Effect of organic scaffold structure on properties of styrene butadiene rubber/ ethylene vinyl acetate composite foams
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摘要: 为提高橡胶发泡材料尺寸稳定性及实现其广泛的工业化应用，基于硫磺和过氧化二异丙苯的交联体系，通过机械共混的方式，以具有结晶性的乙烯-醋酸乙烯共聚物(EVA)构筑有机支架结构，制备了高尺寸稳定性的丁苯橡胶(SBR)/EVA复合发泡材料。研究了不同醋酸乙烯(VA)含量的EVA对SBR/EVA复合材料结晶性、相容性、泡孔形貌、尺寸稳定性和力学性能的影响规律，并探明了EVA结晶区作为有机支架结构的抗收缩机制。结果表明：不同VA含量EVA的SBR/EVA复合材料都具有良好的发泡行为。高结晶度的EVA (VA含量为18%)使SBR/EVA复合发泡材料的收缩率减小至4.7%，硬度和压缩强度(60%)分别增加到70 Shore C和22 MPa。Abstract: In order to improve the dimensional stability of the rubber-based foam material and realize its wide industrialization, an organic scaffold structure was constructed with crystalline ethylene vinyl acetate copolymer (EVA) to enhance the dimensional stability of styrene butadiene rubber (SBR)/EVA composite foam based on the cross-linked structure of sulfur and dicumyl peroxide through mechanical blending. The effects of different content of vinyl ester (VA) content on the crystallinity, compatibility, cell morphology, dimensional stability and mechanical properties of SBR/EVA composites were studied, and the anti-shrinkage mechanism of the EVA crystal area as an organic scaffold structure was explored. The results show that SBR/EVA composites with different VA content of EVA have good foaming behavior. The shrinkage of SBR/EVA composite foam with high crystallinity EVA (18% VA content) is reduced to 4.7% and its hardness and compression stress (60%) are increased to 70 Shore C and 22 MPa, respectively.
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图 1 不同醋酸乙烯(VA)含量的乙烯-醋酸乙烯共聚物(EVA)对丁苯橡胶(SBR)/EVA复合材料结晶行为的影响: (a) DSC曲线; (b) XRD图谱
Figure 1. Effect of ethylene vinyl acetate (EVA) with different vinyl ester (VA) content on crystallization behavior of styrene butadiene rubber (SBR)/EVA composite foams: (a) DSC curves; (b) XRD patterns
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图 2 不同VA含量EVA的SBR/EVA复合材料截面的SEM和超景深3D显微镜图像
Figure 2. SEM and ultra-depth 3D images of cross-sectioned SBR/EVA composites with different VA content EVA
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图 3 不同VA含量EVA的SBR/EVA复合发泡材料的截面泡孔结构的SEM图像
Figure 3. SEM images of cross-sectioned cell structure of SBR/EVA composite foams with different VA content EVA
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图 4 不同VA含量EVA的SBR/EVA复合发泡材料的平均泡孔尺寸和泡孔密度
Figure 4. Mean cell size and cell density of SBR/EVA composite foams with different VA content EVA
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图 5 不同VA含量的EVA对SBR/EVA复合发泡材料尺寸稳定性的影响: (a)收缩率; (b)后收缩率
Figure 5. Effect of EVA with different VA content on dimensional stability of SBR/EVA composite foams: (a) Shrinkage; (b) Post shrinkage
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图 6 EVA结晶区作为有机支架结构的抗收缩机制
Figure 6. Anti-shrinkage mechanism of organic scaffold structure for EVA crystalline region
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图 7 SBR/EVA复合发泡材料的物理和力学性能: (a)密度; (b)硬度; (c)应力-应变曲线; (d)压缩应力-应变(60%)曲线
Figure 7. Physical and mechanical properties of SBR/EVA composite foams: (a) Density; (b) Hardness; (c) Stress-strain curves; (d) Compressive stress-strain (60%) curves
表 1 不同VA含量EVA的SBR/EVA复合材料的结晶行为
Table 1 Crystallization behavior of SBR/EVA composites with different VA content EVA
VA content/% ΔHf/(J·g−1) Tm1/℃ Tm2/℃ χc/% 18 524.8 50.1 89.4 8.15 26 128.4 52.4 73.9 1.99 28 107.3 50.3 75.3 1.67 33 79.7 48.5 66.0 1.24 40 72.3 48.3 — 1.12 Notes: ΔHf —Enthalpy of melting; Tm1, Tm2—Melting temperature; χc—Crystallinity. 
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表 2 VA含量为18%的SBR/EVA复合发泡材料与其他发泡材料的物理和力学性能对比[34-41]
Table 2 Comparison of physical and mechanical properties between SBR/EVA composite foam with VA content of 18% and other foam materials[34-41]
Material Density/(g·cm−3) Shrinkage/% Tensile/MPa Elongation/% Reference EVA/MWCNT 0.15 — 3.83 251 [34] EVA/POE 0.18 — 2.66 268 [35] EVA/CPE 0.12 7.2 1.05 200 [36] EVA/TPU 0.15 — 2.50 244 [37] BR/SBR/NR 0.89±0.006 — 11.10±0.3 538±18 [38] EPDM 0.29 — 2.44 626 [39] CPE — — 1.93 269 [40] SBS/SBR/PS 0.20 5.0 0.92 270 [41] SBR/EVA 0.47±0.03 4.7±0.35 3.15±0.17 642±5.52 This work Notes: MWCNT—Multiwalled carbon nanotube; POE—Polyolefin thermoplastic elastomer; CPE—Chlorinated polyethylene rubber; TPU—Thermoplastic polyurethane; BR—Butadiene rubber; NR—Nature rubber; EPDM—Ethylene-propylene-diene monomer; SBS—Styrene-butadiene-styrene block copolymer; PS—Polystyrene.
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