Construction and enhanced thermal properties of hollow glass beads/ aromatic thermosetting polyester composite foam
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摘要: 本研究将空心玻璃微珠(HGB)引入到全芳香族热固性共聚酯(ATPE)发泡体系中制备了HGB/ATPE复合泡沫，并研究了HGB的含量和泡沫性能对于复合泡沫体系的影响。当玻璃微珠改性后，HGB/ATPE复合泡沫的比强度为26.2 MPa/(g·cm−3)；HGB的加入也使复合体系热性能和阻燃性能有较大提高，HGB/ATPE复合泡沫的热分解温度、玻璃化转变温度及热变形温度分别为494.18℃、230.47℃和191.00℃，极限氧指数可达到35%~37%。Abstract: In this study, hollow glass beads (HGB) were introduced into an aromatic thermosetting polyester (ATPE) based foam to prepare HGB/ATPE composite foam, and effect of content of HGB and foaming conditions on the properties of HGB/ATPE composite foam were investigated. After modification, the specific strength of the HGB/ATPE composite foam can reach 26.2 MPa/(g·cm−3), respectively. Moreover, the addition of HGB also greatly improves thermal properties and flame resistance performance of the HGB/ATPE composite foam. The thermal decomposition temperature, glass transition temperature and heat distortion temperature of the HGB/ATPE composite foam are 494.18℃, 230.47℃ and 191.00℃, respectively, and the limiting oxygen index can reach 35%–37%.
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图 1 含有端羧基预聚物C1和含有端酯基预聚物A1的结构式
Figure 1. Structural formula of prepolymer C1 containing a terminal carboxyl and prepolymer A1 containing a terminal ester
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图 2 空心玻璃微珠(HGB)含量对HGB/全芳香族热固性共聚酯(ATPE)复合泡沫微观形貌的影响
Figure 2. Effect of hollow glass beads (HGB) content on micromorphology of HGB/aromatic thermosetting polyester (ATPE) composite foams ((a) 5.4wt% HGB; (b) 10.3wt% HGB; (c) 11.4wt% HGB; (d) 12.5wt% HGB)
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图 3 发泡温度(a)和发泡时间(b)对HGB/ATPE复合泡沫比强度的影响
Figure 3. Effect of foaming temperature (a) and foaming time (b) on specific strength of HGB/ATPE composite foams
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图 4 HGB/ATPE和泡沫的储能模量和损耗模量
Figure 4. Storage modulus and loss modulus of HGB/ATPE composite foam
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图 6 ATPE泡沫和HGB/ATPE复合泡沫的TG和DTG曲线
Figure 6. TG and DTG curves of ATPE foam and HGB/ATPE composite foam
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图 7 发泡温度对HGB/ATPE复合泡沫阻燃性能的影响
Figure 7. Effect of foaming temperature on flame resistance of HGB/ATPE composite foam
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图 8 发泡时间对HGB/ATPE复合泡沫阻燃性能的影响
Figure 8. Effect of foaming time on flame resistance of HGB/ATPE composite foam
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图 9 HGB/ATPE复合泡沫燃烧后的照片: (a)横截面处; (b)表面发白现象
Figure 9. Photographs of HGB/ATPE composite foam after burning: (a) at cross-section; (b) surface blushing
表 1 对苯二酚二乙酸酯(HQDA)和4-乙酰氧基苯甲酸(ABA)的原料配比
Table 1 Proportion of raw materials of synthesizing hydroquinone diacetate (HQDA) and 4-acetoxybenzoic acid (ABA)
HQDA ABA AA/mL 252 192 HQ/g 132 — HBA/g — 132 Catalyst/g 4.8 (4-MBSA) 7.64 (SH) Oil bath temperature/℃ 100 110 Stirring time/min 30 20 Notes: AA—Acetic anhydride; HQ—Hydroquinone; HBA—p-Hydroxybenzonic acid; SH—NaOH; 4-MBSA—4-Methylbenzenesulfonic acid. 
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表 2 不同固化温度下HGB/ATPE复合泡沫的热变形温度
Table 2 Thermal deformation temperature of HGB/ATPE composite foams under different curing temperatures
Curing temperature/℃ Critical
temperature /℃Strength retention under criticaltemperature/% 230 210 79.0 240 180 76.3 250 165 75.8 260 160 75.9 270 150 70.3 Note: The strength of the sample will drop rapidly when it reaches a certain temperature, which is called critical temperature.
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表 3 HGB/ATPE泡沫高温下的压缩性能
Table 3 Compression properties of HGB/ATPE foam at high temperature
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