A cesium tungsten bronze composite PET material, its preparation method and application

Abstract

The present invention discloses a cesium tungsten bronze composite PET material, its preparation method and application. The cesium tungsten bronze composite PET material, based on 100 parts by total weight, comprises 85 - 95 parts of PET masterbatch and 5 - 15 parts of CWO dispersion liquid; wherein, the CWO dispersion liquid comprises the following components: 20 - 50 parts of cesium tungsten bronze powder; ≤70 parts of organic solvent; 10 - 40 parts of dispersant; in the CWO dispersion liquid, the size of the cesium tungsten bronze powder is 10 - 100 nm. The cesium tungsten bronze composite PET material of the present invention has excellent infrared barrier performance and high visible light transmittance, and the preparation method is simple.

Description

Technical Field

[0001] The present invention specifically relates to a cesium tungsten bronze composite PET material, a preparation method thereof and an application thereof. Background Art

[0002] In summer in our country, extremely hot weather above 35 °C often occurs. The strong solar radiation will cause the internal temperature of relatively enclosed spaces such as buildings or vehicles to increase sharply, accelerating the aging and degradation processes of indoor furniture, automotive leather goods and plastic products. However, traditional building glass lacks heat insulation ability, especially the ability to isolate infrared radiation. In addition, the current building energy consumption shows an increasing trend year by year. Therefore, the development of new heat insulation materials has become a major trend in energy conservation and emission reduction.

[0003] Currently, common traditional heat shielding functional materials for transparent heat insulation include low-emissivity glass (Low-e), indium or antimony doped tin oxide (ITO or ATO), and nano-LaB6. However, these materials still have some obvious disadvantages at present. For example: The core low-emission coating of Low-e is a precious metal silver functional layer, which shows the reflection of solar heat. Usually, it requires a complex coating structure and multiple functional layers, and has relatively high requirements for processes and equipment, resulting in a relatively high application cost. ITO or ATO-based coatings also show heat shielding ability; however, indium is an expensive rare metal resource, resulting in a relatively high application cost. ATO mainly plays a heat insulation role in the infrared band after 1500 nm, and the heat insulation effect is limited. There is still a relatively high transmittance in the wavelength range of 780 - 1500 nm. The shielding ability of lanthanum hexaboride is specifically shown in the wavelength band around 1000 nm, and there is currently no good method to mass-produce nano-scale lanthanum hexaboride, and the production cycle and cost are relatively high.

[0004] Cesium tungsten bronze (CWO) is a nano-scale inorganic material that can absorb near-infrared light with wavelengths of 900 - 2000 nanometers. The heat insulation and infrared-proof products made of cesium tungsten bronze powder can greatly improve the comfort of the human body, save energy significantly, and achieve more effective warm in winter and cool in summer. However, cesium tungsten bronze nano-materials have high surface activity and adsorption, and are prone to agglomeration.

[0005] Polyethylene terephthalate (PET) has rigid groups on the main chain of its molecules and highly symmetric molecular chains, which endow it with excellent physical and mechanical properties, heat resistance, electrical properties, and film-forming properties, and it is also inexpensive. Therefore, PET is widely used in engineering plastics, fiber textiles, and the film industry. Currently, the main method to improve the infrared barrier performance of PET materials is to add a certain amount of inorganic materials with infrared heat insulation absorption. However, when the added inorganic materials are used in combination with organic polymers, there are problems of dispersibility and compatibility between substances, which reduces the light transmittance of the infrared barrier film; especially when cesium tungsten bronze nanomaterials are used in combination with resins, due to the generally high viscosity of the resins, it is difficult to disperse them, which will greatly reduce the performance of cesium tungsten bronze nanomaterials in absorbing infrared rays. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the defect of poor infrared barrier performance when cesium tungsten bronze nanomaterials are used in combination with resins in the prior art, and to provide a cesium tungsten bronze composite PET material, its preparation method and application. The cesium tungsten bronze composite PET material of the present invention has excellent infrared barrier performance and high visible light transmittance, and the preparation method is simple.

[0007] Regarding PET and cesium tungsten bronze powder, some people in the prior art have also used them in combination. As described in Chinese Patent Document CN110713701A, however, during the process of combining the two in that patent, there are defects such as uneven dispersion, large particle size, low visible light transmittance, and high haze value. In this application, the inventors creatively found that by using a specific amount of dispersant in combination with PET masterbatch and cesium tungsten bronze powder, and by adjusting the dosage of each component and the particle size of cesium tungsten bronze powder in the dispersion liquid, the infrared barrier performance and visible light transmittance of the cesium tungsten bronze composite PET material can be effectively improved; further, by adding a specific type of organic solvent to the system, the performance of the cesium tungsten bronze composite PET material can be further optimized.

[0008] The present invention solves the above technical problems through the following technical solutions:

[0009] The present invention provides a cesium tungsten bronze composite PET material. Based on 100 parts by total weight, it includes 85 - 95 parts of PET masterbatch and 5 - 15 parts of CWO dispersion liquid;

[0010] Among them, the CWO dispersion liquid includes the following components:

[0011] 20 - 50 parts of cesium tungsten bronze powder;

[0012] ≤70 parts of organic solvent;

[0013] 10 - 40 parts of dispersant;

[0014] In the CWO dispersion liquid, the size of the cesium tungsten bronze powder is 10 - 100 nm.

[0015] In the present invention, the PET masterbatch can be obtained through conventional commercial channels.

[0016] In the present invention, the dosage of the PET masterbatch is preferably 88 - 92 parts, such as 90 parts.

[0017] In the present invention, the dosage of the CWO dispersion liquid is preferably 8 - 12 parts, such as 10 parts.

[0018] In the present invention, in the CWO dispersion liquid, the size of the cesium tungsten bronze powder is preferably 20 - 60 nm, more preferably 30 - 50 nm, such as 40 nm, 42 nm or 43 nm.

[0019] In the preparation process of the CWO dispersion liquid in the present invention, the organic solvent will volatilize to a certain extent.

[0020] In the present invention, preferably, the CWO dispersion liquid comprises the following raw material components:

[0021] 20 - 50 parts of cesium tungsten bronze powder;

[0022] 20 - 70 parts of organic solvent;

[0023] 10 - 40 parts of dispersant.

[0024] Among them, the dosage of the organic solvent is preferably 25 - 45 parts, such as 30 parts or 40 parts.

[0025] In the present invention, the boiling point of the organic solvent is preferably lower than 100 °C.

[0026] In the present invention, the organic solvent is preferably one or more of alcohol solvents, ketone solvents and ester solvents.

[0027] Among them, the alcohol solvent is preferably ethanol and / or isopropanol, such as isopropanol.

[0028] Among them, the ketone solvent is preferably acetone and / or butanone, such as acetone.

[0029] Among them, the ester solvent is preferably ethyl acetate.

[0030] In the present invention, the dispersant generally refers to a substance that can provide the same charge, make the surface of the powder particles carry the same kind of charge to generate repulsion, and secondly, the branched chain is a high - molecular long chain, which can provide a certain steric hindrance, increase the distance between powder particles, so as to reduce the aggregation of solid or liquid particles in the dispersion system through the action of like - charge repulsion and steric hindrance.

[0031] In the present invention, the dispersant is preferably a polyurethane dispersant.

[0032] Among them, the models of the polyurethane dispersants are preferably EFKA4560 and / or EFKA4063.

[0033] In the present invention, the dosage of the dispersant is preferably 25 - 35 parts, such as 30 parts.

[0034] In the present invention, the cesium tungsten bronze powder can be obtained through conventional commercial channels.

[0035] In the present invention, the dosage of the cesium tungsten bronze powder is preferably 25 - 45 parts, such as 30 parts or 40 parts.

[0036] In a preferred embodiment, the raw materials of the cesium tungsten bronze composite PET material include 90 parts of PET masterbatch, 4 parts of cesium tungsten bronze powder, 3 parts of isopropanol, and 3 parts of EFKA4063 dispersant.

[0037] In a preferred embodiment, the raw materials of the cesium tungsten bronze composite PET material include 90 parts of PET masterbatch, 4 parts of cesium tungsten bronze powder, 3 parts of ethyl acetate, and 3 parts of EFKA4063 dispersant.

[0038] In a preferred embodiment, the raw materials of the cesium tungsten bronze composite PET material include 90 parts of PET masterbatch, 4 parts of cesium tungsten bronze powder, 3 parts of acetone, and 3 parts of EFKA4063 dispersant.

[0039] In a preferred embodiment, the raw materials of the cesium tungsten bronze composite PET material include 90 parts of PET masterbatch, 3 parts of cesium tungsten bronze powder, 4 parts of isopropanol, and 3 parts of EFKA4063 dispersant.

[0040] The present invention also provides a preparation method of the cesium tungsten bronze composite PET material as described above, which includes the following steps:

[0041] Mixing the CWO dispersion liquid after ball milling for 5 - 10 h with the PET masterbatch to obtain it.

[0042] In the present invention, the cesium tungsten bronze composite PET material can be in a paste state.

[0043] In the present invention, the preparation method of the CWO dispersion liquid can be conventional in the art, generally by mixing and ball milling the raw materials.

[0044] Among them, the equipment for mixing can be conventional in the art, such as a high-speed disperser.

[0045] Among them, the rotation speed of the mixing is preferably 1000 - 2000 rpm, such as 1400 rpm.

[0046] Among them, the mixing time is preferably 30 - 90 min, for example, 60 min.

[0047] In the present invention, the equipment for ball milling treatment can be conventional in the art, such as a grinding disperser.

[0048] In the present invention, the rotation speed of the ball milling treatment can be 2500 - 3500 rpm, for example, 3000 rpm.

[0049] In the present invention, the time of the ball milling treatment is preferably 6 - 9 h, for example, 8 h.

[0050] In the present invention, in the ball milling treatment, the grinding balls can be conventional in the art, such as zirconium beads.

[0051] In the present invention, in the ball milling treatment, the diameter of the grinding balls can be 0.1 - 0.6 mm, for example, 0.1 mm.

[0052] In the present invention, the equipment for mixing can be conventional in the art, such as a blender.

[0053] In the present invention, the mixing method can be conventional in the art, such as stirring.

[0054] In the present invention, during the mixing process, the rotation speed of stirring is preferably 500 - 1000 rpm, for example, 800 rpm.

[0055] In the present invention, during the mixing process, the stirring time is preferably 5 - 30 min, for example, 10 min.

[0056] In the present invention, the cesium tungsten bronze composite PET material can be obtained after mixing. The cesium tungsten bronze composite PET material can be in a paste state.

[0057] In the present invention, after mixing, it is preferably followed by melt extrusion and pelletizing. Generally, granular cesium tungsten bronze composite PET material can be obtained after pelletizing.

[0058] Among them, the equipment for melt extrusion and pelletizing can be conventional in the art, such as a twin-screw extruder. The length-diameter ratio of the twin-screw extruder can be conventional in the art, such as 30:1.

[0059] Among them, the temperature of the melt extrusion is preferably 270°C - 280°C, for example, 275°C.

[0060] Among them, during the melt extrusion process, the screw rotation speed is preferably 100 - 150 rpm, for example, 120 rpm.

[0061] In a preferred embodiment, the melting extrusion and granulation are carried out using a twin-screw extruder with a length-diameter ratio of 30:1, the processing temperature is 275 °C, and the melting and plasticization are carried out under the condition of a screw speed of 120 rpm. The cesium tungsten bronze composite PET material is prepared through a T-shaped die with an opening of 0.6 mm.

[0062] The present invention also provides an application of the cesium tungsten bronze composite PET material as described above in heat-insulating and infrared-proof products.

[0063] In the present invention, the heat-insulating and infrared-proof product can be any product, such as a film, a sheet or a heat-generating and warm-keeping fiber.

[0064] On the basis of conforming to the common knowledge in the art, the above preferred conditions can be combined arbitrarily to obtain various preferred examples of the present invention.

[0065] The reagents and raw materials used in the present invention are all commercially available.

[0066] The positive and progressive effects of the present invention are as follows:

[0067] (1) The cesium tungsten bronze composite PET material of the present invention has excellent infrared barrier performance and high visible light transmittance;

[0068] (2) In the cesium tungsten bronze composite PET material of the present invention, the cesium tungsten bronze nanomaterials can be evenly distributed, effectively improving the problem of agglomeration of cesium tungsten bronze nanoparticles;

[0069] (3) The cesium tungsten bronze composite PET material of the present invention has excellent mechanical properties;

[0070] (4) The preparation method of the cesium tungsten bronze composite PET material of the present invention is simple, can be industrially produced, and can be directly used for producing high-transparency and high-heat-insulating films, sheets, heat-generating and warm-keeping fibers, etc. Specific Embodiments

[0071] The present invention will be further illustrated by the following examples, but the present invention is not limited to the scope of the examples. The experimental methods without specific conditions in the following examples are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0072] The information of the raw materials used in the following examples and comparative examples is shown in Table 1 below:

[0073] Table 1

[0074]

[0075] The model and manufacturer of the equipment used in the following examples and comparative examples are shown in Table 2 below:

[0076] Table 2

[0077] Device Name Model Manufacturer Grinding and Dispersing Machine Ashizawa IM Piller High-Speed Dispersing Machine TGM-FL Tongguang Intelligence Twin-Screw Extruder RXT CPM Extrusion Group Solar Film Tester LS182 Linshang Technology Desktop Integrating Sphere Spectrophotometer Ci7 X-Rite

[0078] Example 1

[0079] (1) Preparation of nano CWO nano-dispersion:

[0080] Take 30 parts of isopropanol (organic solvent), 30 parts of EFKA4063 (dispersant), and 40 parts of nano CWO powder respectively in a reaction kettle, pre-mix them for 60 min with a high-speed disperser at 1400 rpm, and then sand mill them for 8 hours on a grinding disperser with 0.1 mm zirconium beads at a rotation speed of 3000 rpm to obtain a CWO dispersion.

[0081] (2) Put 90 parts of PET masterbatch and 10 parts of CWO dispersion into a blender, stir them at a high speed of 800 rpm for 10 minutes to mix evenly, and obtain a cesium tungsten bronze composite PET material.

[0082] Then put the above cesium tungsten bronze composite PET material into a twin-screw extruder with a length-diameter ratio of 30:1 in a metered manner, set the processing temperature at 275 °C, melt and plasticize it under the condition of a screw rotation speed of 120 rpm, and form a cesium tungsten bronze composite PET masterbatch with a uniform diameter through a T-shaped die with an opening of 0.6 mm, and cool and shear it into uniform granular cesium tungsten bronze composite PET masterbatch.

[0083] Example 2

[0084] Except that the isopropanol in step (1) is replaced by ethyl acetate, the rest of the operations and conditions are the same as those in Example 1.

[0085] Example 3

[0086] Except that the isopropanol in step (1) is replaced by acetone, the rest of the operations and conditions are the same as those in Example 1.

[0087] Example 4

[0088] The feeding ratio in step (1) is 40 parts of isopropanol, 30 parts of EFKA4063, and 30 parts of nano CWO powder;

[0089] Except that the dosage of the components added in step (1) is different, the rest of the operations and conditions are the same as those in Example 1.

[0090] Comparative Example 1

[0091] Except that the dispersant EFKA4063 in step (1) is replaced by a modified acrylate dispersant BYK2055, the rest of the operations and conditions are the same as those in Example 1.

[0092] Comparative Example 2

[0093] Except that isopropanol in step (1) is replaced by methyl benzoate, the remaining operations and conditions are the same as those in Example 1.

[0094] Comparative Example 3

[0095] In step (1), the feeding ratio is 30 parts of isopropanol, 5 parts of EFKA 4063, and 40 parts of nano-CWO powder;

[0096] Except that the dosage of the components added in step (1) is different, the remaining operations and conditions are the same as those in Example 1.

[0097] Comparative Example 4

[0098] Respectively take 3 parts of isopropanol, 3 parts of EFKA 4063, 4 parts of nano-CWO powder and 90 parts of PET masterbatch, put them into a blender, and stir at a high speed of 800 rpm for 10 minutes to mix evenly. Then, the above mixture is fed into a twin-screw extruder with a length-diameter ratio of 30:1 in a metered manner. The processing temperature is set at 275 °C, and it is melt-plasticized under the condition of a screw speed of 120 rpm. Through a T-shaped die with an opening of 0.6 mm, an infrared barrier PET composite functional masterbatch with a uniform diameter is formed, and it is cooled and sheared into uniform granular masterbatch.

[0099] Comparative Example 5

[0100] Except that the ball milling time in step (1) is adjusted to 12 h, the remaining operations and conditions are the same as those in Example 1.

[0101] Effect Example

[0102] Use an LS182 solar film tester to measure the infrared barrier and light transmittance of the sample.

[0103] Use a bench-top integrating sphere spectrophotometer to test the haze of the sample.

[0104] Perform performance tests on the cesium tungsten bronze composite PET masterbatches prepared in Examples 1-4 and Comparative Examples 1-5, as shown in the data in Table 3 below:

[0105] Table 3

[0106]

[0107]

[0108] As can be seen from Examples 1-4, the nano-CWO dispersion liquid added with a dispersant can be evenly dispersed and better fused with the organic polymer during the preparation of cesium tungsten bronze composite PET masterbatch by melt blending and extrusion, thereby endowing the cesium tungsten bronze composite PET masterbatch with a high infrared barrier rate and visible light transmittance; as can be seen from Comparative Examples 1-5, when other types of dispersants or organic solvents are used, or the process parameters are adjusted (changing the raw material mixing method or changing the ball milling time), the particle size of the prepared cesium tungsten bronze composite PET masterbatch is relatively large, the dispersion effect is poor, the haze increases, and the infrared barrier and transparency of the obtained products are both poor.

Claims

1. A cesium tungsten bronze composite PET material, characterized in that, Based on 100 parts by total weight, it comprises 85 - 95 parts of PET masterbatch and 5 - 15 parts of CWO dispersion; Among them, the CWO dispersion comprises the following components: 20 - 50 parts of cesium tungsten bronze powder; 20 - 70 parts of organic solvent; 10 - 40 parts of dispersant; In the CWO dispersion, the size of the cesium tungsten bronze powder is 20 - 60 nm; The organic solvent is one or more of alcohol solvents, ketone solvents and ester solvents; The ester solvent is ethyl acetate; The dispersant is a polyurethane dispersant; The preparation method of the CWO dispersion is to mix the raw materials and perform ball milling; The time of the ball milling is 5 - 10 h; The rotation speed of the ball milling treatment is 2500 - 3500 rpm; In the ball milling treatment, the diameter of the grinding balls is 0.1 - 0.6 mm.

2. The cesium tungsten bronze composite PET material according to claim 1, wherein The alcohol solvent is ethanol and / or isopropanol; The ketone solvent is acetone and / or butanone; the model of the polyurethane dispersant is EFKA4560 and / or EFKA4063.

3. The cesium tungsten bronze composite PET material according to claim 2, wherein The alcohol solvent is isopropanol; the ketone solvent is acetone.

4. The cesium tungsten bronze composite PET material according to claim 1, wherein The cesium tungsten bronze composite PET material satisfies one or more of the following conditions: (1) The dosage of the PET masterbatch is 88 - 92 parts; (2) The dosage of the CWO dispersion is 8 - 12 parts; (3) The dosage of the dispersant is 25 - 35 parts; (4) The dosage of the cesium tungsten bronze powder is 25 - 45 parts.

5. The cesium tungsten bronze composite PET material according to claim 1, characterized in that, The cesium tungsten bronze composite PET material satisfies one or more of the following conditions: (1) The dosage of the PET masterbatch is 90 parts; (2) The dosage of the CWO dispersion is 10 parts; (3) The dosage of the dispersant is 30 parts; (4) The dosage of the cesium tungsten bronze powder is 30 parts or 40 parts; (5) In the CWO dispersion, the size of the cesium tungsten bronze powder is 30 - 50 nm.

6. The cesium tungsten bronze composite PET material according to claim 1, wherein In the CWO dispersion, the size of the cesium tungsten bronze powder is 40 nm, 42 nm or 43 nm.

7. The cesium tungsten bronze composite PET material according to claim 1, wherein The dosage of the organic solvent is 25 - 45 parts.

8. The cesium tungsten bronze composite PET material according to claim 1, wherein, The dosage of the organic solvent is 30 parts or 40 parts.

9. The cesium tungsten bronze composite PET material according to claim 1, wherein The raw materials of the cesium tungsten bronze composite PET material include 90 parts of PET masterbatch, 4 parts of cesium tungsten bronze powder, 3 parts of isopropanol and 3 parts of EFKA4063 dispersant; Or, the raw materials of the cesium tungsten bronze composite PET material include 90 parts of PET masterbatch, 4 parts of cesium tungsten bronze powder, 3 parts of ethyl acetate and 3 parts of EFKA4063 dispersant; Or, the raw materials of the cesium tungsten bronze composite PET material include 90 parts of PET masterbatch, 4 parts of cesium tungsten bronze powder, 3 parts of acetone and 3 parts of EFKA4063 dispersant; Or, the raw materials of the cesium tungsten bronze composite PET material include 90 parts of PET masterbatch, 3 parts of cesium tungsten bronze powder, 4 parts of isopropanol and 3 parts of EFKA4063 dispersant.

10. A method for preparing a cesium tungsten bronze composite PET material according to any one of claims 1-9, characterized in that, It comprises the following steps: Mix the CWO dispersion after ball milling treatment for 5 - 10 h with the PET masterbatch to obtain it.

11. The preparation method of the cesium tungsten bronze composite PET material according to claim 10, wherein, In the method for preparing the CWO dispersion liquid, the rotation speed of mixing is 1000 - 2000 rpm; In the method for preparing the CWO dispersion liquid, the mixing time is 30 - 90 min.

12. The preparation method of the cesium tungsten bronze composite PET material according to claim 11, characterized in that, In the method for preparing the CWO dispersion liquid, the rotation speed of mixing is 1400 rpm; In the method for preparing the CWO dispersion liquid, the mixing time is 60 min.

13. The preparation method of the cesium tungsten bronze composite PET material according to claim 10, characterized in that, The time for the ball milling treatment is 6 - 9 h.

14. The preparation method of the cesium tungsten bronze composite PET material according to claim 13, characterized in that, The rotation speed of the ball milling treatment is 3000 rpm; and / or, the time for the ball milling treatment is 8 h.

15. The preparation method of the cesium tungsten bronze composite PET material according to claim 10, characterized in that, During the mixing process, the rotation speed of stirring is 500 - 1000 rpm; and / or, during the mixing process, the stirring time is 5 - 30 min.

16. The preparation method of the cesium tungsten bronze composite PET material according to claim 15, characterized in that, During the mixing process, the rotation speed of stirring is 800 rpm; and / or, during the mixing process, the stirring time is 10 min.

17. Application of a cesium tungsten bronze composite PET material as described in any one of claims 1 - 9 in a heat-insulating and infrared-proof product.

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