Enhancement of antistatic properties of conductive carbon black/waterborne polyurethane UV-curable coatings by metal-organic framework materials
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摘要: 紫外光固化水性聚氨酯(UV-WPUA)作为绿色环保高性能的高分子涂料，适用于塑料、金属、纸张、皮革等多种基材，但是水性聚氨酯本身绝缘，随着静电荷的累积，对设备及人体产生不良影响，严重的甚至会引发爆炸火灾等危险情况，所以赋予水性聚氨酯抗静电属性成为当下热点。本研究采用导电炭黑(CB)作为UV-WPUA的导电填料，制备具有抗静电性能的紫外光固化涂料。再加入不同含量的金属有机框架材料MOF-801，进一步降低涂层的表面电阻。采用傅立叶变换红外光谱(FT-IR)、核磁共振氢谱仪(1H NMR)，确定UV-WPUA结构。采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)，确定MOF-801结构和微观形貌，以及MOF-801-CB/UV-WPUA涂层的分散性。结果表明，成功合成UV-WPUA乳液和MOF-801材料。在实验室恒温25 ℃，恒湿67%下，当CB质量比为15 wt%时，复合涂层表面电阻率为2.3×106 Ω。当在此涂料中加入1 wt%的MOF-801，涂层表面电阻率下降至1.7×105 Ω，且涂层硬度、附着力较好，双键转化率为70%，满足抗静电涂料的要求，证明金属有机框架材料的加入可以进一步提升紫外光固化涂层的抗静电性能。
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关键词:
- 紫外光固化水性聚氨酯 /
- MOF-801 /
- CB /
- 抗静电 /
- 涂料
Abstract: UV curable waterborne polyurethane (UV-WPUA) is a green, environmentally friendly, efficient and high performance polymer coating suitable for a wide range of substrates such as plastics, metals, paper, leather and so on. However, waterborne polyurethane itself is insulated, and with the accumulation of static charges, it can have adverse effects on equipment and human health, and even cause dangerous situations such as explosions and fires. Therefore, endowing waterborne polyurethane with anti-static properties has become a current hot topic. This study used conductive carbon black (CB) as a conductive filler for UV-WPUA to prepare UV curable coatings with anti-static properties. The surface resistivity of the coating can be further reduced by adding MOF-801, an organic framework material with varying levels of content. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (1H NMR) were used to determine the structure of UV-WPUA. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to determine the structure and microscopic morphology of MOF-801 and the dispersion of the MOF-801-CB/UV-WPUA coating. The results showed that the experiments were successful in synthesising UV-WPUA emulsion and MOF-801 materials. Under the constant temperature of 25℃ and humidity of 67% in the laboratory,the surface resistivity of the coating was 2.3×106 Ω when the mass content of CB was 15 wt%. When 1 wt% MOF-801 is added to this coating, the surface resistivity of the coating decreases to 1.7×105 Ω, the conversion of double bond is 70%, and the coating has good hardness and adhesion, meeting the requirements of anti-static coatings. It can be demonstrated that the addition of organic framework materials can further improve the antistatic performance of UV-cured coatings.-
Key words:
- UV-curable waterborne polyurethane /
- MOF-801 /
- CB /
- antistatic /
- coating
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图 4 UV-WPUA乳液、UV-WPUA固化膜、MOF-801-CB/UV-WPUA固化膜、CB和MOF-801的红外光谱
Figure 4. FT-IR spectra of UV-WPUA emulsion、UV-WPUA film、MOF801-CB/UV-WPUAfilm、CB and MOF-801
图 8 CB含量对涂层表面电阻的影响
Figure 8. The effect of CB content on the surface resistance of coatings
图 9 MOF-801含量对涂层表面电阻的影响
Figure 9. The effect of MOF-801 content on the surface resistance of coatings
图 10 不同相对湿度下对复合涂层的表面电阻
Figure 10. Surface resistance of composite coatings at different relative humidities
图 11 涂层脆断截面的SEM照片和EDS谱图
Figure 11. SEM image and EDS patterns of brittle fracture cross-section of coating
图 12 CB 30wt% /UV-WPUA涂层脆断截面的SEM照片
Figure 12. SEM photographs of brittle cross section of CB 30wt%/UV-WPUA coating
图 13 UV-WPUA、CB 15wt%/UV-WPUA和MOF-801 1wt%-CB 15wt%/UV-WPUA涂层的双键转化率
Figure 13. The double bond conversion of UV-WPUA、CB 15wt%/UV-WPUA and MOF-801 1wt%/CB 15wt%/UV-WPUA coatings
图 14 UV-WPUA、CB/UV-WPUA和MOF-801-CB/UV-WPUA涂层的热重曲线
Figure 14. Thermogravimetric curves of UV-WPUA、CB/UV-WPUA and MOF-801-CB/UV-WPUA
表 1 CB/UV-WPUA复合涂层配方
Table 1. CB/UV-WPUA Coating formula
Sample CB/wt% MOF-801/wt% 2959/wt% 1173/wt% UV-WPUA/wt% CB/UV-WPUA-1 0 0 4 3 93 CB/UV-WPUA-2 1 0 4 3 92 CB/UV-WPUA-3 3 0 4 3 90 CB/UV-WPUA-4 5 0 4 3 88 CB/UV-WPUA-5 7 0 4 3 85 CB/UV-WPUA-6 10 0 4 3 83 CB/UV-WPUA-7 15 0 4 3 78 CB/UV-WPUA-8 20 0 4 3 73 CB/UV-WPUA-9 25 0 4 3 68 CB/UV-WPUA-10 30 0 4 3 63 Notes: CB is a conductive carbon black; MOF-801 is a metal-organic framework; 2959 is a photoinitiator with the full name of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone; 1173 is a photoinitiator with the full name of 2-hydroxy-2-methyl-1-phenyl-1-propanone; UV-WPUA is a UV-curing waterborne polyurethane acrylate. 
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表 2 MOF-801-CB/UV-WPUA复合涂层配方
Table 2. MOF-801-CB/UV-WPUA Coating formula
Sample CB/wt% MOF-801/wt% 2959/wt% 1173/wt% UV-WPUA/wt% MOF-801-CB/UV-WPUA-1 15 0.5 4 3 77.5 MOF-801-CB/UV-WPUA-2 15 1 4 3 77 MOF-801-CB/UV-WPUA-3 15 1.5 4 3 76.5 MOF-801-CB/UV-WPUA-4 15 2 4 3 76 MOF-801-CB/UV-WPUA-5 15 2.5 4 3 75.5 MOF-801-CB/UV-WPUA-6 15 3 4 3 75
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表 3 CB含量对涂层表面电阻的影响
Table 3. The effect of CB content on the surface resistance of coatings
Sample CB wt/% surface resistance /Ω CB/UV-WPUA-1 5 5.3×1010 CB/UV-WPUA-2 10 2.5×109 CB/UV-WPUA-3 15 2.3×106 CB/UV-WPUA-4 20 3.4×104 CB/UV-WPUA-5 25 2.3×103 CB/UV-WPUA-6 30 4.3×102
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表 4 涂层的基本性能
Table 4. Basic properties of coatings
Sample CBwt/% MOF-801/wt/% Pencil Hardness Pendulum Hardness/s Adhesion CB/UV-WPUA-1 0 0 2 H 324 0 CB/UV-WPUA-2 1 0 3 H 347 0 CB/UV-WPUA-3 3 0 3 H 359 0 CB/UV-WPUA-4 5 0 3 H 371 0 CB/UV-WPUA-5 7 0 HB 312 0 CB/UV-WPUA-6 10 0 B 247 0 CB/UV-WPUA-7 15 0 B 269 0 CB/UV-WPUA-8 20 0 B 224 2 CB/UV-WPUA-9 25 0 B 165 4 CB/UV-WPUA-10 30 0 B 169 4
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表 5 MOF-801-CB/UV-WPUA复合涂层的基本性能
Table 5. Basic properties of MOF-801-CB/UV-WPUA composite coatings
Sample CBwt/% MOF-801 wt/% Pencil Hardness Pendulum Hardness/s Adhesion MOF-801-CB/UV-WPUA-1 15 0.5 B 237 0 MOF-801-CB/UV-WPUA-2 15 1 B 233 0 MOF-801-CB/UV-WPUA-3 15 1.5 B 238 0 MOF-801-CB/UV-WPUA-4 15 2 B 244 0 MOF-801-CB/UV-WPUA-5 15 2.5 B 248 2 MOF-801-CB/UV-WPUA-6 15 3 B 256 2
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表 6 MOF-801 1wt%-CB 15wt%/UV-WPUA复合涂层在不同相对湿度下的基本性能
Table 6. Basic properties of MOF-801 1wt%-CB 15wt%/UV-WPUA composite coatings at different relative humidity
Sample Relative Humidity/% Pencil Hardness Pendulum Hardness/s Adhesion MOF-801 1wt%-CB 15wt%/UV-WPUA-1 11% B 238 0 MOF-801 1wt%-CB 15wt%/UV-WPUA-2 33% B 229 0 MOF-801 1wt%-CB 15wt%/UV-WPUA-3 43% B 225 0 MOF-801 1wt%-CB 15wt%/UV-WPUA-4 67% B 233 0 MOF-801 1wt%-CB 15wt%/UV-WPUA-5 75% B 241 0 MOF-801 1wt%-CB 15wt%/UV-WPUA-6 98% B 219 0
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