Modified ETFE material and application thereof

Abstract

The invention discloses a modified ETFE material and application thereof, and the modified ETFE material comprises 90-100 parts by mass of ETFE, 0.5-2 parts by mass of an anti-ultraviolet agent, 0.2-0.6 part by mass of an antioxidant, 0.2-1 part by mass of a light stabilizer, 0.2-1 part by mass of a heat stabilizer, 0.5-10 parts by mass of modified ATO and 3-12 parts by mass of a coupling agent. The modified ETFE material provided by the invention has the characteristics of excellent mechanical strength, weather resistance, self-cleaning property and the like, also has excellent infrared barrier property, and is particularly suitable for being applied to preparation of ETFE films for high infrared barrier buildings.

Description

Technical Field

[0001] This invention relates to ETFE films for use in the construction field, and particularly to a modified ETFE material and its applications. Background Technology

[0002] ETFE (ethylene tetrafluoroethylene copolymer) membranes are lightweight, highly transparent, possess excellent mechanical strength, weather resistance, and self-cleaning properties, earning them the nickname "soft glass." In architectural applications, ETFE membranes can achieve a visible light transmittance of up to 95%, approaching that of glass but weighing only 1 / 100th of glass, significantly reducing the structural load on buildings. However, while ETFE membranes offer excellent light transmittance, they also suffer from excessively high solar radiation heat transmittance, directly impacting the building's energy efficiency.

[0003] With the continuous improvement of global building energy efficiency standards and the in-depth promotion of green building concepts, the development of ETFE architectural membrane materials with high-efficiency infrared blocking performance has become an urgent need for the industry. Research shows that solar radiation energy is mainly concentrated in the visible and near-infrared bands, with near-infrared light (780-2500nm) carrying a large amount of heat. Therefore, it is possible to try adding infrared blocking fillers to ETFE membrane materials to block infrared heat from solar radiation, achieving building energy conservation while maintaining good light transmittance. However, due to the poor compatibility of ETFE materials, the infrared blocking fillers have poor dispersion and are prone to aggregation, severely affecting infrared blocking performance. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a modified ETFE material and its application, which can modify ETFE material to give it excellent infrared blocking performance.

[0005] To address the aforementioned technical problems, the first aspect of this invention provides a modified ETFE material comprising the following components in parts by mass: ETFE, 90-100 parts by weight; UV protectant, 0.5-2 parts by weight; Antioxidant, 0.2-0.6 parts by weight; Light stabilizer, 0.2-1 parts by weight; Heat stabilizer, 0.2-1 parts by weight Modified ATO, 0.5-10 parts by weight; Coupling agent, 3-12 parts by weight.

[0006] In this invention, ETFE material is used as the base material to ensure that the modified ETFE material possesses excellent mechanical strength, weather resistance, and self-cleaning properties. Simultaneously, UV stabilizers are added to improve its UV resistance, antioxidants to improve its oxidation resistance, light stabilizers to extend its service life under light exposure, heat stabilizers to increase its thermal stability, and modified ATO (modified antimony tin oxide) to increase its infrared blocking properties. Furthermore, by adding modified ATO and coupling agents, the dispersibility of the modified ATO filler in EFTE and its interfacial compatibility with the ETFE material are significantly improved, greatly enhancing the infrared blocking effect. Moreover, through synergistic effects with other additives such as UV stabilizers, the modified ETFE material provided in this application has better heat insulation performance and a longer service life. It should be noted that the modified ETFE provided in this invention can also have pigments added as needed to change the film color, such as adding ultramarine blue (e.g., 0.005-0.05 parts by weight).

[0007] It should also be noted that ETFE can be, for example, ETFE granules with a melt index of 5-8 g / 10 min, ETFE granules with a melt index of 8-13 g / 10 min, or ETFE granules with a melt index of 25-35 g / 10 min; the UV absorber can be, for example, a benzotriazole organic UV absorber, a triazine organic UV absorber, or a combination of both (e.g., a 1:1 mixture); the antioxidant can be, for example, one or more of antioxidant S60, antioxidant 608, or antioxidant 1010; and the light stabilizer can be, for example, the hindered amine light stabilizer RIASORB. ® UV-119; the heat stabilizer may be, for example, SiO2 nanoparticles (particle size range, for example, 10-50 nm).

[0008] In one specific embodiment, ATO modification involves altering the surface of ATO to achieve a water contact angle greater than 120°. Preferably, the ATO modification method utilizes a fluorinated silane. Specifically, this involves dispersing ATO in a solvent (a mixture of isopropanol and methyl ethyl ketone, or a mixture of ethanol and methyl isobutyl ketone), adding the fluorinated silane, and stirring at 60°C-80°C for 2-4 hours to complete the modification. The preferred mass ratio of ATO to the fluorinated silane is 100:1.4-1.8. More preferably, the fluorinated silane is selected from one or more of perfluorooctyltriethoxysilane, perfluorododecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, and heptadecafluorodecyltrimethoxysilane.

[0009] In this specific implementation scheme, since conventional ATO is prone to agglomeration in ETFE, has poor dispersion, and poor interfacial compatibility with ETFE materials, its surface is modified to improve its agglomeration and poor dispersibility. At the same time, it is combined with a coupling agent to increase its interfacial compatibility with ETFE materials, thereby further improving its dispersed phase in ETFE.

[0010] In one specific embodiment, the coupling agent is prepared as follows: ETFE and GMA (glycidyl methacrylate) are grafted in a solvent under an inert atmosphere and in the presence of a photocatalyst, under ultraviolet light irradiation. After the reaction, post-treatment is performed to obtain ETFE-g-PGMA (ethylene tetrafluoroethylene copolymer-grafted-glycidyl methacrylate polymer), i.e., the coupling agent. Preferably, the solvent is DMF (N,N-dimethylformamide) organic solvent, and the photocatalyst is TMPd (N,N,N',N'-tetramethyl-p-phenylenediamine). More preferably, the post-treatment includes: first, solid-liquid separation of the product, then washing the solid phase with an organic solvent, and then drying to obtain the coupling agent. The organic solvent washing includes washing in a mixed solution of dichloromethane and methanol, followed by rinsing with acetone.

[0011] In this specific implementation scheme, grafting is performed because ETFE has poor interfacial compatibility, making it difficult to interact effectively with coupling agents. Therefore, it is preferable to first graft ETFE material with GMA, and then add the grafted product as a coupling agent to the reaction system. This effectively improves the coupling effect, enabling the coupling between ETFE material and filler, avoiding filler agglomeration, and preventing interfacial delamination between filler and ETFE material. This is beneficial for the modification of ETFE material.

[0012] In one specific embodiment, the modified ETFE material is obtained by the following method: S1. Add ETFE, UV stabilizer, antioxidant, light stabilizer, heat stabilizer, ultramarine blue, modified ATO, and coupling agent to a high-speed mixer and mix for 10 minutes. After mixing evenly, add the mixture to a twin-screw granulator for granulation. The temperature is controlled between 190-300℃. During the granulation process, the temperature of the cooling water is controlled between 0-30℃. After granulation, dry the mixture to obtain the primary granulated modified particles. S2. The modified particles obtained from the initial granulation in S1 are added to a high-speed mixer for mixing, and then granulated again using a twin-screw granulator. The temperature is controlled between 190-300℃, and the temperature of the cooling water during the granulation process is controlled between 0-30℃. After granulation, the particles are dried to obtain modified ETFE composite material particles.

[0013] In this specific implementation plan, the two-stage granulation process can result in more uniform dispersion and mixing of the components, thereby improving the modification effect of the ETFE material.

[0014] To address the aforementioned technical problems, a second aspect of this invention is the application of the aforementioned modified ETFE material in the preparation of high infrared-blocking ETFE films for building applications. Understandably, due to the excellent infrared blocking properties of the modified ETFE material, the ETFE films obtained using it possess at least excellent infrared blocking rates. Furthermore, they also exhibit superior performance in tensile strength, elongation at break, visible light transmittance, haze, and heat recovery, making them suitable for application in the building sector. Detailed Implementation

[0015] The technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. Example 1

[0016] ATO modification: Commercially available ATO powder was dispersed in a mixed solvent, perfluorooctyltriethoxysilane was added, and the mixture was stirred at 60℃-80℃ for 2-4 hours. After drying, modified ATO was obtained. Table 1 shows the materials and experimental conditions. Table 1 Dosage of perfluorooctyltriethoxysilane / % Solvent (type, ratio, etc.) v / v Temperature (°C) Reaction time (h) Contact angle (°) Modified Group 1 0 Ethanol: Methyl isobutyl ketone = 1:1 60 2 54 Modified Group 2 0.5 Ethanol: Methyl isobutyl ketone = 1:1 60 2 82 Modified Group 3 1.4 Ethanol: Methyl isobutyl ketone = 1:1 60 2 121 Modified Group 4 1.5 Ethanol: Methyl isobutyl ketone = 1:1 60 2 132 Modified Group 5 1.8 Ethanol: Methyl isobutyl ketone = 1:1 60 2 125 The amount (by mass) of perfluorooctyltriethoxysilane is relative to the amount (by mass) of ATO. It should be noted that ATO without fluorosilane modification exhibits strong hydrophilicity. After modification (i.e., after surface coating with fluorosilane), the organic groups of the fluorosilane are exposed on the outer surface, making the modified ATO hydrophobic and improving its compatibility with ETFE materials. Furthermore, it was found that the interfacial compatibility between modified ATO and ETFE is even better when the water contact angle is greater than 120°. Example 2

[0017] Preparation of coupling agent: First, 0.5 g ETFE and 5 mg photocatalyst TMPd were placed in a 10 ml quartz reaction tube and replaced with a nitrogen atmosphere. Then, GMA (glycidyl methacrylate) and solvent (DMF solvent) were added. The grafting reaction was carried out under ultraviolet light (386 nm, 10 W) for 1 h. After the reaction, the solid phase was centrifuged (speed controlled between 10000-12000 r / min) for 20 min. The separated solid phase was added to a mixture of dichloromethane and methanol (dichloromethane:methanol = 10:1), stirred and washed, then washed twice with acetone, and then dried under vacuum at 50 °C to obtain ETFE-g-PGMA coupling agent. Example 3

[0018] Preparation of modified ETFE materials: 1. Experimental materials The substrate is ETFE particles (commercially available); The UV protectant is a mixture of Tinuvin 326 (benzotriazole) and Tinuvin 400 (triazine) in a 1:1 weight ratio. The antioxidant is antioxidant 1010, which is commercially available. The light stabilizer is the hindered amine light stabilizer RIASORB. ® UV-119 is commercially available. The heat stabilizer is nano-SiO2 with a particle size of 10-50nm, which is commercially available. Ultramarine blue, commercially available; The modified ATO (modified antimony tin oxide) was obtained from Example 1; The coupling agent was obtained from Example 2; 2. The preparation process is as follows: S1. Add ETFE particles, UV stabilizer, antioxidant, light stabilizer, heat stabilizer, ultramarine blue, modified ATO, and coupling agent to a high-speed mixer and mix for 10 minutes. After mixing evenly, add to a twin-screw granulator for granulation. The temperature is controlled between 190-300℃. During the granulation process, the temperature of the cooling water is controlled between 0-30℃. After granulation, dry to obtain the primary granulated modified particles. S2. Add the primary granulated modified particles obtained in S1 to a high-speed mixer and mix for 10 minutes. After mixing evenly, add the particles to a twin-screw granulator for secondary granulation. The temperature is controlled between 190-300℃. During the granulation process, the temperature of the cooling water is controlled between 0-30℃. After granulation, dry the particles to obtain modified ETFE composite material particles.

[0019] The material addition ratios are shown in Table 3: Table 2 Comparison Group 1 Comparison Group 2 Comparison Group 3 Experimental group 1 Experimental group 2 Experimental group 3 Experimental group 4 Experimental group 5 Experimental group 6 ETFE 100 100 100 95 95 95 95 92 90 Tinuvin 326 / Tinuvin 400 1 1 1 1 1 1 1 1 1 Antioxidant 1010 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 RIASORB® UV-119 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 <![CDATA[Nanometer SiO2]]> 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Ultramarine 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Unmodified ATO 0 5 5 0 0 0 0 0 0 Modified ATO 0 0 0 3 5 7 9 5 5 ETFE-g-PGMA 0 0 5 5 5 5 5 8 10 in: No coupling agent or modified ATO component was added in control group 1; The modified ATO added in control group 2 was the modified product from control group 1; no coupling agent was added. The modified ATO added in control group 3 was the modified product from control group 1, with the addition of a coupling agent; The modified ATO added in experimental group 1 was the modified product in modified group 2; The modified ATO added in experimental group 2 was the modified product in modified group 3; The modified ATO added in experimental group 3 was the modified product from modified group 4. The modified ATO added in experimental group 4 was the modified product in modified group 5. The modified ATO added in experimental group 5 is the modified product in modified group 5; The modified ATO added in experimental group 6 was the modified product from modified group 5. Example 4

[0020] Preparation of high infrared blocking ETFE film: The modified ETFE composite material particles obtained in Example 3 were added to a casting extruder for casting film formation. The temperature was controlled between 230-350℃. After extrusion, the film was first cooled by a cooling roller and then traction and winding to obtain a high infrared blocking ETFE film. Example 5

[0021] Test example: 1. Test sample: The ETFE film prepared in Example 4 was used, with a thickness of 100 μm.

[0022] 2. Testing Method: 1) The visible light transmittance and infrared blocking rate of the infrared blocking film were tested and determined using an ultraviolet-visible-near-infrared spectrophotometer.

[0023] 2) Tensile strength and elongation at break shall be tested in accordance with the test method of GB / T 1040.3 2006.

[0024] 3) Heat shrinkage test. The test temperature is 160℃ and the test time is 30 minutes.

[0025] 3. Test results: As shown in Table 3 Table 3 Thickness / μm Tensile strength / MPa Elongation at break / % Visible light transmittance / % Haze / % Infrared blocking rate / % Heat shrinkage / % Comparison Group 1 100 36 420 88 8 15 -2.5 Comparison Group 2 100 33 310 81 12 41 -2.8 Comparison Group 3 100 35 324 82 11 51 -2.3 Experimental group 1 100 42 360.5 85 10 65 -1.9 Experimental group 2 100 45.6 337 83 11 72 -2.0 Experimental group 3 100 41 364 82 13 74 -2.7 Experimental group 4 100 42.5 387 78 14 80 -2.4 Experimental group 5 100 45 378 83 11 76 -2.3 Experimental group 6 100 43 355 84 10 78 -2.9 As can be seen from Table 3, the infrared blocking performance of Examples 1 to 6 is superior to that of Comparative Examples 1, 2 and 3, and the tensile strength is also superior to that of Comparative Groups 1, 2 and 3, making them suitable for use in the construction field.

[0026] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A modified ETFE material characterized in that, The modified ETFE material comprises the following components by mass parts: ETFE, 90-100 mass parts; ultraviolet inhibitor, 0.5-2 mass parts; antioxidant, 0.2-0.6 mass parts; light stabilizer, 0.2-1 mass parts; thermal stabilizer, 0.2-1 mass parts modified ATO, 0.5-10 mass parts; coupling agent, 3-12 mass parts.

2. The modified ETFE material of claim 1, wherein, The modified ATO is modified on the surface of ATO to have a water contact angle greater than 120°.

3. The modified ETFE material of claim 2, wherein, The method for modifying the modified ATO is to modify the ATO with fluorine-containing silane.

4. The modified ETFE material of claim 3, wherein, The fluorine-containing silane is selected from one or more of perfluorooctyltriethoxysilane, perfluorododecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, and heptadecafluorodecyltrimethoxysilane.

5. The modified ETFE material of claim 1, wherein, The preparation method of the coupling agent is: ETFE and GMA are subjected to grafting reaction in a solvent under the presence of an inert atmosphere and a photocatalyst under ultraviolet light irradiation, and after the reaction is completed, post-treatment is performed to obtain ETFE-g-PGMA, i.e., the coupling agent.

6. The modified ETFE material of claim 5, wherein, The solvent is DMF organic solvent, and the photocatalyst is TMPd.

7. The modified ETFE material of claim 5, wherein, The post-treatment comprises: solid-liquid separation of the product is performed first, then the solid phase is washed with an organic solvent, and then drying is performed to obtain the coupling agent.

8. The modified ETFE material of claim 7, wherein, The organic solvent washing comprises washing in a mixed solution of dichloromethane and methanol first, and then washing with acetone.

9. The modified ETFE material of any of claims 1-8, wherein, The modified ETFE material is obtained by the following method: S1, ETFE, ultraviolet inhibitor, antioxidant, light stabilizer, thermal stabilizer, ultramarine blue, modified ATO, and coupling agent are added into a high-speed mixer and mixed for 10 minutes, and after uniform mixing, a double-screw granulator is used for granulation, the temperature is controlled to be between 190-300°C, the temperature of cooling water during the granulation process is controlled to be between 0-30°C, after the granulation is completed, drying is performed to obtain primary granulation modified particles; S2, the primary granulation modified particles obtained in S1 are added into a high-speed mixer for mixing, and then a double-screw granulator is used for secondary granulation, the temperature is controlled to be between 190-300°C, the temperature of cooling water during the granulation process is controlled to be between 0-30°C, after the granulation is completed, drying is performed to obtain modified ETFE composite material particles.

10. Use of the modified ETFE material according to any one of claims 1-8 in the preparation of high-infrared-shielding ETFE film for buildings.