CN114316790A - Preparation method of hydrangeal-shaped nano zinc oxide-doped heat-conducting polyurethane coating - Google Patents
Preparation method of hydrangeal-shaped nano zinc oxide-doped heat-conducting polyurethane coating Download PDFInfo
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Abstract
The invention relates to a preparation method of a thermal conductive polyurethane coating doped with hydrangeal nano zinc oxide, belonging to the technical field of functional coatings. Firstly, preparing embroidered spherical nano zinc oxide powder by a template-free solvothermal method; then, preparing aqueous polyurethane emulsion by adopting diisocyanate, polyester diol and an additive; and finally, dispersing the hydrangea-shaped nano zinc oxide powder in the waterborne polyurethane emulsion, and curing to obtain the heat-conducting polyurethane coating. The method can prepare the photocuring waterborne polyurethane coating with high heat conductivity, corrosion resistance and excellent physical properties, enables heat to be rapidly transferred along a heat conducting network, and has the unique functions of resisting and inhibiting bacteria, removing odor and preventing mildew.
Description
Technical Field
The invention relates to a preparation method of a thermal conductive polyurethane coating doped with hydrangeal nano zinc oxide, in particular to preparation of a photocuring waterborne polyurethane coating with high thermal conductivity, corrosion resistance and excellent physical properties, and belongs to the technical field of functional coatings.
Background
In recent years, electronic devices tend to be light, thin and lightweight, and the degree of integration of internal electronic components is increasing, which inevitably leads to heat accumulation inside the devices and difficulty in heat dissipation. The increase of the internal temperature of the electronic device will seriously affect the service performance and the service life thereof. The use of coating technology to increase the efficiency of heat dissipation within a device or fixture is an effective approach. Therefore, designing and preparing a novel heat-conducting polymer coating becomes a hot spot of current research.
The photocuring waterborne polyurethane has the characteristics of safe and energy-saving photocuring technology, short curing time, high speed, environmental friendliness and excellent performance. However, because the polyurethane has poor heat conductivity, the heat conductivity is only 0.19W/mK, and heat-conducting powder needs to be added to enhance the heat conductivity.
The nano zinc oxide has high thermal conductivity (60w/mK), the heat conductivity of the matrix resin can be greatly improved by using the nano zinc oxide as heat conducting powder, and in addition, the nano zinc oxide also has the unique functions of resisting and inhibiting bacteria, removing odor and preventing mildew.
Disclosure of Invention
The invention aims to overcome the defects and provide the preparation method of the thermal conductive polyurethane coating doped with the hydrangeal nano zinc oxide, so that the photocuring waterborne polyurethane coating with excellent thermal conductivity can be prepared, and meanwhile, the coating has excellent weather resistance and heat resistance.
The technical scheme of the invention is a preparation method of a heat-conducting polyurethane coating doped with embroidered spherical nano zinc oxide, and the method comprises the following steps of firstly preparing embroidered spherical nano zinc oxide powder by a template-free solvothermal method; then, preparing aqueous polyurethane emulsion by adopting diisocyanate, polyester diol and an additive; and finally, dispersing the hydrangea-shaped nano zinc oxide powder in the waterborne polyurethane emulsion, and curing to obtain the heat-conducting polyurethane coating.
Further, the preparation process of the embroidered spherical nano zinc oxide powder comprises the following steps: firstly, adding zinc acetate dihydrate and sodium citrate into a reaction vessel, then adding deionized water, and uniformly stirring until the zinc acetate dihydrate and the sodium citrate are completely dissolved; stirring and dispersing sodium hydroxide in ethanol; mixing the two solutions, heating, and stirring for reaction; the obtained mixture is transferred into a high-pressure autoclave after ultrasonic treatment and is placed in a constant-temperature drying box for heating reaction; after the high-pressure reaction kettle is cooled to room temperature, opening the device, and collecting the obtained solution; and (4) carrying out suction filtration to obtain a white product, washing until the filtrate is neutral, and drying to obtain the hydrangea-shaped nano zinc oxide.
Further, the preparation process of the embroidered spherical nano zinc oxide powder comprises the following steps: adding 1.60-1.68g of zinc acetate dihydrate and 2.20-2.25g of sodium citrate into a reaction vessel, then adding 150-200mL of deionized water, and uniformly stirring at room temperature until the zinc acetate dihydrate and the sodium citrate are completely dissolved; dispersing 2.90-3.15g of sodium hydroxide in 70-80mL of ethanol; mixing the two solutions, heating to 38-42 deg.C, mixing and stirring for 1-3 h; carrying out ultrasonic treatment on the obtained mixture at 30-40kHz for 20-40min, and transferring the mixture into a high-pressure reaction container; heating the high-pressure reaction vessel at the temperature of 140 ℃ and 160 ℃ for reaction for 23-25h, cooling to room temperature, and collecting the obtained reaction liquid; filtering by suction filtration to obtain a white product, and washing with deionized water and ethanol for multiple times until the filtrate is neutral; and finally, drying the obtained product at 58-62 ℃ for 24h to obtain hydrangeal nano zinc oxide powder.
Further, the preparation process of the aqueous polyurethane emulsion comprises the following steps: mixing diisocyanate, polyester diol and a catalyst, and reacting at constant temperature; after the free-NCO in the titration system reaches a theoretical value, adding a chain extender, and heating for continuous reaction; keeping the temperature, dropwise adding a polymerization inhibitor and an active blocking agent, and continuing to react; adding a micromolecular cross-linking agent for reaction after the-NCO content reaches a theoretical value; detecting 2270cm by infrared spectrometer-1Completely eliminating the characteristic absorption peak of-NCO to obtain a target product; closing the heating device, cooling to normal temperature, adding neutralizer, stirring at high speed, addingDeionized water, and then stirring at high speed to obtain the photocuring waterborne polyurethane emulsion.
Further, the preparation of the aqueous polyurethane emulsion comprises the following specific steps: mixing 5.8-6.0g of diisocyanate, 11.5-13.2g of polyester diol and 1-2d of catalyst at 40-50 ℃, and reacting for 2-4h at constant temperature; after the free-NCO in the titration system reaches a theoretical value, adding 0.91-0.95g of chain extender, heating to 60-70 ℃, and continuing to react for 2-4 h; keeping the temperature at 60-70 ℃, dropwise adding 0.04-0.05g of polymerization inhibitor and 2.04-2.10g of active blocking agent, and continuing to react for 2-4 h; after the-NCO content reaches a theoretical value, adding 0.30-0.32g of micromolecule crosslinking agent, and reacting for 4-8 h; detecting 2270cm by infrared spectrometer-1Completely eliminating the characteristic absorption peak of-NCO to obtain a target product; and (3) closing the heating device, cooling to normal temperature, adding a neutralizer with the same amount of the chain extender, stirring at a high speed for 1h, adding 45-50mL of deionized water, and stirring at a high speed for 1h to obtain the photocuring waterborne polyurethane emulsion.
Further, the diisocyanate is at least one of toluene diisocyanate TDI, 4' -diphenylmethane diisocyanate MDI and isophorone diisocyanate IPDI;
the polyester dihydric alcohol is specifically polycarbonate dihydric alcohol PCDL;
the catalyst is dibutyltin dilaurate or stannous octoate;
the chain extender is dimethylolpropionic acid DMPA or dimethylbenzene anthracene DMBA;
the polymerization inhibitor is 4-methoxyphenol;
the active end-capping reagent is at least one of hydroxyethyl acrylate HEA, hydroxyethyl methacrylate HEMA and pentaerythritol triacrylate PETA;
the micromolecule cross-linking agent is trimethylolpropane TMP;
the neutralizer is triethanolamine TEA.
Further, the preparation process of the heat-conducting polyurethane coating comprises the following steps: adding the embroidered spherical nano zinc oxide into ethanol, treating the mixture in an ultrasonic device, adding the prepared waterborne polyurethane emulsion under the stirring state, keeping out of the sun at room temperature, continuously stirring the mixture, adding a photoinitiator, uniformly dispersing, pouring the mixture into a polytetrafluoroethylene groove, standing, drying, and carrying out UV curing to obtain the heat-conducting polyurethane coating doped with the embroidered spherical nano zinc oxide.
Further, according to the measurement that each gram of the spherical nano zinc oxide is dispersed in 10mL of ethanol, 0.20-0.26g of the spherical nano zinc oxide is added into the ethanol, and ultrasonic treatment is carried out for 2-4h at 30-40 kHz; slowly adding 10-12mL of prepared aqueous polyurethane emulsion under the stirring state; continuously stirring the mixture for 1-3h at room temperature in a dark place, adding a photoinitiator accounting for 2-5% of the mass of the aqueous polyurethane emulsion, uniformly dispersing, pouring into a polytetrafluoroethylene groove, standing for 1-2d, then placing in an oven at 45-50 ℃ for drying for 4-10h, and finally curing for 20-70s by using an ultraviolet curing machine to obtain the hydrangeal-shaped nano zinc oxide-doped heat-conducting polyurethane coating.
Further, the photoinitiator is 1173 photoinitiator.
The thermal conductive polyurethane coating doped with the hydrangeal nano zinc oxide is prepared by the method.
The invention has the beneficial effects that: the method can prepare the photocuring waterborne polyurethane coating with high heat conductivity, corrosion resistance and excellent physical properties, enables heat to be rapidly transferred along a heat conducting network, and has the unique functions of resisting and inhibiting bacteria, removing odor and preventing mildew.
Drawings
FIG. 1 is SEM image of hydrangeal nano zinc oxide prepared in example 1.
Fig. 2 is an XRD characterization pattern of commercial zinc oxide and the hydrangeal nano zinc oxide prepared in example 1.
Detailed Description
EXAMPLE 1 Synthesis of hydrangeal-like Nano Zinc oxide
Firstly, adding 1.66g of zinc acetate dihydrate and 2.22g of sodium citrate into a dry beaker, then adding 150mL of deionized water, and uniformly stirring the mixture on a magnetic stirring device at room temperature until the mixture is completely dissolved; and 3g of sodium hydroxide was dispersed in 70mL of ethanol in the same manner. The two solutions were then added to a beaker and, after heating to 40 ℃, mixed and stirred for 2 hours. The resulting mixture was treated at 40kHz for 30min in an ultrasonic device and transferred to a 500mL stainless steel autoclave lined with Teflon. The autoclave was placed in a constant temperature drying oven and heated at 150 ℃ for 24 h. After the high-pressure reaction kettle is cooled to room temperature, the device is opened, and the obtained solution is collected in a beaker for later use. And filtering by using a suction filtration device, collecting a white product, and washing the white product with deionized water and ethanol for multiple times until the pH value of the filtrate is 7. And finally, drying the obtained product in a constant-temperature drying oven at 60 ℃ for 24 hours to prepare the hydrangea-shaped nano zinc oxide.
The SEM image of the embroidered spherical nano zinc oxide is shown in figure 1. It can be seen from fig. 1 that the flower-like zinc oxide is uniformly distributed, and the nanoflowers are tightly stacked layer by self-assembly to form a radioactive structure similar to an embroidered ball, which is a three-dimensional layered structure. The thickness of the nanosheets constituting these flowers was 20nm, and the diameter of the flowers was about 2 μm.
XRD characterization is respectively carried out on the commercial zinc oxide and the prepared spherical nano zinc oxide, and the specific result is shown in figure 2. The respective diffraction peaks of ZnO in fig. 2 coincide with the peak positions of the diffraction peaks of standard wurtzite crystalline form ZnO, and the corresponding crystal planes are (100), (002), (101), (102), (110), (103), (200), (112), (201), respectively, indicating that the sample coincides with the ZnO standard card JCPDS 79-2205. The lattice constant a is 3.35, b is 3.25 and c is 5.27, and no other impurity peaks are found, which indicates that the synthesized sample has higher purity.
From fig. 2, it can be seen that the crystal structures of the materials are not changed by the trisodium citrate dihydrate and the ethanol, which shows that the two materials are used as surfactants, only participate in the regulation of the zinc oxide structure and do not participate in the actual chemical reaction.
Example 2 preparation of Heat-conducting polyurethane coating doped with embroidered spherical Nano Zinc oxide
5.92g of IPDI, 2 drops of DBTDL and 11g of PCDL are mixed uniformly at 45 ℃ and reacted for 3 h. After the free-NCO in the titration system reaches a theoretical value, adding 0.91g of DMPA, heating to 65 ℃, and reacting for 3 hours; 0.04g of 4-methoxy group was added dropwise while maintaining the temperature at 65 ℃The phenylphenol (EMHQ) and 2.04g of PETA continue to react for 3 h; after the-NCO content reached the theoretical value, 0.3g of TMP was added and the reaction was carried out for 6 hours. Detecting 2270cm by infrared spectrometer-1And (4) completely eliminating the characteristic absorption peak of-NCO to obtain the target product. And (3) closing the heating device, cooling to normal temperature, adding 0.76g of TEA, stirring at high speed for 1h, adding 45g of deionized water, and stirring at high speed for 1h to obtain the photocuring waterborne polyurethane emulsion.
Weighing 10g of polyurethane emulsion, adding 0.5g of photoinitiator 1173, and uniformly dispersing 0.2g, 0.5g, 1g, 1.5g and 2g of hydrangeal nano ZnO in ethanol respectively, wherein the amount of ethanol is 10 mL/g of photoinitiator; and then mixing with polyurethane emulsion, uniformly stirring at normal temperature in a dark place, pouring into a polytetrafluoroethylene tank, standing at normal temperature for 48 hours, drying at 50 ℃ for 8 hours, and curing the coating in a photocuring machine for 35 seconds to obtain the thermal-conductive polyurethane coating of the hybrid spherical nano zinc oxide.
Application example 1
The thermal conductivity of the heat-conducting polyurethane coating prepared in example 2 was tested, and the test procedure was: the thermal conductivity of the coating is tested by using an LFA467 type laser thermal conductivity instrument of Germany Nachi company; the results are shown in Table 1.
TABLE 1
| Sample name | Thermal conductivity |
| WPU | 0.19 |
| WPU-2％ZnO | 0.28 |
| WPU-5％ZnO | 0.33 |
| WPU-10％ZnO | 0.52 |
| WPU-15％ZnO | 0.64 |
| WPU-20％ZnO | 0.69 |
As can be seen from the above table, with the increase of the amount of the hydrangeal nano zinc oxide, the thermal conductivity of the coating film is continuously increased, because the manufactured hydrangeal ZnO is composed of nanosheets building blocks, and some peeled small pieces are used as bridges to connect the hydrangeal ZnO superstructures with each other, which is beneficial to forming a compact three-dimensional (3-D) heat conducting network in a polyurethane matrix. So that heat can be quickly transferred along the thermally conductive network.
Claims (10)
1. A preparation method of a thermal conductive polyurethane coating doped with hydrangeal nano zinc oxide is characterized by comprising the following steps: firstly, preparing embroidered spherical nano zinc oxide powder by a template-free solvothermal method; then, preparing aqueous polyurethane emulsion by adopting diisocyanate, polyester diol and an additive; and finally, dispersing the hydrangea-shaped nano zinc oxide powder in the waterborne polyurethane emulsion, and curing to obtain the heat-conducting polyurethane coating.
2. The method for preparing the thermal conductive polyurethane coating doped with the embroidered spherical nano zinc oxide as claimed in claim 1, wherein the preparation process of the embroidered spherical nano zinc oxide powder is as follows: firstly, adding zinc acetate dihydrate and sodium citrate into a reaction vessel, then adding deionized water, and uniformly stirring until the zinc acetate dihydrate and the sodium citrate are completely dissolved; stirring and dispersing sodium hydroxide in ethanol; mixing the two solutions, heating and stirring for reaction; the obtained mixture is transferred into a high-pressure autoclave after ultrasonic treatment and is placed in a constant-temperature drying box for heating reaction; after the high-pressure reaction kettle is cooled to room temperature, opening the device, and collecting the obtained solution; and (4) carrying out suction filtration to obtain a white product, washing until the filtrate is neutral, and drying to obtain the hydrangea-shaped nano zinc oxide.
3. The method for preparing the thermal conductive polyurethane coating doped with the embroidered spherical nano zinc oxide as claimed in claim 2, wherein the preparation process of the embroidered spherical nano zinc oxide powder is as follows: adding 1.60-1.68g of zinc acetate dihydrate and 2.20-2.25g of sodium citrate into a reaction vessel, then adding 150-200mL of deionized water, and uniformly stirring at room temperature until the zinc acetate dihydrate and the sodium citrate are completely dissolved; dispersing 2.90-3.15g of sodium hydroxide in 70-80mL of ethanol; mixing the two solutions, heating to 38-42 deg.C, mixing and stirring for 1-3 h; carrying out ultrasonic treatment on the obtained mixture at 30-40kHz for 20-40min, and transferring the mixture into a high-pressure reaction container; heating the high-pressure reaction vessel at the temperature of 140 ℃ and 160 ℃ for reaction for 23-25h, cooling to room temperature, and collecting the obtained reaction liquid; filtering by suction filtration to obtain a white product, and washing with deionized water and ethanol for multiple times until the filtrate is neutral; and finally, drying the obtained product at 58-62 ℃ for 24h to obtain hydrangeal nano zinc oxide powder.
4. The preparation method of the thermal conductive polyurethane coating doped with the hydrangeal nano zinc oxide as claimed in claim 2, wherein the preparation process of the aqueous polyurethane emulsion is as follows: mixing diisocyanate, polyester diol and a catalyst, and reacting at constant temperature; after the free-NCO in the titration system reaches a theoretical value, adding a chain extender, and heating for continuous reaction; keeping the temperature, dropwise adding a polymerization inhibitor and an active blocking agent, and continuing to react; adding a micromolecular cross-linking agent for reaction after the-NCO content reaches a theoretical value; detecting 2270cm by infrared spectrometer-1Completely eliminating the characteristic absorption peak of-NCO to obtain a target product; and (3) closing the heating device, cooling to normal temperature, adding a neutralizing agent, stirring at high speed, adding deionized water, and stirring at high speed to obtain the photocuring waterborne polyurethane emulsion.
5. The preparation method of the heat-conducting polyurethane coating doped with the embroidered spherical nano zinc oxide as claimed in claim 4, which is characterized in thatThe method comprises the following steps: mixing 5.8-6.0g of diisocyanate, 11.5-13.2g of polyester diol and 1-2d of catalyst at 40-50 ℃, and reacting for 2-4h at constant temperature; after the free-NCO in the titration system reaches a theoretical value, adding 0.91-0.95g of chain extender, heating to 60-70 ℃, and continuing to react for 2-4 h; keeping the temperature at 60-70 ℃, dropwise adding 0.04-0.05g of polymerization inhibitor and 2.04-2.10g of active blocking agent, and continuing to react for 2-4 h; after the-NCO content reaches a theoretical value, adding 0.30-0.32g of micromolecule crosslinking agent, and reacting for 4-8 h; detecting 2270cm by infrared spectrometer-1Completely eliminating the characteristic absorption peak of-NCO to obtain a target product; and (3) closing the heating device, cooling to normal temperature, adding a neutralizer with the same amount of the chain extender, stirring at a high speed for 1h, adding 45-50mL of deionized water, and stirring at a high speed for 1h to obtain the photocuring waterborne polyurethane emulsion.
6. The preparation method of the heat-conducting polyurethane coating doped with the embroidered spherical nano zinc oxide, which is characterized by comprising the following steps of: the diisocyanate is at least one of toluene diisocyanate TDI, 4' -diphenylmethane diisocyanate MDI and isophorone diisocyanate IPDI;
the polyester dihydric alcohol is specifically polycarbonate dihydric alcohol PCDL;
the catalyst is dibutyltin dilaurate or stannous octoate;
the chain extender is dimethylolpropionic acid DMPA or dimethylbenzene anthracene DMBA;
the polymerization inhibitor is 4-methoxyphenol;
the active end-capping reagent is at least one of hydroxyethyl acrylate HEA, hydroxyethyl methacrylate HEMA and pentaerythritol triacrylate PETA;
the micromolecule cross-linking agent is trimethylolpropane TMP;
the neutralizer is triethanolamine TEA.
7. The method for preparing the thermal conductive polyurethane coating doped with the hydrangeal nano zinc oxide as claimed in claim 2, wherein the preparation process of the thermal conductive polyurethane coating is as follows: adding the embroidered spherical nano zinc oxide into ethanol, treating the mixture in an ultrasonic device, adding the prepared waterborne polyurethane emulsion under the stirring state, keeping out of the sun at room temperature, continuously stirring the mixture, adding a photoinitiator, uniformly dispersing, pouring the mixture into a polytetrafluoroethylene groove, standing, drying, and carrying out UV curing to obtain the heat-conducting polyurethane coating doped with the embroidered spherical nano zinc oxide.
8. The preparation method of the thermal conductive polyurethane coating doped with the hydrangeal nano zinc oxide as claimed in claim 2, which is characterized by comprising the following steps: according to the measurement that each gram of the spherical nano zinc oxide is dispersed in 10mL of ethanol, 0.20-0.26g of the spherical nano zinc oxide is added into the ethanol, and ultrasonic treatment is carried out for 2-4h at 30-40 kHz; slowly adding 10-12mL of prepared aqueous polyurethane emulsion under the stirring state; continuously stirring the mixture for 1-3h at room temperature in a dark place, adding a photoinitiator accounting for 2-5% of the mass of the aqueous polyurethane emulsion, uniformly dispersing, pouring into a polytetrafluoroethylene groove, standing for 1-2d, then placing in an oven at 45-50 ℃ for drying for 4-10h, and finally curing for 20-70s by using an ultraviolet curing machine to obtain the hydrangeal-shaped nano zinc oxide-doped heat-conducting polyurethane coating.
9. The method for preparing the thermal conductive polyurethane coating doped with the hydrangeal nano zinc oxide as claimed in claim 8, which is characterized in that: the photoinitiator was 1173 photoinitiator.
10. The thermal conductive polyurethane coating doped with hydrangeal nano zinc oxide prepared by the method of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114956159A (en) * | 2022-06-20 | 2022-08-30 | 江南大学 | Preparation method of hydrangea-shaped nano zinc oxide |
| CN115043400A (en) * | 2022-05-18 | 2022-09-13 | 黄河科技学院 | Nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal pitch as raw material, and preparation method and application thereof |
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| CN106188482A (en) * | 2016-07-13 | 2016-12-07 | 华南理工大学 | Nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043400A (en) * | 2022-05-18 | 2022-09-13 | 黄河科技学院 | Nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal pitch as raw material, and preparation method and application thereof |
| CN115043400B (en) * | 2022-05-18 | 2024-01-12 | 黄河科技学院 | Nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as raw material, and preparation method and application thereof |
| CN114956159A (en) * | 2022-06-20 | 2022-08-30 | 江南大学 | Preparation method of hydrangea-shaped nano zinc oxide |
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