Preparation and properties of durable fluorinated acrylate-epoxy waterproof adhesive layer for steel bridge deck
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摘要: 钢桥面铺装层由于防水粘结层失效导致其使用寿命远远低于桥梁结构的使用年限。为了延长钢桥面铺装层的使用寿命,改善层间粘结状况,制备了一种耐久型聚合物防水粘结层。利用自由基溶液聚合法合成了一系列含氟量不同的聚丙烯酸丁酯-甲基丙烯酸十二氟庚酯-甲基丙烯酸甲酯-苯乙烯嵌段共聚物,将上述共聚物与双酚A型环氧树脂E-51物理共混得到5种自分层防水涂料,再将其涂覆于钢桥面板表面静置干燥即可得到防水粘结层。通过傅里叶变换红外光谱、静态接触角测试、扫描电子显微镜研究了涂料在固化阶段的自分层行为,利用表面能理论对自分层行为进行了理论验证。最后研究了不同含氟量粘结层的高低温性能、力学性能、不透水性能、粘结强度及紫外老化耐久性。结果表明:当含氟量为20wt%时,其拉伸强度与断裂伸长率达到最大值,分别可达到7.04 MPa,128.9%;同时表现出最佳的粘结强度与紫外老化耐久性,综合性能达到最优。Abstract: The service life of steel deck pavement is far shorter than that of bridge structure due to the failure of waterproof adhesive layer. In order to prolong the service life of steel bridge deck pavement and improve the bonding condition between layers, a durable polymer waterproof bonding layer was prepared. A series of poly(butyl acrylate)-dodecafluoroheptyl methacrylate-methyl methacrylate-styrene block copolymers with different fluorine contents were synthesized by free radical solution polymerization. Five kinds of self-stratified waterproof coatings were obtained by physical blending of the above copolymers with bisphenol A epoxy resin E-51, and then they were coated on the surface of steel bridge deck to get a waterproof bonding layer after standing and drying. The self-stratification behavior of coatings in curing stage was studied by Fourier transform infrared spectroscopy, static contact angle test and scanning electron microscope. The self-stratification behavior was theoretically verified by surface energy theory. Finally, the high and low temperature properties, mechanical properties, impermeability, bonding strength and ultraviolet aging durability of the bonding layers with different fluorine contents were studied. The results show that when the fluorine content is 20wt%, the tensile strength and elongation at break reach the maximum, reaching 7.04 MPa and 128.9% respectively. At the same time, it shows the best bonding strength and ultraviolet aging durability, and the comprehensive performance reaches the best.
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表 1 实验试剂
Table 1. Experimental materials
Material Purity Manufacturer Methyl methacrylate (MMA) AR Shandong Chuanghe New Materials CO., LTD. Butyl acrylate (BA) AR Shandong Chuanghe New Materials CO., LTD. Styrene (St) AR Tianjin Damao Chemical Reagent Factory Azodiisobutyronitrile AR Tianjin Damao Chemical Reagent Factory Ethyl acetate (EA) AR Tianjin Damao Chemical Reagent Factory Diiodomethane AR Shanghai Merck Chemical Reagent CO., LTD. Xylene AR Shandong Chuanghe New Materials CO., LTD. N-Butanol AR Shandong Chuanghe New Materials CO., LTD. Epoxy 51 AR Danbao Epoxy Resin CO., LTD. Polyamide curing agent AR Meidong Chemical Materials CO., LTD. Dodecafluoroheptyl methacrylate (DFHMA) AR Harbin Xuejia Fluorosilicone Chemical CO., LTD. 表 2 含氟量不同的含氟丙烯酸嵌段聚合物的命名
Table 2. Naming of fluorinated acrylic block polymers with different fluoride content
Sample Fluorine
content/wt%Mass ratio of
FRx: Epoxy (E51)FR1 5 — FR2 10 — FR3 15 — FR4 20 — FR5 25 — FR1-E51 5 3∶7 FR2-E51 10 3∶7 FR3-E51 15 3∶7 FR4-E51 20 3∶7 FR5-E51 25 3∶7 Note: x=1−5. 表 3 含氟丙烯酸树脂的物化性能
Table 3. Physicochemical properties of fluorinated resin
Sample Appearance Viscosity/(mPa·s) Solid
content/%Monomer conversion
rate/%Shore hardness A FR1 Light yellow transparent viscous liquid 1690 56 85 58 FR2 Light yellow transparent viscous liquid 1720 54 90 65 FR3 Light yellow transparent viscous liquid 1726 55 93 75 FR4 Light yellow transparent viscous liquid 1730 56 91 87 FR5 Light yellow transparent viscous liquid 1735 58 94 92 表 4 防水涂料各个组分的接触角及其表面能
Table 4. Contact angle and surface energy of each component of waterproof coatings
Sample Contact angle (H2O)/(°) Contact angle (CH2I2)/(°) γd/(mN·m−1) γp/(mN·m−1) γ/(mN·m−1) FR1 103 50 35.7 0.1 35.8 FR2 106 45 24.7 0.2 24.9 FR3 108 42 18.1 0.5 18.6 FR4 107 37 18.5 0.6 19.1 FR5 105 35 22.8 0.4 23.2 E51 71 26 40.4 6.7 47.1 Substrate 36 17 35.7 28.2 63.9 Notes: γd—Dispersion component of surface energy; γp—Polarity component of surface energy; γ—Surface energy. 表 5 自分层防水涂料的界面能参数
Table 5. Interface energy parameters of self-stratifying coatings
Sample ${\gamma _{{\text{12}}}}$ ${\gamma _{{\rm{s}}1}}$ ${\gamma _{{\rm{{{s}}2}}}}$ ${\gamma _{{\rm{s}}1}} - {\gamma _{{\rm{s}}2}} - {\gamma _{12}}$ ${\gamma _{\rm{s}}} - ({\gamma _{ {\rm{s} }2} } + {\gamma _{12} } + {\gamma _1})$ ${\gamma _{{\rm{s}}1}} - {\gamma _{\text{1}}} - {\gamma _{{\rm{s}}2}} + {\gamma _2}$ FR1-E51 6.69 27.9 13.5 7.71 7.91 25.7 FR2-E51 9.90 29.6 13.5 6.2 15.6 38.3 FR3-E51 13.83 32.49 13.5 5.16 17.97 47.49 FR4-E51 13.24 31.9 13.5 5.16 18.06 46.4 FR5-E51 10.49 29.8 13.5 5.81 16.71 40.2 Notes: γ12—Interface energy between components 1 and 2; γs1—Interface energy between components 1 and substrate; γs2—Interface energy between components 2 and substrate. 表 6 不同含氟量防水粘结层的高温稳定性
Table 6. High temperature stability test with different fluorine contents
Sample Test result FR1-E51 Without flowing and dripping FR2-E51 Without flowing and dripping FR3-E51 Without flowing and dripping FR4-E51 Without flowing and dripping FR5-E51 Flowing and dripping 表 7 防水粘结层不透水性测试结果
Table 7. Impermeability test of waterproof coatings
Sample Test result FR1-E51 Impermeable FR2-E51 Impermeable FR3-E51 Impermeable FR4-E51 Impermeable FR5-E51 Impermeable -
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