CN115703893A - Preparation method of thermochromic polyester film - Google Patents
Preparation method of thermochromic polyester film Download PDFInfo
- Publication number
- CN115703893A CN115703893A CN202110933937.4A CN202110933937A CN115703893A CN 115703893 A CN115703893 A CN 115703893A CN 202110933937 A CN202110933937 A CN 202110933937A CN 115703893 A CN115703893 A CN 115703893A
- Authority
- CN
- China
- Prior art keywords
- thermochromic
- polyester film
- reaction
- polyester
- spherical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003094 microcapsule Substances 0.000 claims abstract description 41
- 229920000728 polyester Polymers 0.000 claims abstract description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000009998 heat setting Methods 0.000 claims abstract description 7
- 238000005096 rolling process Methods 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000010345 tape casting Methods 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 38
- 238000005886 esterification reaction Methods 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 tin oxide rare earth metal compound Chemical class 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- XJRPTMORGOIMMI-UHFFFAOYSA-N ethyl 2-amino-4-(trifluoromethyl)-1,3-thiazole-5-carboxylate Chemical compound CCOC(=O)C=1SC(N)=NC=1C(F)(F)F XJRPTMORGOIMMI-UHFFFAOYSA-N 0.000 claims description 5
- KQSBZNJFKWOQQK-UHFFFAOYSA-N hystazarin Natural products O=C1C2=CC=CC=C2C(=O)C2=C1C=C(O)C(O)=C2 KQSBZNJFKWOQQK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 5
- LXMSZDCAJNLERA-ZHYRCANASA-N spironolactone Chemical compound C([C@@H]1[C@]2(C)CC[C@@H]3[C@@]4(C)CCC(=O)C=C4C[C@H]([C@@H]13)SC(=O)C)C[C@@]21CCC(=O)O1 LXMSZDCAJNLERA-ZHYRCANASA-N 0.000 claims description 5
- 229960002256 spironolactone Drugs 0.000 claims description 5
- 239000011162 core material Substances 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000009966 trimming Methods 0.000 claims description 2
- 238000012695 Interfacial polymerization Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 39
- 230000008859 change Effects 0.000 abstract description 20
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000005034 decoration Methods 0.000 abstract 1
- 239000000155 melt Substances 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 238000005507 spraying Methods 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a preparation method of a thermochromic polyester film, which comprises the steps of adding purified terephthalic acid, ethylene glycol, a catalyst, a thermochromic spherical microcapsule and a heat stabilizer into a reaction kettle, and preparing a thermochromic polyester chip through polymerization reaction, melt extrusion, cooling, grain cutting and drying; then mixing the thermochromic polyester film with bright polyester chips, drying, and then performing the processes of melt extrusion, tape casting, longitudinal stretching, transverse stretching, heat setting, traction edge cutting, rolling and the like to obtain the thermochromic polyester film. The film of the invention can change color at different temperatures and can change reversibly with the change of environmental temperature, has the advantages of high color change reaction rate, good openness, high light transmittance, good thermal stability, strong aging resistance, high mechanical strength and the like, is suitable for military protective covers, safety warning boards, color-changing toys, window films for buildings and automobiles, decorative articles and the like, and has the characteristics of military camouflage, safety warning, entertainment interest, beautification and decoration and the like.
Description
Technical Field
The invention belongs to the technical field of polymer chemical industry, and particularly relates to a preparation method of a thermochromic polyester film.
Background
Along with the development of science and technology and the improvement of the living standard of people, the demand of people on polyethylene terephthalate (PET) films is gradually changed into diversity and functionality from practicability, and thermochromic products can meet the demand of people on the functionality and diversity of polyester films.
The thermochromic polyester film is a functional material which can generate reversible color change along with the change of environmental temperature. The military protective cover, the safety warning board, the color-changing toy, the window film for buildings and automobiles, the decorative article and the like prepared by the material can present different colors or patterns under different temperature conditions, and have the characteristics of safety warning, military camouflage, environment beautification, entertainment interest and the like. In recent years, the research work of the domestic thermochromic film has made some progress, and the thermochromic film has attracted the wide attention of related enterprises.
The thermochromic polyester film developed at home at present is mainly characterized in that a thermochromic substance is coated on the surface of a base film, and the thermochromic substance is utilized to generate reversible color change at different temperatures, so that thermochromic regulation and control are realized; however, the thermochromic polyester film prepared by adopting the coating technology has the problems of slow discoloration reaction rate, short discoloration duration, poor thermal stability, easy shedding of thermochromic spherical microcapsules coated on the film surface and the like in a severe environment.
The Chinese patent database discloses a reversible thermochromic film and a preparation method thereof, and the application number of the reversible thermochromic film is as follows: CN201710025395.4; application date: 13/01/2017; publication No.: CN106750466B, published date: 11 month 08 in 2019; the reversible thermochromic polyester film is prepared by directly spraying a solution containing thermochromic vanadium oxide (VO 2) nano powder on the surface of a PET film by adopting a spraying technology and then drying. Although the preparation technology of the reversible thermochromic film is simple, the defects are as follows: the thermochromism composite film prepared by adopting the spraying technology has Vanadium Oxide (VO) on the surface of the film in severe environment 2 ) The thermochromic powder is easy to fall off and has the defects of slow discoloration reaction rate, poor discoloration stability and short service life; in addition, the thermochromic vanadium oxide (VO 2) nanopowder can undergo color change at a high temperature of 45 ℃, thus being disadvantageous to the wide application of the product.
Disclosure of Invention
The invention aims to provide a thermochromic polyester film and a preparation method thereof, aiming at overcoming the technical problems that the thermochromic polyester film prepared by adopting the existing spraying technology is slow in color change reaction rate, poor in color change stability, easy in falling of thermochromic powder and the like. The film prepared by the invention has the characteristics of good opening performance, thermal stability, aging resistance, light transmittance and the like.
The invention aims to realize the following technical scheme that the preparation method of the thermochromic polyester film comprises the following steps:
(1) Adding purified terephthalic acid, ethylene glycol, a thermochromic spherical microcapsule suspension, a catalyst and a heat stabilizer into a polymerization reaction kettle, and preparing a thermochromic polyester chip by esterification polycondensation, melt extrusion, cooling, grain cutting and drying; wherein the weight percentage of the thermochromic spherical microcapsules in the thermochromic polyester chips is 5-15%.
(2) Uniformly mixing and drying the thermochromic polyester chips prepared in the step (1) and the bright polyester chips, and then preparing a thermochromic polyester film through the working procedures of melt extrusion, tape casting, longitudinal stretching, transverse stretching, heat setting, traction trimming, rolling and the like; the mixing ratio of the thermochromic polyester chip to the luminous polyester chip is 1-1.
Preferably, the catalyst in the step (1) is any one of tetrabutyl titanate or antimony trioxide.
Preferably, in the step (1), the heat stabilizer is a tin oxide rare earth metal compound.
Preferably, the thickness of the thermochromic polyester film in step (1) is 50-150 μm.
Further, the thermochromic spherical microcapsule in the step (1) is prepared by adopting an interface polymerization method by taking a thermochromic compound as a core material and taking a high polymer of 2, 6-naphthalene dicarboxylic acid and ethylene glycol as a wall material; the thermochromic compound is prepared by compounding crystal violet lactone, bromocresol purple, spirolactone, 1, 2-dihydroxy anthraquinone and tetra-n-propyl zirconate, and the weight ratio of the components in the thermochromic compound is that the crystal violet lactone: bromocresol purple: spironolactone: 1, 2-dihydroxyanthraquinone: tetra-n-propyl zirconate =1: (0.6-0.7), (0.4-0.5), (0.2-0.3), (0.1-0.15), (0.08-0.15); the thermochromic spherical microcapsule not only has the characteristics of good mechanical strength, thin capsule wall, small gap and the like, but also has good thermochromic characteristic, can change color at different temperatures, can reversibly change along with the change of the ambient temperature, and realizes thermochromic regulation and control.
Further, the preparation method of the thermochromic spherical microcapsule suspension in the step (1) comprises the following steps: pre-dispersing 10-20% of thermochromic spherical microcapsules and 78-89% of ethylene glycol, adding 1-2% of monoalkoxy titanate/triethyl phosphate compound coupling agent, and magnetically stirring at room temperature for 60-90 min to obtain uniformly dispersed thermochromic spherical microcapsule suspension.
Preferably, in the thermochromic spherical microcapsule suspension, the mass fraction of the microcapsules is 10-30%, and the particle size is 1.0-5 μm.
Further, the preparation process of the thermochromic polyester chip in the step (1) is as follows: respectively adding 5000-5500 g of purified terephthalic acid, 2500-3500 g of ethylene glycol, 350-360 g of thermochromic spherical microcapsule suspension, 1.65-1.68 g of tetrabutyl titanate or antimony trioxide and 0.10-0.16 g of tin oxide rare earth metal compound into a 20L general polymerization reaction kettle, and then heating and pressurizing to perform esterification polycondensation reaction. The esterification polycondensation reaction is divided into two stages, namely esterification reaction and polycondensation reaction, wherein the esterification reaction is an endothermic reaction, and the polycondensation reaction is an exothermic reaction. In the initial stage of the esterification reaction, the reaction temperature is 220-225 ℃. Along with the increase of the reaction degree, the temperature gradually rises, the esterification reaction is carried out for 80-90 min under the kettle pressure of 0.30-0.38 Mpa, the pressure is released to normal pressure when the water yield reaches 1000ml, and the temperature reaches 256-260 ℃ after the esterification reaction is finished. At the initial stage of polycondensation reaction, the reaction temperature is 256-260 ℃, after 45-48 min of pre-polycondensation, the reaction temperature is gradually increased to 270-280 ℃, and the final polycondensation stage is carried out, at the initial stage of polycondensation reaction, the reaction temperature is 280-285 ℃, the polycondensation reaction is carried out for 80-95 min under the condition of kettle pressure of 150-200 pa, after the reaction is finished, the polymer with the intrinsic viscosity (eta) of 0.82-0.85 is obtained, and finally, the thermochromic polyester slice with the thermochromic spherical microcapsule mass fraction of 5-15% is obtained by extrusion, grain cutting and drying through a melt pump.
Further, the preparation process of the thermochromic polyester film in the step (2) is that 1000-1500 g of thermochromic polyester slices and 1500-3000 g of bright polyester slices are blended and dried for 5-6 hours at 65-75 ℃; then, the melt extrusion is carried out through a single screw extruder, and the thermochromic polyester film with the stretching ratio of 4-5 times and the film thickness of 50-150 mu m is prepared through the procedures of casting sheets by casting, longitudinal stretching, transverse stretching, heat setting, traction, rolling, slitting and the like.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method has reasonable preparation process and strong operability, and is easy for industrial production. The wall material of the thermochromic spherical microcapsule prepared by the invention is a high polymer of 2, 6-naphthalene dicarboxylic acid and ethylene glycol, has good compatibility with a melt, and can be better dispersed in the polymer melt. According to the thermochromic spherical microcapsule prepared by the invention, the core material is compounded by crystal violet lactone, bromocresol purple, spirolactone, 1, 2-dihydroxy anthraquinone and tetra-n-propyl zirconate, so that the thermochromic spherical microcapsule has the advantages of good color change stability and high color change reaction rate, can generate reversible color change at different temperatures, and has good openness, light transmittance and ageing resistance. Compared with the thermochromic polyester film prepared by adopting spraying and coating technologies, the preparation method has the advantages of low production cost, no environmental pollution and the like, and the thermochromic polyester film prepared by the method has good economic and social benefits.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Pre-dispersing 10% of thermochromic spherical microcapsules and 89% of ethylene glycol, adding 1% of monoalkoxy titanate/triethyl phosphate compound coupling agent, and magnetically stirring at room temperature for 60min to obtain uniformly dispersed thermochromic spherical microcapsule suspension; the weight percentage of the microcapsules in the thermochromic spherical microcapsule suspension is 10%, and the particle size is 1.0 mu m.
5000g of purified terephthalic acid, 2500g of ethylene glycol, 350g of thermochromic spherical microcapsule suspension, 1.65g of tetrabutyl titanate or antimony trioxide and 0.10g of tin oxide rare earth metal compound are respectively added into a 20L general polymerization reaction kettle, and then the esterification polycondensation reaction is carried out by heating and pressurizing. The esterification polycondensation reaction is divided into two stages, namely esterification reaction and polycondensation reaction, wherein the esterification reaction is an endothermic reaction, and the polycondensation reaction is an exothermic reaction. At the initial stage of the esterification reaction, the reaction temperature was 220 ℃. With the increase of the reaction degree, the temperature gradually rises, the esterification reaction is carried out for 80min under the kettle pressure of 0.30Mpa, the pressure is released to the normal pressure when the water yield reaches 1000ml, and the temperature reaches 256 ℃ after the esterification reaction is finished. At the initial stage of polycondensation reaction, the reaction temperature is 256 ℃, after 45min of pre-polycondensation, the reaction temperature is gradually increased to 270 ℃, and a final polycondensation stage is carried out, at the initial stage of polycondensation reaction, the reaction temperature is 280 ℃, the polycondensation reaction is carried out for 80min under the condition of 150pa of kettle pressure, after the reaction is finished, a polymer with the intrinsic viscosity (eta) of 0.82 is obtained, and finally, the polymer is extruded by a melt pump, granulated and dried, so that the thermochromic polyester slice with the thermochromic spherical microcapsule mass fraction of 5% is obtained.
Blending 1000g of thermochromic polyester chips with 1500g of light polyester chips, and drying at 65 ℃ for 5 hours; then, the melt is extruded by a single screw extruder, and the thermochromic polyester film with the stretching ratio of 4 times and the film thickness of 50 mu m is prepared by the procedures of casting sheets by casting, longitudinal stretching, transverse stretching, heat setting, traction, rolling, slitting and the like.
Example 2
Pre-dispersing 15 mass percent of thermochromic spherical microcapsules and 83.5 mass percent of ethylene glycol, then adding 1.5 mass percent of monoalkoxy titanate/triethyl phosphate compound coupling agent, and magnetically stirring at room temperature for 80min to prepare uniformly dispersed thermochromic spherical microcapsule suspension; the weight percentage of the microcapsules in the thermochromic spherical microcapsule suspension is 20%, and the particle size is between 3 mu m.
5200g of purified terephthalic acid, 2800g of ethylene glycol, 355g of a thermochromic spherical microcapsule suspension, 1.66g of tetrabutyl titanate or antimony trioxide and 0.13g of a tin oxide rare earth metal compound were put into a 20L general polymerization reactor, and then, the mixture was heated and pressurized to effect esterification polycondensation. The esterification polycondensation reaction is divided into two stages, namely esterification reaction and polycondensation reaction, wherein the esterification reaction is endothermic reaction, and the polycondensation reaction is exothermic reaction. At the initial stage of the esterification reaction, the reaction temperature was 223 ℃. Along with the increase of the reaction degree, the temperature gradually rises, the esterification reaction is carried out for 85min under the kettle pressure of 0.35Mpa, the pressure is released to the normal pressure when the water yield reaches 1000ml, and the temperature reaches 258 ℃ when the esterification reaction is finished. At the initial stage of polycondensation reaction, the reaction temperature is 258 ℃, after 46min of pre-polycondensation, the reaction temperature is gradually increased to 275 ℃, and the final polycondensation stage is carried out, at the initial stage of polycondensation reaction, the reaction temperature is 282 ℃, the polycondensation reaction is carried out for 85min under the condition of kettle pressure 180, after the reaction is finished, a polymer with the intrinsic viscosity (eta) of 0.84 is obtained, and finally, the polymer is extruded by a melt pump, granulated and dried, so that the thermochromic polyester slice with the thermochromic spherical microcapsule mass fraction of 10% is obtained.
1200g of thermochromic polyester chips and 2000g of light polyester chips are blended and dried for 6 hours at 70 ℃; then, the melt extrusion is carried out through a single screw extruder, and the thermochromic polyester film with the stretching multiple of 5 times and the film thickness of 80 mu m is prepared through the procedures of casting sheets by casting, longitudinal stretching, transverse stretching, heat setting, traction, rolling, slitting and the like.
Example 3
Pre-dispersing 20% of thermochromic spherical microcapsules and 78% of ethylene glycol, adding 2% of monoalkoxy titanate/triethyl phosphate compound coupling agent, and magnetically stirring at room temperature for 90min to obtain uniformly dispersed thermochromic spherical microcapsule suspension; the weight percentage of the microcapsules in the thermochromic spherical microcapsule suspension is 30%, and the particle size is between 5 mu m.
5500g of purified terephthalic acid, 3500g of ethylene glycol, 360g of thermochromic spherical microcapsule suspension, 1.68g of tetrabutyl titanate or antimony trioxide and 0.16g of tin oxide rare earth metal compound are respectively added into a 20L general polymerization reaction kettle, and then the esterification polycondensation reaction is carried out by heating and pressurizing. The esterification polycondensation reaction is divided into two stages, namely esterification reaction and polycondensation reaction, wherein the esterification reaction is an endothermic reaction, and the polycondensation reaction is an exothermic reaction. At the initial stage of the esterification reaction, the reaction temperature was 225 ℃. With the increase of the reaction degree, the temperature gradually rises, the esterification reaction is carried out for 90min under the kettle pressure of 0.38Mpa, the pressure is released to normal pressure when the water yield reaches 1000ml, and the temperature reaches 260 ℃ when the esterification reaction is finished. At the initial stage of polycondensation reaction, the reaction temperature is 260 ℃, after 48min of pre-polycondensation, the reaction temperature is gradually increased to 280 ℃, and the final polycondensation stage is carried out, at the initial stage of polycondensation reaction, the reaction temperature is 285 ℃, the polycondensation reaction is carried out for 95min under the condition of 200pa of kettle pressure, after the reaction is finished, a polymer with the intrinsic viscosity (eta) of 0.85 is obtained, and finally, the thermochromic polyester slice with the thermochromic spherical microcapsule mass fraction of 15% is obtained by extrusion, grain cutting and drying of a melt pump.
1500g of thermochromic polyester chips and 3000g of luminous polyester chips are mixed and dried for 6 hours at 75 ℃; then, the melt extrusion is carried out through a single screw extruder, and the thermochromic polyester film with the stretching multiple of 5 times and the film thickness of 150 mu m is prepared through the procedures of casting sheets by casting, longitudinal stretching, transverse stretching, heat setting, traction, rolling, slitting and the like.
The thermochromic polyester film prepared by the invention has the following main performance technical indexes:
from the above table, the thermochromic polyester film disclosed by the invention is high in color change reaction rate, good in opening (blocking resistance), high in light transmittance, good in thermal stability and high in tensile strength, can change color at different environmental temperatures, can change reversibly with the change of the environmental temperature, and can meet the use requirements of products such as military shields, safety warning boards, color-changing toys, buildings, window films for automobiles and the like.
The present invention is not limited to the above embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make modifications to some technical features without creative efforts according to the disclosed technical contents, and these modifications should be included in the scope of the present invention.
Claims (7)
1. The preparation method of the thermochromic polyester film is characterized by comprising the following preparation steps of:
(1) Adding purified terephthalic acid, ethylene glycol, a thermochromic spherical microcapsule suspension, a catalyst and a heat stabilizer into a polymerization reaction kettle, and preparing a thermochromic polyester chip by esterification polycondensation, melt extrusion, cooling, grain cutting and drying; wherein the mass fraction of the thermochromic spherical microcapsules in the thermochromic polyester slice is 5-15%;
(2) Mixing and drying the thermochromic polyester chips prepared in the step (1) and the bright polyester chips, and then preparing a thermochromic polyester film through the working procedures of melt extrusion, tape casting, longitudinal stretching, transverse stretching, heat setting, traction trimming, rolling and the like; the mixing ratio of the thermochromic polyester chip to the luminous polyester chip is 1-1.
2. The method for preparing a thermochromic polyester film as claimed in claim 1, wherein the catalyst in step (1) is tetrabutyl titanate or antimony trioxide.
3. The method of claim 1, wherein the heat stabilizer in step (1) is a tin oxide rare earth metal compound.
4. The preparation method of the thermochromic polyester film according to claim 1, wherein the thermochromic spherical microcapsules in step (1) are prepared by an interfacial polymerization method by using a thermochromic compound as a core material and a high polymer of 2, 6-naphthalenedicarboxylic acid and ethylene glycol as a wall material; the thermochromic compound is prepared by compounding crystal violet lactone, bromocresol purple, spirolactone, 1, 2-dihydroxy anthraquinone and tetra-n-propyl zirconate, wherein the weight ratio of the components is that of the crystal violet lactone: bromocresol purple: spironolactone: 1, 2-dihydroxyanthraquinone: tetra-n-propyl zirconate =1: (0.6-0.7), (0.4-0.5), (0.2-0.3), (0.1-0.15) and (0.08-0.15).
5. The preparation method of the thermochromic polyester film according to claim 4, wherein 10-20% by mass of thermochromic spherical microcapsules and 78-89% by mass of ethylene glycol are pre-dispersed, then 1-2% by mass of monoalkoxy titanate/triethyl phosphate compound coupling agent is added, and the mixture is magnetically stirred at room temperature for 60-90 min to obtain a uniformly dispersed thermochromic spherical microcapsule suspension.
6. The method for preparing a thermochromic polyester film as claimed in claim 1, wherein the thermochromic spherical microcapsule suspension of step (1) comprises 10 to 30% by weight of thermochromic spherical microcapsules and has a particle size of 1.0 to 5 μm.
7. The method of claim 1, wherein the thickness of the thermochromic polyester film of step (1) is 50 to 150 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110933937.4A CN115703893A (en) | 2021-08-13 | 2021-08-13 | Preparation method of thermochromic polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110933937.4A CN115703893A (en) | 2021-08-13 | 2021-08-13 | Preparation method of thermochromic polyester film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115703893A true CN115703893A (en) | 2023-02-17 |
Family
ID=85181222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110933937.4A Pending CN115703893A (en) | 2021-08-13 | 2021-08-13 | Preparation method of thermochromic polyester film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115703893A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172990A (en) * | 2013-03-26 | 2013-06-26 | 江苏双星彩塑新材料股份有限公司 | Preparation method of heat shrinkable polyester film |
| CN104877065A (en) * | 2015-04-30 | 2015-09-02 | 武汉轻工大学 | Organic reversible thermochromic microcapsule with long service life and large color difference and preparation method thereof |
-
2021
- 2021-08-13 CN CN202110933937.4A patent/CN115703893A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172990A (en) * | 2013-03-26 | 2013-06-26 | 江苏双星彩塑新材料股份有限公司 | Preparation method of heat shrinkable polyester film |
| CN104877065A (en) * | 2015-04-30 | 2015-09-02 | 武汉轻工大学 | Organic reversible thermochromic microcapsule with long service life and large color difference and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101320228B1 (en) | Masterbatch with high heat resistance, heat-ray-shielding transparent molded resin, and heat-ray-shielding transparent layered product | |
| CN110116538B (en) | Antibacterial anti-slip biaxially oriented polyester film and preparation method thereof | |
| JP5257626B2 (en) | High heat resistant masterbatch, heat ray shielding transparent resin molding, and heat ray shielding transparent laminate | |
| JP2008024902A (en) | Highly heat-resistant masterbatch, heat ray-shielding transparent resin molding, and heat ray-shielding transparent laminate | |
| CN106750466A (en) | reversible thermochromic film and preparation method thereof | |
| CN109627430A (en) | A kind of phosphor-containing flame-proof polyester and its preparation method and application | |
| CN111944411B (en) | Low-rainbow-pattern polyester optical film coating liquid and preparation method thereof | |
| CN114479747A (en) | Yellowing-resistant polyurethane glue for runway and preparation method and application thereof | |
| JP2012082326A (en) | Master batch containing high heat-resistant heat ray shielding component, production method of the master batch, high heat-resistant heat ray shielding transparent resin molded article, and high heat-resistant heat ray shielding transparent laminate | |
| CN103753924A (en) | High-transparency polyester film and preparation method thereof | |
| CN103923543A (en) | Compound intelligent temperature control coating and preparation method thereof | |
| CN103951815A (en) | Preparation method of polyester for highlight flame-retardant polyester thin film | |
| KR20130089583A (en) | Biaxially oriented white polyethylene terephthalate film and back protective film for use in solar cell modules | |
| CN115703893A (en) | Preparation method of thermochromic polyester film | |
| JPH02173060A (en) | Heat ray screening plate | |
| CN110421938B (en) | Preparation method of easy-to-tear polyester film | |
| CN111002677B (en) | Colored matte flame-retardant polyester film and preparation method thereof | |
| CN116330790B (en) | Furanyl high-barrier transparent heat-resistant polyester film and preparation method thereof | |
| CN113754907A (en) | Photochromic polyester film and preparation method thereof | |
| CN101362630A (en) | Insulating mold coating of transparent glass and manufacturing method thereof | |
| CN108676279A (en) | A kind of flexible light light bar PVC modified materials and preparation method thereof of high brightness | |
| CN113817425A (en) | Photochromic polyester release film and preparation method thereof | |
| CN108641229A (en) | A kind of V0 grades of flame-retarded PVC modified material and preparation method thereof | |
| KR102316251B1 (en) | Metal paint composition and method for preparing polymer molding product with metal film using the same | |
| CN117106323B (en) | Organic-inorganic composite functional pigment dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |