wall material solution into the mixed solution D, and stirring for 20 to 40 minutes under the conditions that the stirring speed is 1000 to 2000r/min and the constant temperature is 60 to 80 ℃ to obtain mixed solution E;
(3) regulating the pH value of the mixed solution E to be 3-4 by using glacial acetic acid with the concentration of more than 99.5%, and stirring for 20-40 min under the conditions that the stirring speed is 1000-2000 r/min and the constant temperature is 60-80 ℃ to obtain a mixed solution F;
(4) adding 0.05 to 0.15 part of potassium hydrogen phthalate catalyst into the mixed solution F, stirring for 1 to 2 hours at the stirring speed of 1000 to 2000r/min and the constant temperature of 60 to 80 ℃, and standing for 20 to 40 minutes at the constant temperature of 60 to 80 ℃ to obtain a color-changing microcapsule suspension;
(5) and repeatedly cleaning the color-changing microcapsule suspension with distilled water, filtering out insoluble substances, and drying the insoluble substances to obtain the frozen reversible color-changing microcapsule material.
The beneficial effects of this embodiment are:
according to the intelligent sensing and warning requirements of the road surface in winter, a reversible color-changing compound solution is prepared under a freezing condition, and the compound solution is obviously changed into blue when the temperature is lower than 0 ℃; above 0 ℃ it turns colorless. The compound solution is prepared into the frozen reversible color-changing microcapsule powder by adopting an in-situ polymerization method, so that the frozen reversible color-changing material can still keep the original color-changing performance in the processes of temperature rise and temperature reduction, meanwhile, the wall material plays a role in protecting the core material, the durability of the reversible color-changing material is improved, and the frozen reversible color-changing warning material is better and more widely combined with road materials. The material can automatically sense the temperature of the road surface, change the color of the road in extremely severe weather, warn a driver, improve the safety of travel in winter, reduce the occurrence of traffic accidents to the maximum extent and provide guarantee for the traffic safety of the road in frozen weather.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: and (2) heating 10 to 90 parts of the weighed organic solvent in a constant-temperature water bath at the temperature of 80 to 90 ℃, adding 1 to 10 parts of the color developing agent and 1 to 5 parts of the leuco agent under the constant temperature condition of 80 to 90 ℃, stirring for 0.5 to 1 hour at the stirring speed of 1000 to 1500r/min, and naturally cooling to obtain the frozen reversible thermochromic compound solution. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: and step two (2), adding anhydrous sodium carbonate powder into the mixed solution A until the pH value is 8.5-9 to obtain a mixed solution B. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: and in the second step (3), under the conditions that the stirring speed is 1000 r/min-1500 r/min and the constant temperature is 70-80 ℃, stirring the mixed solution B until the mixed solution B is completely dissolved, putting the mixed solution B into ice water to cool to 40-45 ℃, and then adding distilled water to obtain a wall material solution. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and step three (2), adding 0.05 to 0.2 part of polycarboxylate dispersant into 1 to 4 parts of reversible thermochromic compound solution, and stirring for 15 to 30 minutes under the conditions that the stirring speed is 1500 to 2000r/min and the constant temperature is 70 to 80 ℃ to obtain mixed liquid D. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is: and step three (2), adding 3 to 10 parts of wall material solution into the mixed solution D, and stirring for 30 to 40 minutes under the conditions that the stirring speed is 1500 to 2000r/min and the constant temperature is 70 to 80 ℃ to obtain a mixed solution E. The rest is the same as the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is: and in the third step (3), stirring for 30-40 min at the stirring speed of 1500-2000 r/min and the constant temperature of 70-80 ℃ to obtain a mixed solution F. The others are the same as in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: and step three (3) adjusting the pH value of the mixed solution E to 3.5-4 by using glacial acetic acid with the concentration of more than 99.5%. The others are the same as in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and step three (4), adding 0.05 to 0.15 part of potassium hydrogen phthalate catalyst into the mixed solution F, stirring for 1.5 to 2 hours at the stirring speed of 1500 to 2000r/min and at the constant temperature of 70 to 80 ℃, and standing for 30 to 40 minutes at the constant temperature of 70 to 80 ℃ to obtain the color-changing microcapsule suspension. The others are the same as in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and the drying in the step three (5) is drying in a vacuum drying box at the temperature of 60-80 ℃. The others are the same as in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a method for preparing a frozen reversible color-changing warning material for roads comprises the following steps:
1. preparing a core material:
(1) weighing 40g of organic solvent, 4g of color developing agent and 1g of latent color agent;
the organic solvent is decanol; the color developing agent is bisphenol A; the leuco agent is crystal violet lactone;
(2) heating 40g of weighed organic solvent in a constant-temperature water bath at the temperature of 90 ℃, adding 4g of color developing agent and 1g of color hiding agent under the constant-temperature condition of 90 ℃, stirring for 1h at the stirring speed of 1000r/min, and naturally cooling to obtain a frozen reversible thermochromic compound solution;
2. preparing a wall material:
(1) mixing 6.212g of melamine, 5.916g of urea, 23.984g of 40 mass percent aqueous formaldehyde solution and 23.892g of distilled water to obtain a mixed solution A;
(2) adding anhydrous sodium carbonate powder into the mixed solution A until the pH value is 8.5 to obtain mixed solution B;
(3) stirring the mixed solution B until the mixed solution B is completely dissolved under the conditions that the stirring speed is 1000r/min and the constant temperature is 70 ℃, putting the mixed solution B into ice water, cooling the mixed solution to 40 ℃, and then adding 150g of distilled water to obtain a wall material solution;
3. preparing the frozen reversible color-changing material microcapsule by adopting an in-situ polymerization method:
(1) weighing 30g of the frozen reversible thermochromic compound solution, 190g of the wall material solution, 3.52g of the polycarboxylate dispersant and 2.2g of the potassium hydrogen phthalate catalyst in parts by mass;
(2) adding 3.52g of polycarboxylate dispersant into 30g of the frozen reversible thermochromic compound solution, stirring for 15min under the conditions of a stirring speed of 1500r/min and a constant temperature of 70 ℃ to obtain a mixed solution D, adding 190g of wall material solution into the mixed solution D, and stirring for 30min under the conditions of a stirring speed of 1500r/min and a constant temperature of 70 ℃ to obtain a mixed solution E;
(3) regulating the pH value of the mixed solution E to be 3.5 by using glacial acetic acid with the concentration of more than 99.5%, and stirring for 30min under the conditions that the stirring speed is 1500r/min and the constant temperature is 70 ℃ to obtain a mixed solution F;
(4) adding 2.2g of potassium hydrogen phthalate catalyst into the mixed solution F, stirring for 1.5h at the stirring speed of 1500r/min and at the constant temperature of 70 ℃, and standing for 30min at the constant temperature of 70 ℃ to obtain a color-changing microcapsule suspension;
(5) repeatedly cleaning the color-changing microcapsule suspension with distilled water, filtering out insoluble substances, and drying the insoluble substances to obtain the frozen reversible color-changing microcapsule material;
and the drying in the step three (5) is drying in a vacuum drying oven at the temperature of 70 ℃.
The color change temperature point of the frozen reversible thermochromic compound solution prepared in the first step of the embodiment is 0 ℃, and the temperature is higher than 0 ℃ and shows colorless; the temperature was below 0 ℃ and blue color was exhibited.
The frozen reversible color-changing microcapsule material prepared in the embodiment is subjected to color-changing and color difference and color-changing temperature tests, and is placed in a low-temperature environment box, the initial temperature in the heating process is set to-10 ℃, after constant temperature treatment is carried out for 10min, a colorimetry parameter of the surface of a test piece is tested by using a color difference meter, and the test is repeated for 3 times. Then, after the temperature is increased by 2 ℃ every time, the colorimetry parameters of the surface of the test piece are tested after constant temperature treatment for 10min till 10 ℃. The initial temperature of the cooling process is set to be 10 ℃, after constant temperature treatment is carried out for 10min, the colorimetry parameters of the surface of the test piece are tested by using a color colorimeter, and the test is repeated for 3 times. Then, after the temperature is reduced by 2 ℃ every time, the surface of the test piece is subjected to constant temperature treatment for 10min until the colorimetric parameters reach minus 10 ℃. Calculating the total color difference of the surface of the test piece, wherein the total color difference calculation formula adopts a color system of CIELAB (1976),
wherein,
the total color difference is calculated; Δ L is the lightness index difference; delta a is the red and green axis chromaticity index difference; Δ b is the difference in the yellow-blue axial chromaticity indices.
FIG. 1 is a graph of total color difference versus temperature change of a frozen reversible color-changing microcapsule material prepared in accordance with example one, wherein 1 is a color restoration process of the frozen reversible color-changing microcapsule material with total color difference decreasing with temperature, and 2 is a color elimination process of the frozen reversible color-changing microcapsule material with total color difference increasing with temperature; as can be seen from the figure, the color of the sample surface was slightly changed at the initial stage of the temperature rise. With the increase of the test temperature, the total color difference value delta Ea of the color-changing material sample gradually increases, and the color of the surface of the sample is obvious from feeling to completely disappear. In the cooling process, the color change of the surface of the sample is just opposite to the change of the surface of the sample. When the temperature is reduced to a certain degree, the color of the surface of the sample is restored to the color of the initial temperature rise. As can be seen from the figure, the decoloring temperature range of the color-changing material is-4 to 2 ℃ and the decoloring temperature range is 0 to-6 ℃.
FIG. 2 is a diagram of a pre-frozen material of the frozen reversible color-changing microcapsule prepared in the first example before freezing at a temperature of 5 ℃; FIG. 3 is a diagram of a frozen reversible color-changing microcapsule material prepared in the first example after freezing at a temperature of-8 ℃; as can be seen, the temperature is higher than 0 ℃ and a white powder is shown; the temperature was below 0 ℃ showing a blue powder.
Claims (10)
1. A preparation method of a frozen reversible color-changing warning material for roads is characterized by comprising the following steps:
1. preparing a core material:
(1) weighing 40 parts of organic solvent, 4 parts of color developing agent and 1 part of leuco agent according to the parts by weight;
the organic solvent is decanol; the color developing agent is bisphenol A; the leuco agent is crystal violet lactone;
(2) placing 40 parts of weighed organic solvent in a constant-temperature water bath at the temperature of 70-90 ℃ for heating, adding 4 parts of color developing agent and 1 part of leuco agent under the constant-temperature condition of 70-90 ℃, stirring for 0.5-1 h at the stirring speed of 500-1500 r/min, and naturally cooling to obtain a frozen reversible thermochromic compound solution;
2. preparing a wall material:
(1) mixing melamine, urea, 30-40% by mass of formaldehyde aqueous solution and distilled water to obtain mixed solution A;
the molar ratio of the melamine to the urea is 1 (1-3); the molar ratio of the melamine to the formaldehyde in the 30-40% formaldehyde aqueous solution is 1 (6-8); the mass ratio of the melamine in the step two (1) to the distilled water in the step two (1) is 1 (3-5);
(2) adding anhydrous sodium carbonate powder into the mixed solution A until the pH value is 8-9 to obtain mixed solution B;
(3) stirring the mixed solution B until the mixed solution B is completely dissolved under the conditions that the stirring speed is 500-1500 r/min and the constant temperature is 60-80 ℃, putting the mixed solution B into ice water to cool to 35-45 ℃, and then adding distilled water to obtain a wall material solution;
the mass ratio of the melamine in the step two (1) to the distilled water in the step two (3) is 1 (20-30);
3. preparing the frozen reversible color-changing material microcapsule by adopting an in-situ polymerization method:
(1) weighing 1 to 4 parts of frozen reversible thermochromic compound solution, 3 to 10 parts of wall material solution, 0.05 to 0.2 part of polycarboxylate dispersant and 0.05 to 0.15 part of potassium hydrogen phthalate catalyst in parts by mass;
(2) adding 0.05 to 0.2 part of polycarboxylate dispersant into 1 to 4 parts of the frozen reversible thermochromic compound solution, stirring for 15 to 30 minutes under the conditions that the stirring speed is 1000 to 2000r/min and the constant temperature is 60 to 80 ℃ to obtain a mixed solution D, adding 3 to 10 parts of wall material solution into the mixed solution D, and stirring for 20 to 40 minutes under the conditions that the stirring speed is 1000 to 2000r/min and the constant temperature is 60 to 80 ℃ to obtain a mixed solution E;
(3) regulating the pH value of the mixed solution E to be 3-4 by using glacial acetic acid with the concentration of more than 99.5%, and stirring for 20-40 min under the conditions that the stirring speed is 1000-2000 r/min and the constant temperature is 60-80 ℃ to obtain a mixed solution F;
(4) adding 0.05 to 0.15 part of potassium hydrogen phthalate catalyst into the mixed solution F, stirring for 1 to 2 hours at the stirring speed of 1000 to 2000r/min and at the constant temperature of 60 to 80 ℃, and standing for 20 to 40 minutes at the constant temperature of 60 to 80 ℃ to obtain a color-changing microcapsule suspension;
(5) and repeatedly cleaning the color-changing microcapsule suspension with distilled water, filtering out insoluble substances, and drying the insoluble substances to obtain the frozen reversible color-changing microcapsule material.
2. The preparation method of the frozen reversible color-changing warning material for the road according to claim 1, characterized in that 40 parts of the weighed organic solvent is placed in a constant-temperature water bath at a temperature of 80-90 ℃ for heating, 4 parts of the color developing agent and 1 part of the leuco agent are added under the constant-temperature condition at the temperature of 80-90 ℃, the mixture is stirred at a stirring speed of 1000-1500 r/min for 0.5-1 h, and the mixture is naturally cooled to obtain the frozen reversible thermochromic compound solution.
3. The method for preparing a reversible discoloration caution material for roads by freezing as claimed in claim 1, wherein in the second step (2), anhydrous sodium carbonate powder is added to the mixed solution A until the pH is 8.5-9, to obtain a mixed solution B.
4. The preparation method of the frozen reversible color-changing warning material for the road according to claim 1, wherein in the second step (3), the mixed solution B is stirred to be completely dissolved under the conditions that the stirring speed is 1000 r/min-1500 r/min and the constant temperature is 70-80 ℃, the mixed solution B is placed into ice water to be cooled to 40-45 ℃, and then distilled water is added to obtain a wall material solution.
5. The preparation method of the frozen reversible color-changing warning material for the road according to claim 1, characterized in that 0.05-0.2 part of polycarboxylate dispersant is added into 1-4 parts of reversible thermochromic compound solution in the third step (2), and the mixture is stirred for 15-30 min at the stirring speed of 1500-2000 r/min and the constant temperature of 70-80 ℃ to obtain a mixed solution D.
6. The preparation method of the frozen reversible color-changing warning material for the road according to claim 1, wherein 3 to 10 parts of wall material solution are added into the mixed solution D in the step three (2), and the mixed solution E is obtained by stirring for 30 to 40 minutes at a stirring speed of 1500 to 2000r/min and at a constant temperature of 70 to 80 ℃.
7. The method for preparing the frozen reversible color-changing warning material for the road according to claim 1, wherein in the third step (3), the mixture is stirred for 30-40 min at a stirring speed of 1500-2000 r/min and at a constant temperature of 70-80 ℃ to obtain a mixed solution F.
8. The method for preparing a reversible color-changing frozen warning material for roads as claimed in claim 1, wherein in step three (3), glacial acetic acid with a concentration of more than 99.5% is used to adjust the pH of the mixed solution E to 3.5-4.
9. The preparation method of the frozen reversible color-changing warning material for the road according to claim 1, characterized in that 0.05 to 0.15 part of potassium hydrogen phthalate catalyst is added into the mixed solution F in the third step (4), the mixed solution is stirred for 1.5 to 2 hours at a stirring speed of 1500 to 2000r/min and at a constant temperature of 70 to 80 ℃, and the mixed solution is allowed to stand for 30 to 40 minutes at a constant temperature of 70 to 80 ℃ to obtain a color-changing microcapsule suspension.
10. The method for preparing the frozen reversible color-changing warning material for the road according to claim 1, wherein the drying in the step three (5) is drying in a vacuum drying oven at a temperature of 60-80 ℃.
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| CN114989714B (en) * | 2022-07-04 | 2023-04-21 | 哈尔滨工业大学 | Preparation method and construction method of pavement low-temperature dynamic early warning coating material |
| WO2024054128A1 (en) * | 2022-09-06 | 2024-03-14 | Общество С Ограниченной Ответственностью "Термоэлектрика" | Device for visually indicating excess temperature and method for manufacturing same |
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