CN118638296A - Intelligent temperature control TPU material applied to automobile glass film and preparation method thereof - Google Patents
Intelligent temperature control TPU material applied to automobile glass film and preparation method thereof Download PDFInfo
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- CN118638296A CN118638296A CN202411109707.6A CN202411109707A CN118638296A CN 118638296 A CN118638296 A CN 118638296A CN 202411109707 A CN202411109707 A CN 202411109707A CN 118638296 A CN118638296 A CN 118638296A
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- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 55
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Abstract
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to an intelligent temperature control TPU material applied to an automobile glass film and a preparation method thereof. The material is prepared from the following raw materials in percentage by mass: polyester polyol: 42-55%; isocyanate: 22-34%; chain extender: 3-10%; thermosensitive temperature-control filler: 10-25%; ultraviolet absorber: 0.1-0.5%; catalyst: 0.05-0.1%; the thermosensitive temperature-control filler is nano AuNPs@MoO 3/VO2. And by adopting an in-situ synthesis technology, the thermosensitive temperature-control filler is fused into the TPU molecular chain segment, so that the high light transmittance of the TPU molecular chain segment is maintained, and the solar energy regulation and control efficiency of the TPU molecular chain segment is obviously improved. Meanwhile, the TPU material has excellent temperature control performance under high-temperature illumination, reduced influence of temperature fluctuation, excellent precipitation resistance and mechanical property, and has wide application prospect in the field of automobile glass films.
Description
Technical Field
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to an intelligent temperature control TPU material applied to an automobile glass film and a preparation method thereof.
Background
Thermoplastic polyurethane elastomer (TPU) is a green environment-friendly high polymer material which can be melted by heating and is soluble in solvents, has excellent physical and mechanical properties such as high modulus, high strength, high elongation, high elasticity, high wear resistance and the like, and has the advantages of oil resistance, corrosion resistance, ultraviolet light resistance, microorganism resistance and the like. With the high-speed development of the TPU industry, new technology, new products and new application are continuously emerging, and the TPU material is widely applied to a plurality of fields such as sheets, shoe materials, automobiles, cables, medical treatment, films and the like at present. The TPU film has excellent flexibility and impact resistance, can effectively attach to the cambered surface and prevent the attach cambered surface from cracking; meanwhile, the glass film has the characteristics of no smell and no toxicity and can be processed by heat sealing, and is widely applied to the field of automobile glass films.
In hot summer, under the strong radiation of the sun, the heat of the solar radiation is rapidly conducted to the interior of a carriage through a glass window of an automobile, so that the temperature in the automobile is rapidly increased, and the safety driving of a driver is adversely affected. Unfortunately, although the conventional TPU film material has good impact resistance and scratch resistance, the conventional TPU film material cannot combine the functions of high visible light transmittance and dynamic regulation and control of solar radiation heat, so that the urgent requirements of intelligent temperature control of an automobile glass film cannot be effectively met. In view of the above, innovative modification of the intelligent temperature control function of the TPU film material is particularly important and urgent. Vanadium dioxide (VO 2) is a thermochromic material with unique properties that when a specific phase transition temperature (Tc, about 68 ℃) is reached, it is capable of undergoing a reversible metal-insulator transition (MIT) that is such that it exhibits a significant change from high transmission to high barrier in the near infrared band (780-2500 nm) of sunlight, while the transmission in the visible band (380-780 nm) remains relatively stable. Therefore, the vanadium dioxide has very wide application potential and prospect in the field of intelligent temperature control, in particular in the application scene requiring thermochromic temperature regulation. The modified TPU film material is introduced into modification research of the TPU film material, and is expected to realize important breakthrough of the intelligent temperature control function of the automobile glass film.
Currently, a vanadium dioxide (VO 2) thermochromic thin film is recognized as the most ideal thermochromic material in the field of intelligent windows because of its structural simplicity and significant advantages of realizing functional operation without additional energy consumption. However, there are two major core challenges in applying VO 2 specifically: the phase transition temperature of the material is obviously higher than that of the normal temperature environment, so that the material is limited to be directly applied under the normal temperature condition; secondly, the process flow for depositing the VO 2 film on the rigid substrate is very complex, and the film forming quality of the prepared film is poor, thereby further influencing the efficiency and stability of the film in practical application. In addition, the common thermochromic functional film preparation scheme at present also has the problems that the preparation method is complex, the cost is high, and the low phase transition temperature and the high film performance (such as high film forming property, scratch resistance and excellent mechanical property) cannot be simultaneously combined.
Chinese patent CN117987086a discloses a method for preparing flexible vanadium dioxide film, which uses polyacrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylidene fluoride hexafluoropropylene, polyethylene oxide, polyethylene, polystyrene and other polymer resin as flexible base material, and physically blends nano-scale vanadium dioxide to synthesize a flexible vanadium dioxide film, the synthesis method is simple and safe, and easy to prepare. However, the method is only used for preparing the composite film material by simply and physically blending the nano vanadium dioxide, the phase transition temperature of the composite film material is far higher than the room temperature, the temperature control adjustment under the room temperature condition can not be realized, and the sensitivity, the stability and the reliability of the thermal control temperature are low.
Chinese patent CN11439476a discloses a preparation method of novel VO 2 -based thermochromic composite film, and by means of pulse laser deposition, a metal nanoparticle layer and a plurality of vanadium dioxide thermochromic functional layers are introduced into a thermochromic functional film system to form a transparent functional film with excellent performance, so that a high-performance vanadium dioxide thermochromic functional film is produced. Chinese patent CN117551970a discloses a composite film of VO 2/W-VO2/VO2 and a preparation method thereof, wherein a pulse laser deposition system is adopted to prepare a multilayer composite film structure of VO 2/W-VO2/VO2, thereby realizing the comprehensive improvement of three aspects of a thermochromic film Tlum with a VO 2 base, Δtsol and Tc. Chinese patent CN116426265B discloses a method for preparing a tungsten-magnesium doped vanadium dioxide thermochromic film, which adopts a simple solution method to prepare a tungsten-magnesium doped vanadyl ammonium citrate precursor, and synthesizes the tungsten-magnesium doped vanadium dioxide thermochromic film by a film coating forming method. The phase transition temperature of vanadium dioxide can be reduced, the width of a loop can be reduced and the optical performance can be improved by utilizing the doping energy of tungsten and magnesium. However, the preparation methods of the vanadium dioxide film used in the three patents all deposit the vanadium dioxide film on the rigid substrate by a magnetron sputtering method, a pulse laser deposition method, a chemical vapor deposition method, a wet chemical deposition method and the like, and the film forming property of the pulse deposition on the rigid substrate is poor, the film is easy to wash off and not scratch-resistant, and the production steps are complicated, so that the large-scale production is not facilitated. Meanwhile, the preparation of the multilayer film and the matching of the film layers are involved, so that the preparation cost of the composite film is increased intangibly, and the balance between high performance and low cost is difficult to realize. Therefore, how to prepare an intelligent control TPU film material with the temperature close to the corresponding room temperature and good scratch resistance and excellent mechanical properties at the same time becomes a technical problem to be solved at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an intelligent temperature control TPU material applied to an automobile glass film, and adopts an in-situ synthesis technology to integrate a thermosensitive temperature control filler into a TPU molecular chain segment, so that the high light transmittance of the TPU molecular chain segment is maintained, and the solar energy regulation and control efficiency of the TPU molecular chain segment is obviously improved. Meanwhile, the TPU material has excellent temperature control performance under high-temperature illumination, reduced influence of temperature fluctuation, excellent precipitation resistance and mechanical property, and wide application prospect in the field of automobile glass films;
the invention further aims to provide a preparation method of the intelligent temperature control TPU material applied to the automobile glass film, which is scientific, reasonable, simple and easy to implement.
The technical scheme adopted by the invention is as follows:
The intelligent temperature control TPU material applied to the automobile glass film is prepared from the following raw materials in percentage by mass:
Polyester polyol: 42-55%;
isocyanate: 22-34%;
chain extender: 3-10%;
thermosensitive temperature-control filler: 10-25%;
Ultraviolet absorber: 0.1-0.5%;
catalyst: 0.05-0.1%;
the thermosensitive temperature-control filler is nano AuNPs@MoO 3/VO2, the size is 500-1000 nm, and the preparation method comprises the following steps:
(1) Adding nano vanadium dioxide into deionized water, and uniformly stirring to obtain suspension A;
(2) Adding ammonium heptamolybdate into deionized water, stirring until the ammonium heptamolybdate is completely dissolved to obtain an ammonium heptamolybdate solution, dropwise adding dilute nitric acid into the ammonium heptamolybdate solution, and adjusting the pH value of the ammonium heptamolybdate solution to 1.5-3 through the dilute nitric acid to obtain a solution B;
(3) Mixing the suspension A and the solution B, adding the mixture into a polytetrafluoroethylene hydrothermal high-pressure reaction cup, uniformly stirring, sealing and carrying out hydrothermal reaction, naturally cooling the reaction cup to room temperature after the reaction is finished, and carrying out centrifugal separation on the reaction liquid to obtain nano MoO 3/VO2, namely a precursor C;
(4) Adding hexadecyl trimethyl ammonium bromide solution into the precursor C, stirring uniformly, adding HAuCl 4 solution, stirring and carrying out ultrasonic treatment for 20min, finally slowly adding ascorbic acid solution, stirring uniformly, reacting in a water bath to obtain nano AuNPs@MoO 3/VO2, centrifugally separating, washing with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for later use.
The polyester polyol is polycaprolactone dihydric alcohol, and the number average molecular weight is 750-2000.
The isocyanate is 4,4 '-dicyclohexylmethane diisocyanate (H12 MDI) or isophorone diisocyanate (IPDI), preferably 4,4' -dicyclohexylmethane diisocyanate.
The chain extender is a straight-chain small molecular dihydric alcohol, and is specifically one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or 1, 6-hexanediol.
The ultraviolet absorber is one or more of UV-1, UV-P, UV-328 or UV-312, and two or more of the above components can be mixed in any proportion.
The catalyst is an organobismuth catalyst or an organotin catalyst, preferably stannous octoate.
In the nano AuNPs@MoO 3/VO2, the mass ratio of AuNPs, moO 3 to VO 2 is (0.001-0.003): 0.5-1): 1.
The concentration of the suspension A in the step (1) is 6mol/L; the concentration of the ammonium heptamolybdate solution in the step (2) is 0.1-0.25 mol/L.
In the step (3), the volume ratio of the suspension A to the solution B is 1 (1-5); the hydrothermal reaction temperature is 160-180 ℃ and the time is 20-24 h.
In the step (4), the concentration of the cetyltrimethylammonium bromide solution is 0.2-0.5 mol/L; the concentration of the HAuCl 4 solution is 0.01-0.05 mol/L; the concentration of the ascorbic acid solution is 0.09-0.15 mol/L; the reaction temperature is 25-30 ℃ and the reaction time is 35-40 h.
The preparation method of the intelligent temperature control TPU material applied to the automobile glass film comprises the following steps:
s1, heating and dehydrating polyester polyol at 80 ℃, adding a thermosensitive temperature-control filler and an ultraviolet absorbent into the dehydrated polyester polyol, uniformly stirring, and performing ultrasonic dispersion for 1h to obtain a mixed solution;
s2, respectively adding a chain extender and a catalyst into the mixed solution, uniformly stirring, adding isocyanate, vigorously stirring, curing for 8 hours in a gel and 120 ℃ oven, and crushing to obtain granules;
and S3, carrying out injection molding on the material particles by using an injection molding machine, and extruding the material particles into a film by using a film drawing machine to obtain the intelligent temperature control TPU material applied to the automobile glass film.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, the thermosensitive temperature-control filler nano AuNPs@MoO 3/VO2 is successfully introduced into a TPU (thermoplastic polyurethane) molecular chain system through an in-situ synthesis technology, so that the high light transmittance characteristic of the TPU material in a visible light region is maintained, the solar energy regulation efficiency is improved, the specific expression of delta Tsol (solar energy regulation efficiency) is improved from 0.7% to 8.2%, and the intelligent temperature control function enhancement from no to no and spanning performance is realized. The TPU material shows excellent temperature control performance under high temperature and illumination environment, and has obvious intelligent temperature control effect.
In addition, the TPU material prepared by the method has excellent precipitation resistance, and ensures the stability and reliability of the material in the long-term use process; meanwhile, the mechanical properties of the glass film are also kept good, the strict requirements of the application in multiple fields on the material strength are met, and the glass film has wide application prospects in the field of automobile glass films.
Drawings
FIG. 1 is a schematic diagram of a device for testing the performance of light control and temperature control according to the present invention;
in the figure: 1. a TPU film; 2. a heat insulation dark box; 3. a thermometer; 4. a solar light.
Detailed Description
The invention is further illustrated below with reference to examples, which are not intended to limit the practice of the invention.
The raw materials used in examples and comparative examples are conventional commercial raw materials unless otherwise specified, and the process methods used in examples and comparative examples are conventional in the art unless otherwise specified.
Some of the raw materials used in the examples and comparative examples are described below:
Nano gold powder, available from ala Ding Shiji (Shanghai) limited;
Nanometer vanadium dioxide, purchased from Guangzhou Hongwu materials science and technology Co., ltd;
Molybdenum trioxide, purchased from Ningbo gold nano materials technologies limited;
the thermosensitive temperature-control filler is nano AuNPs@MoO 3/VO2, the size is 750+/-250 nm, and the preparation method comprises the following steps:
(1) Adding 99.6g of nano vanadium dioxide into 200mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 30min to obtain a suspension A with the concentration of 6 mol/L;
(2) 57.54g of ammonium heptamolybdate is added into 200mL of deionized water, stirred until the ammonium heptamolybdate is completely dissolved, an ammonium heptamolybdate solution with the concentration of 0.25mol/L is obtained, then 2mol/L of dilute nitric acid is dropwise added into the ammonium heptamolybdate solution, and the pH value of the ammonium heptamolybdate solution is adjusted to 2 through the dilute nitric acid, so that a solution B is obtained;
(3) Mixing 200mL of suspension A and 200mL of solution B, adding into a polytetrafluoroethylene hydrothermal high-pressure reaction cup, uniformly stirring, sealing, performing hydrothermal reaction at 180 ℃ for 20 hours, naturally cooling the reaction cup to room temperature after the reaction is finished, and performing centrifugal separation on the reaction liquid to obtain nano MoO 3/VO2, namely a precursor C;
(4) Adding 200mL of cetyltrimethylammonium bromide solution (with the concentration of 0.2 mol/L) into 90g of precursor C, stirring uniformly, adding 90mL of HAuCl 4 solution (with the concentration of 0.01 mol/L), stirring and carrying out ultrasonic treatment for 20min, finally slowly adding 15mL of ascorbic acid solution (with the concentration of 0.09 mol/L), stirring uniformly, reacting in a water bath at 27 ℃ for 36h to prepare nano AuNPs@MoO 3/VO2, centrifuging, washing with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for later use; wherein the mass ratio of AuNPs, moO 3 and VO 2 is 0.003:0.5:1.
Example 1
The intelligent temperature control TPU material applied to the automobile glass film is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 1000): 47.78%;
4,4' -dicyclohexylmethane diisocyanate: 23.32%;
1, 4-butanediol: 3.55%;
Nano aunps@moo 3/VO2: 25%;
UV-1：0.1%；
UV-312：0.2%；
Stannous octoate: 0.05%;
the preparation method of the intelligent temperature control TPU material applied to the automobile glass film comprises the following steps:
S1, heating and dehydrating polycaprolactone dihydric alcohol at 80 ℃, adding nano AuNPs@MoO 3/VO2, UV-1 and UV-312 into dehydrated polyester polyol, uniformly stirring, and performing ultrasonic dispersion for 1h to obtain a mixed solution;
s2, respectively adding 1, 4-butanediol and stannous octoate into the mixed solution, uniformly stirring, adding 4,4' -dicyclohexylmethane diisocyanate, vigorously stirring, pouring the mixture into a drying tray after the mixture is gelled, curing for 8 hours in a 120 ℃ oven, and crushing the product to obtain granules;
and S3, carrying out injection molding on the material particles by using an injection molding machine, and extruding the material particles into a film by using a film drawing machine to obtain the intelligent temperature control TPU material applied to the automobile glass film.
Example 2
The intelligent temperature control TPU material applied to the automobile glass film is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 1500): 54.07%;
4,4' -dicyclohexylmethane diisocyanate: 22.41% of the total weight of the product;
ethylene glycol: 3.04%;
Nano aunps@moo 3/VO2: 20% of a base;
UV-P：0.2%；
UV-328：0.2%；
stannous octoate: 0.08%;
The preparation method of the intelligent temperature control TPU material applied to the automobile glass film comprises the following steps of example 1.
Example 3
The intelligent temperature control TPU material applied to the automobile glass film is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 2000): 53.66%;
isophorone diisocyanate: 28.22% of the total weight of the product;
1, 3-propanediol: 7.56%;
Nano aunps@moo 3/VO2: 10%;
UV-1：0.2%；
UV-328：0.3%；
stannous octoate: 0.06%;
The preparation method of the intelligent temperature control TPU material applied to the automobile glass film comprises the following steps of example 1.
Example 4
The intelligent temperature control TPU material applied to the automobile glass film is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 750): 42.4%;
4,4' -dicyclohexylmethane diisocyanate: 33.29% of the total weight of the product;
1, 6-hexanediol: 9.11%;
nano aunps@moo 3/VO2: 15%;
UV-328：0.1%；
Bismuth neodecanoate: 0.1%;
The preparation method of the intelligent temperature control TPU material applied to the automobile glass film comprises the following steps of example 1.
Comparative example 1
The TPU material is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 1000): 63.78% of the total weight of the product;
4,4' -dicyclohexylmethane diisocyanate: 31.01%;
1, 4-butanediol: 4.86%;
UV-1：0.1%；
UV-312：0.2%；
Stannous octoate: 0.05%;
Otherwise, the same as in example 1 was conducted.
Comparative example 2
Using an equal amount of nano MoO 3/VO2 prepared in step (3) instead of nano AuNPs@MoO 3/VO2 in example 1;
The TPU material is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 1000): 47.78%;
4,4' -dicyclohexylmethane diisocyanate: 23.32%;
1, 4-butanediol: 3.55%;
nanometer MoO 3/VO2: 25%;
UV-1：0.1%；
UV-312：0.2%；
Stannous octoate: 0.05%;
Otherwise, the same as in example 1 was conducted.
Comparative example 3
Equivalent amount of nano vanadium dioxide is used to replace nano AuNPs@MoO 3/VO2 in example 1;
The TPU material is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 1000): 47.78%;
4,4' -dicyclohexylmethane diisocyanate: 23.32%;
1, 4-butanediol: 3.55%;
nano vanadium dioxide: 25%;
UV-1：0.1%；
UV-312：0.2%；
Stannous octoate: 0.05%;
Otherwise, the same as in example 1 was conducted.
Comparative example 4
Taking nano gold powder, molybdenum trioxide and nano vanadium dioxide with the mass ratio of 0.003:0.5:1 for physical blending, and marking the mixture obtained by blending the three as filler AMV; equivalent amount of filler AMV is used to replace nano AuNPs@MoO 3/VO2 in example 1;
The TPU material is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 1000): 47.78%;
4,4' -dicyclohexylmethane diisocyanate: 23.32%;
1, 4-butanediol: 3.55%;
filler AMV:25%;
UV-1：0.1%；
UV-312：0.2%；
Stannous octoate: 0.05%;
Otherwise, the same as in example 1 was conducted.
Comparative example 5
The TPU material is prepared from the following raw materials in percentage by mass:
Polycaprolactone diol (number average molecular weight 1000): 58.66% of the total weight of the product;
4,4' -dicyclohexylmethane diisocyanate: 28.63%;
1, 4-butanediol: 4.36%;
Nano aunps@moo 3/VO2: 8%;
UV-1：0.1%；
UV-312：0.2%；
Stannous octoate: 0.05%;
Otherwise, the same as in example 1 was conducted.
Comparative example 6
The TPU material is prepared from the following raw materials in percentage by mass:
polycaprolactone diol (number average molecular weight 1000): 44.57%;
4,4' -dicyclohexylmethane diisocyanate: 21.76%;
1, 4-butanediol: 3.32%;
Nano aunps@moo 3/VO2: 30%;
UV-1：0.1%；
UV-312：0.2%；
Stannous octoate: 0.05%;
Otherwise, the same as in example 1 was conducted.
The TPU materials prepared in examples 1 to 4 and comparative examples 1 to 6 were subjected to performance test, and the test method is as follows:
Tensile strength (MPa): reference GB/T528-2009;
optical performance test: and testing the optical properties of the TPU film with the thickness of 0.5mm in the wavelength range of 350-2600 nm by adopting a U-3010 ultraviolet-visible-near infrared spectrophotometer. The equipment is externally connected with a temperature control thermocouple, the temperature of a sample can be controlled, the visible light transmittance Tlum (%) and the solar energy transmittance Tsol (%) of the sample are respectively detected in a temperature range of 25-50 ℃, and the solar energy control capability (%) is calculated through a formula of delta tsol=tsol (25 ℃) to Tsol (50 ℃);
And (3) testing the illumination temperature control performance: the structure of the device is shown in figure 1, a modified TPU film with the size of 150mm multiplied by 80mm and the thickness of 0.5mm is stuck on a window of a heat insulation and preservation camera bellows (all the bellows are coated with heat insulation materials except the uppermost window, the size of the window is 150mm multiplied by 80 mm), and a thermometer is inserted into the camera bellows. Placing the camera bellows in a temperature control lamp box (GT-7035-EUAB of high-speed rail detection instrument Co., ltd.), respectively setting the temperature of the temperature control lamp box to 25 ℃ and 50 ℃, irradiating the temperature control lamp box with a 300W sunlight lamp for 8 hours, wherein the distance between the sunlight lamp and a TPU film is 300mm, and recording the temperature change condition of a thermometer in the camera bellows, namely the temperature of the camera bellows (DEG C); temperature change value (°c) =darkroom temperature (°c) -temperature control lamp box set temperature (°c);
Migration resistance: TPU film with the size of 150mm multiplied by 80mm and thickness of 0.5mm is placed in a constant temperature and humidity box with the temperature of 85 ℃ and the humidity of 85% for 24 hours, and the precipitation condition of the surface of the TPU film is observed.
The test results are shown in Table 1.
TABLE 1 Performance test results
As can be seen from the data in table 1, the TPU material prepared by the embodiment of the invention introduces the nano aunps@moo 3/VO2 thermosensitive temperature control material into the TPU molecular chain system through in-situ synthesis, so that the high light transmittance of the material in visible light is ensured, the solar energy regulation and control capability of the TPU material is improved, and the intelligent temperature control effect is obvious; in addition, the TPU material prepared by the embodiment has the characteristics of precipitation resistance and good mechanical property, and can be widely applied to the field of automobile glass films.
Compared with example 1, the comparative example 1 is not added with nano AuNPs@MoO 3/VO2, the solar energy control capability (delta Tsol) is relatively poor, the delta Tsol is only 0.7% under the condition of 50 ℃, and the intelligent temperature control performance is basically not provided. Equal amounts of MoO 3/VO2、VO2 and filler AMV are adopted in comparative examples 2-4 to replace nano AuNPs@MoO 3/VO2 in example 1, the solar energy regulation and control capacity (delta Tsol) of the prepared TPU material is lower than that of example 1, and the temperature change value under the condition of 50 ℃ is higher than that of example 1, so that the components of nano AuNPs@MoO 3/VO2 added in example 1 have obvious synergistic effect, and the intelligent temperature control performance of the material can be obviously improved; the addition amount of nano AuNPs@MoO 3/VO2 in comparative example 5 is only 8%, and the solar energy regulation and control capacity (delta Tsol) of the prepared TPU material is low; the addition amount of nano AuNPs@MoO 3/VO2 in comparative example 6 is 30%, and the solar energy regulation and control capability (delta Tsol) of the prepared TPU material is higher than that of example 1, but the mechanical property of the modified TPU material is obviously reduced due to the addition of a large amount of modified filler, the modified TPU material is unevenly distributed in the material, the visible light transmittance of the material is obviously reduced, and the material is easy to separate out.
Claims (8)
1. An intelligent temperature control TPU material applied to an automobile glass film is characterized by being prepared from the following raw materials in percentage by mass
Polyester polyol: 42-55%;
isocyanate: 22-34%;
chain extender: 3-10%;
thermosensitive temperature-control filler: 10-25%;
Ultraviolet absorber: 0.1-0.5%;
catalyst: 0.05-0.1%;
The thermosensitive temperature-control filler is nano AuNPs@MoO 3/VO2, and the preparation method comprises the following steps:
(1) Adding nano vanadium dioxide into deionized water, and uniformly stirring to obtain suspension A;
(2) Adding ammonium heptamolybdate into deionized water, stirring and dissolving to obtain an ammonium heptamolybdate solution, and adjusting the pH value of the ammonium heptamolybdate solution to 1.5-3 by dilute nitric acid to obtain a solution B;
(3) Mixing the suspension A and the solution B, and performing hydrothermal reaction to obtain nano MoO 3/VO2, namely a precursor C;
(4) Adding cetyl trimethyl ammonium bromide solution into the precursor C, stirring uniformly, adding HAuCl 4 solution, performing ultrasonic treatment, and finally adding ascorbic acid solution, and reacting to obtain the nano AuNPs@MoO 3/VO2.
2. The intelligent temperature-control TPU material applied to the automobile glass film according to claim 1, wherein the polyester polyol is polycaprolactone diol and has a number average molecular weight of 750-2000.
3. The intelligent temperature-controlled TPU material applied to an automotive glass film according to claim 1, wherein said isocyanate is 4,4' -dicyclohexylmethane diisocyanate or isophorone diisocyanate.
4. The intelligent temperature-controlled TPU material applied to an automotive glass film according to claim 1, wherein the chain extender is one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, or 1, 6-hexanediol.
5. The intelligent temperature-control TPU material applied to an automobile glass film according to claim 1, wherein the ultraviolet absorber is one or more of UV-1, UV-P, UV-328 and UV-312.
6. The intelligent temperature-control TPU material applied to an automotive glass film according to claim 1, wherein the catalyst is an organobismuth catalyst or an organotin catalyst.
7. The intelligent temperature control TPU material applied to the automobile glass film according to claim 1, wherein the mass ratio of AuNPs to MoO 3/VO2 to the mass ratio of AuNPs to MoO 3 to VO 2 is (0.001-0.003): (0.5-1): 1.
8. A method for preparing the intelligent temperature control TPU material applied to an automobile glass film according to any one of claims 1-7, which is characterized by comprising the following steps:
s1, adding a thermosensitive temperature-control filler and an ultraviolet absorbent into dehydrated polyester polyol, and uniformly stirring to obtain a mixed solution;
s2, respectively adding a chain extender and a catalyst into the mixed solution, uniformly stirring, adding isocyanate, and obtaining material particles through gel, curing and crushing;
and S3, carrying out injection molding and extrusion film forming on the material particles to obtain the intelligent temperature control TPU material applied to the automobile glass film.
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| WO2018092502A1 (en) * | 2016-11-16 | 2018-05-24 | コニカミノルタ株式会社 | Thermochromic composition and thermochromic film |
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