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2222材料工程  2022, Vol. 50 Issue (8): 99-106    DOI: 10.11868/j.issn.1001-4381.2021.000408
  研究论文 本期目录 | 过刊浏览 | 高级检索 |
氧化石墨烯接枝聚乙二醇对左旋聚乳酸结晶行为和热稳定性的影响
李守佳1, 罗春燕1,2,*(), 陈卫星1,2, 方铭港1, 孙健鑫1
1 西安工业大学 材料与化工学院, 西安 710021
2 陕西省光电功能材料与器件重点实验室, 西安 710021
Effects of graphene oxide grafted polyethylene glycol on crystallization behavior and thermal stability of poly(L-lactic acid)
Shoujia LI1, Chunyan LUO1,2,*(), Weixing CHEN1,2, Minggang FANG1, Jianxin SUN1
1 School of Materials Science and Chemical Engineering, Xi'an Technological University, Xi'an 710021, China
2 Shaanxi Key Laboratory of Photoelectric Functional Materials and Devices, Xi'an 710021, China
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摘要 

为改善聚乳酸的结晶性能和热稳定性，通过酯化反应将聚乙二醇(PEG)接枝到氧化石墨烯(GO)表面，制备出表面修饰PEG的GO(GO-g-PEG)作为聚乳酸的结晶促进剂。利用溶液共混法制备出不同GO-g-PEG含量的GO-g-PEG/左旋聚乳酸(PLLA)复合材料，通过傅里叶变换红外光谱仪(FTIR)和X射线衍射仪(XRD)表征分析证实PEG成功接枝到GO表面。通过差示扫描热量仪(DSC)、热台偏光显微镜(POM)和热重分析仪(TGA)研究GO-g-PEG对PLLA结晶行为和热稳定性的影响。结果表明：在GO-g-PEG的异相成核及增塑作用下，GO-g-PEG/PLLA复合材料结晶成核密度明显增大，结晶能力和结晶度提高；在PEG接枝量为11.8%(质量分数)时，GO-g-PEG/PLLA复合材料的热分解温度较纯PLLA提高20 ℃左右。
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李守佳
罗春燕
陈卫星
方铭港
孙健鑫
关键词 ： 氧化石墨烯,  聚乙二醇,  左旋聚乳酸,  异相成核,  结晶行为,  热稳定性    
Abstract：

In order to improve the crystallization properties of polylactic acid, the crystallization accelerator of graphene oxide grafted polyethylene glycol (GO-g-PEG) was prepared by esterification. The GO-g-PEG/poly(L-lactic acid) (PLLA) composite materials with different GO-g-PEG contents were prepared by solution blending method, and the structure was confirmed by Fourier transform infrared spectroscopy (FTIR) and X-ray diffractometer (XRD). The effect of GO-g-PEG on the crystallization behavior and thermal stability of PLLA was studied by differential scanning calorimeter (DSC), polarizing microscope (POM) and thermogravimetric analyzer (TGA). The results show that under the heterogeneous nucleation and plasticization of GO-g-PEG, the crystallization nucleation density of GO-g-PEG/PLLA composites is increased significantly, the crystallization ability and crystallinity are improved; when the grafting amount of PEG is 11.8%(mass fraction), comparing the thermal stability of GO-g-PEG/PLLA composites with PLLA neat, the thermal decomposition temperature of GO-g-PEG/PLLA composites is increased by about 20 ℃.
Key words： graphene oxide    polyethylene glycol    polylactic(L-lactic acid)    heterogeneous nucleation    crystallization behavior    thermal stability
收稿日期: 2021-04-28      出版日期: 2022-08-16
中图分类号:  O631  
基金资助:国家自然科学基金青年科学基金项目(21506167);陕西省自然科学基础研究计划资助项目(2021 JM-431);西北大学文化遗产研究与保护技术教育部重点实验室开放课题(wysys201906)
通讯作者: 罗春燕     E-mail: luochunyan@xatu.edu.cn
作者简介: 罗春燕(1981—)，女，副教授，博士，研究方向为生物可降解材料的制备和改性，联系地址：陕西省西安市西安工业大学材料与化工学院(710021)，E-mail: luochunyan@xatu.edu.cn
引用本文:   
李守佳, 罗春燕, 陈卫星, 方铭港, 孙健鑫. 氧化石墨烯接枝聚乙二醇对左旋聚乳酸结晶行为和热稳定性的影响[J]. 材料工程, 2022, 50(8): 99-106.
Shoujia LI, Chunyan LUO, Weixing CHEN, Minggang FANG, Jianxin SUN. Effects of graphene oxide grafted polyethylene glycol on crystallization behavior and thermal stability of poly(L-lactic acid). Journal of Materials Engineering, 2022, 50(8): 99-106.
链接本文:  
http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2021.000408      或      http://jme.biam.ac.cn/CN/Y2022/V50/I8/99
Fig.1  GO-g-PEG枝接产物的制备流程示意图
Fig.2  GO，PEG和GO-g-PEG的FTIR谱图(a)和XRD谱图(b)
Fig.3  均聚物PLLA(a)和GO-g-PEG质量分数分别为0.5%(b)，1.0%(c)，1.5%(d)的复合材料在不同温度下等温结晶20 min的偏光显微图(1)135 ℃；(2)140 ℃；(3)145 ℃；(4)150 ℃
Fig.4  GO-g-PEG，PLLA和不同GO-g-PEG质量分数的GO-g-PEG/PLLA复合材料的DSC降温(a)和第二次升温(b)曲线
Sample Mass fraction/% Cooling process Second heating process
Tc/℃ ΔHc/(J·g-1) Tcc/℃ ΔHcc/(J·g-1) Tm1/℃ Tm2/℃ ΔHm/(J·g-1) Xc/%
PLLA — — 134.8 17.4 — 167.2 15.4 16.4
GO-g-PEG 0.2 — — 131.4 21.3 — 166.9 24.6 26.5
GO-g-PEG 0.5 101.1 20.9 — — — 168.2 30.2 32.6
GO-g-PEG 1.0 101.9 21.5 — — — 168.2 33.1 35.9
GO-g-PEG 1.5 115.4 31.9 — — — 165.5 39.6 43.2
GO-g-PEG 2.0 107.3 30.4 — — 163.5 168.5 37.2 40.8
Table 1  降温和第二次升温过程中GO-g-PEG/PLLA复合材料的DSC焓值
Fig.5  0.5%GO-g-PEG/PLLA(a)，1%GO-g-PEG/PLLA(b)，1.5%GO-g-PEG/PLLA(c)和2%GO-g-PEG/PLLA(d) 在不同温度下的等温结晶曲线
Mass fraction of GO-g-PEG/% Tc/℃ n k/10-7 t1/2-1/ 10-3 s-1
0.5 90 2.78 50.47 4.68
95 2.72 30.30 4.01
100 2.47 27.15 4.41
105 2.36 14.42 3.61
110 2.65 18.6 3.46
1.0 90 2.65 31.00 4.19
95 2.60 23.33 3.86
100 2.54 19.94 3.74
105 2.35 14.36 3.62
110 2.53 9.61 2.82
115 2.74 7.27 2.34
1.5 90 3.06 13.82 2.65
95 2.84 26.93 3.62
100 2.69 16.51 3.24
105 2.47 14.96 3.46
110 2.36 11.37 3.26
115 2.40 3.81 2.03
120 2.53 1.75 1.42
2.0 90 2.79 5.28 2.05
95 2.60 38.16 4.66
100 2.52 60.86 5.90
105 2.73 45.32 4.62
110 2.81 12.23 2.77
115 2.93 4.61 1.90
Table 2  GO-g-PEG/PLLA复合材料的等温结晶动力学参数
Fig.6  GO-g-PEG/PLLA复合材料的结晶速率-温度曲线
Fig.7  GO，PLLA和GO-g-PEG的TG(a)和GO-g-PEG/PLLA，PLLA均聚物的DTG(b)曲线
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