羧基化表面修饰纳米二氧化硅增强热塑性淀粉基生物降解塑料

马宏鹏; 秦文博; 郭斌; 李盘欣

doi:10.13801/j.cnki.fhclxb.20210817.002

羧基化表面修饰纳米二氧化硅增强热塑性淀粉基生物降解塑料

doi: 10.13801/j.cnki.fhclxb.20210817.002

马宏鹏¹,
秦文博¹,
郭斌^{1, 2, 3, ,},
李盘欣^{2, 3}

1.
南京林业大学　理学院，南京 210037
2.
河南省农林产品深加工院士工作站，漯河 462600
3.
南街村集团博士后科研工作站，漯河 462600

基金项目: 江苏省政府留学基金；南京林业大学“青年拔尖人才”；江苏省研究生科研与实践创新计划项目(SJCX22_0318)

详细信息

通讯作者:
郭斌，博士，教授，硕士生导师，研究方向为天然高分子材料　E-mail: gbm@ustc.edu

中图分类号: TQ321.2；TQ342.41
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- 被引次数: 0
出版历程
- 收稿日期: 2021-07-09
- 修回日期: 2021-08-03
- 录用日期: 2021-08-06
- 网络出版日期: 2021-08-17
- 刊出日期: 2022-07-30

Thermoplastic starch-based biodegradable plastics reinforced by carboxylated surface modification of nano silica

MA Hongpeng¹,
QIN Wenbo¹,
GUO Bin^{1, 2, 3
, ,},
LI Panxin^{2, 3}

1.
College of Science, Nanjing Forestry University, Nanjing 210037, China
2.
Agricultural and Forest Products Processing Academician Workstation of Henan Province, Luohe 462600, China
3.
Post-Doctoral Research Center of Nanjiecun Group, Luohe 462600, China

摘要

摘要: 为了提高热塑性淀粉(TPS)的力学和耐水性能，用硅烷偶联剂KH550及丁二酸酐对纳米SiO₂微球(SM-COOH)表面进行羧基化改性以提高界面结合力，并通过挤出注塑工艺制备SM-COOH/TPS复合材料，研究了不同含量的SM-COOH对复合材料力学、动态热力学、热稳定、表面耐水及流变加工性能的影响。结果表明：SM-COOH的加入可显著提高TPS的性能。当SM-COOH含量为2.0wt%时，复合材料的拉伸强度及冲击强度分别达到最大值12.71 MPa和15.918 kJ/m²，相比纯TPS，分别提高近4倍和2.6倍；复合材料的热稳定性能达到最大值，最大分解速率所对应的温度为322.1℃；此时，复合材料的峰值和平衡扭矩适中，也具有较好的流变加工性能。此外，复合材料的转变温度和表面接触角则随着SM-COOH含量的增加而提高。因此，羧基化表面改性纳米SiO₂是一种能有效提高SM-COOH/TPS复合材料的力学和耐水等性能的方法，在淀粉基生物降解塑料领域具有广阔的发展和应用前景。
- 热塑性淀粉 /
- 二氧化硅 /
- 羧基化改性 /
- 复合材料 /
- 力学性能 /
- 生物降解塑料
Abstract: In order to improve the mechanical properties and water resistance of thermoplastic starch (TPS), the carboxylated silica microspheres (SM-COOH) modified by coupling agent KH550 and succinic anhydride were used to prepare the SM-COOH/TPS composites by extrusion and injection molding process. The effects of different contents of SM-COOH on the mechanical properties, dynamic thermodynamics, thermal stability, surface water resistance and rheological properties of the composites were studied in details. The results show that the added SM-COOH can improve the performance of TPS. When the content of SM-COOH is 2.0wt%, the tensile strength and impact strength of the composites reach the maximum value of 12.71 MPa and 15.918 kJ/m², respectively, which are nearly 4 times and 2.6 times higher than that of pure TPS. The temperature corresponding to the maximum decomposition rate in DTG curves reaches the maximum of 322.1℃, and the peak value and equilibrium torque of the composites are moderate, which shows the better rheological processing properties. In addition, with the increased SM-COOH content, the transition temperature and surface contact angle of composites also increase. Therefore, adding the carboxylated modified nano-SiO₂ into TPS is an effective method to improve the performance of SM-COOH/TPS composites, and will be useful in the area of starch-based biodegradable plastics.
- thermoplastic starch /
- silicon dioxide /
- carboxylation modification /
- composites /
- mechanical property /
- biodegradable plastics

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图 1 纳米二氧化硅羧基化改性及与淀粉大分子反应机制图

Figure 1. Mechanism of carboxylation modified SiO₂ microspheres and reaction between SM-COOH and starch molecule

下载: 全尺寸图片幻灯片

图 2 不同SM-COOH含量的SM-COOH /TPS复合材料的力学性能：(a)拉伸强度和断裂伸长率；(b)冲击强度

Figure 2. Mechanical properties of SM-COOH /TPS composites with different SM-COOH contents: (a) Tensile strength and elongation at break; (b) Impact strength

SM-COOH—Carboxylated silica microspheres

下载: 全尺寸图片幻灯片

图 3 不同SM-COOH添加量的SM-COOH/TPS复合材料的动态热力学分析(DMA)曲线(频率1 Hz)：(a)储能模量；(b)损耗因子

Figure 3. DMA curves of SM-COOH /TPS composites with different SM-COOH contents (Frequency 1 Hz): (a) Storage modulus; (b) Loss factor

TPS—Thermoplastic starch

下载: 全尺寸图片幻灯片

图 4 不同SM-COOH含量的SM-COOH/TPS复合材料的TG (a)和 DTG (b) 曲线

Figure 4. TG (a) and DTG (b) curves of SM-COOH/TPS composites with different SM-COOH contents

下载: 全尺寸图片幻灯片

图 5 不同SM-COOH含量SM-COOH/TPS复合材料的接触角

Figure 5. Contact angles of SM-COOH/TPS composites with different SM-COOH contents

下载: 全尺寸图片幻灯片

图 6 不同SM-COOH含量的SM-COOH/TPS复合材料的流变曲线

Figure 6. Rheological curves of SM-COOH/TPS composites with different SM-COOH contents

下载: 全尺寸图片幻灯片

表 1 不同SM-COOH添加量的SM-COOH/TPS复合材料的转变温度(频率：1 Hz)

Table 1. Transition temperature of SM-COOH /TPS composites with different SM-COOH contents (Frequency: 1 Hz)

Sample	T_α/℃	T_β/℃
TPS	35.20	−50.97
0.5wt%SM-COOH/TPS	44.89	−47.03
1.0wt%SM-COOH/TPS	47.87	−46.86
1.5wt%SM-COOH/TPS	49.43	−46.15
2.0wt%SM-COOH/TPS	53.43	−43.13
2.5wt%SM-COOH/TPS	60.03	−41.12
3.0wt%SM-COOH/TPS	61.55	−41.03
Notes：T_α—High temperature peak; T_β—Low temperature peak; SM-COOH—Carboxylated silica microspheres; TPS—Thermoplastic starch.

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表 2 不同SM-COOH含量的SM-COOH/TPS复合材料的流变数据

Table 2. Rheological data of SM-COOH/TPS composites with different SM-COOH contents

Sample	TPS	1.0wt%SM-COOH/TPS	2.0wt%SM-COOH/TPS	3.0wt%SM-COOH/TPS
Initial torque/(N·m)	0	0	0	0
Peak torque/(N·m)	32.01	38.34	47.32	52.47
Equilibrium torque/(N·m)	9.04	10.02	11.32	11.78

下载: 导出CSV

参考文献(25)

[1]	查东东, 郭斌, 李本刚, 等. 热塑性淀粉耐水性的化学与物理作用机制[J]. 化学进展, 2019, 31(1):156-166. ZHA Dongdong, GUO Bin, LI Bengang, et al. Chemical and physical mechanism of water resistance for thermoplastic starch[J]. Progress in Chemistry,2019,31(1):156-166(in Chinese).
[2]	查东东, 周文, 银鹏, 等. 热塑性淀粉力学性能的提升途径及作用机理[J]. 化学进展, 2019, 31(7):1044-1055. ZHA Dongdong, ZHOU Wen, YIN Peng, et al. Ways and mechanism of improving the mechanical properties of thermoplastic starch[J]. Progress in Chemistry,2019,31(7):1044-1055(in Chinese).
[3]	周文, 张鑫, 马宏鹏, 等. 热塑性淀粉制备的化学与物理机制及方法[J]. 化学进展, 2021, 33(11): 1972-1982. ZHOU Wen, ZHANG Xin, MA Hongpeng, et al. Chemical and physical mechanism and method of preparation of thermoplastic starch[J]. Progress in Chemistry, 2021, 33(11): 1972-1982(in Chinese).
[4]	周茜, 张瑶, 陈蓉, 等. SiO₂表面改性对高填充SiO₂/聚四氟乙烯复合薄膜性能的影响[J]. 复合材料学报, 2020, 37(9):2144-2151. ZHOU Qian, ZHANG Yao, CHEN Rong, et al. Effect of surface modification of SiO₂ on properties of highly filled SiO₂/polytetrafluoroethylene composite films[J]. Acta Materiae Compositae Sinica,2020,37(9):2144-2151(in Chinese).
[5]	杨威, 詹迎青, 奉庆萤, 等. 低介电耐温改性空心SiO₂填充含氟聚芳醚腈复合材料的制备及性能[J]. 复合材料学报, 2022, 39(5):2095-2106. YANG Wei, ZHAN Yingqing, FENG Qingying, et al. Preparation and properties of low dielectric and temperature-resistant poly (aryl ether nitrile) composites filled with modified hollow SiO₂[J]. Acta Materiae Compositae Sinica,2022,39(5):2095-2106(in Chinese).
[6]	赵莉, 杜蘅, 刘虎, 等. 纳米SiO₂微球在PMMA凝胶聚合物电解质中的尺寸效应及其在全固态电致变色器件中的应用[J]. 复合材料学报, 2021, 38(5):1446-1454. ZHAO Li, DU Heng, LIU Hu, et al. Size effect of nano SiO₂ microspheres in PMMA gel polymer electrolyte and its application in all-solid-state electrochromic devices[J]. Acta Materiae Compositae Sinica,2021,38(5):1446-1454(in Chinese).
[7]	LIU W Y, CHEN Y, TU X, et al. Processing and mechanical properties of starch and PVA composite reinforced by nano-SiO₂[J]. Advanced Materials Research,2012,557-559:201-204. doi: 10.4028/www.scientific.net/AMR.557-559.201
[8]	LIU W Y, CHEN Y, OUYANG L, et al. Processing and mechanical properties of starch and PCL composite reinforced by nano-SiO₂[J]. Advanced Materials Research,2012,496:134-137. doi: 10.4028/www.scientific.net/AMR.496.134
[9]	FROST K, BARTHES J, KAMINSKI D, et al. Thermoplastic starch–silica–polyvinyl alcohol composites by reactive extrusion[J]. Carbohydrate Polymers,2011,84(1):343-350. doi: 10.1016/j.carbpol.2010.11.042
[10]	JIE Z, WEI G, BWA B, et al. Preparation and evaluation of starch-based extrusion-blown nanocomposite films incorporated with nano-ZnO and nano-SiO₂[J]. International Journal of Biological Macromolecules,2021,183:1371-1378. doi: 10.1016/j.ijbiomac.2021.05.118
[11]	LIU Y, FAN L, MO X, et al. Effects of nanosilica on retrogradation properties and structures of thermoplastic cassava starch[J]. Journal of Applied Polymer Science,2018,135(2):45687. doi: 10.1002/app.45687
[12]	YAO K, CAI J, LIU M, et al. Structure and properties of starch/PVA/nano-SiO₂ hybrid films[J]. Carbohydrate Polymers,2011,86(4):1784-1789. doi: 10.1016/j.carbpol.2011.07.008
[13]	HUANG C, WANG D. Surface modification of nano-SiO₂ particles with polycarboxylate ether-based superplasticizer under microwave irradiation[J]. ChemistrySelect,2017,2(29):9349-9354. doi: 10.1002/slct.201701493
[14]	SOLEYMANIBROJENI M, SHI H, LIU F, et al. Effects of surface modification of nano-SiO₂ imbedded in organic matrix on interfacial accumulation of water molecules: An atomistic simulation study[J]. Surfaces and Interfaces,2021,23:100942. doi: 10.1016/j.surfin.2021.100942
[15]	SHANG Q Q, ZHOU Y H. Facile fabrication of hollow mesoporous silica microspheres with hierarchical shell structure via a sol-gel process[J]. Journal of Sol-Gel Science and Technology,2015,75(1):206-214. doi: 10.1007/s10971-015-3691-7
[16]	YU Y X, GUO D Q, FANG J Y. Synthesis of silica aerogel microspheres by a two-step acid-base sol-gel reaction with emulsification technique[J]. Journal of Porous Materials,2015,22(3):621-628. doi: 10.1007/s10934-015-9934-8
[17]	TIAN S J, GAO W, LIU Y J, et al. Effects of surface modification nano-SiO₂ and its combination with surfactant on interfacial tension and emulsion stability[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2020,595:124682. doi: 10.1016/j.colsurfa.2020.124682
[18]	李传习, 李游, 高有为, 等. 纳米SiO₂质量分数对胶粘碳纤维增强树脂复合材料板-钢搭接界面黏结性能的影响[J]. 复合材料学报, 2020, 37(10):2619-2635. LI Chuanxi, LI You, GAO Youwei, et al. Effect of nano-SiO₂ mass fraction on the interface performance of glued carbon fiber reinforced polymer composite-steel specimen[J]. Acta Materiae Compositae Sinica,2020,37(10):2619-2635(in Chinese).
[19]	王成江, 范正阳, 赵宁, 等. 硅烷偶联剂修饰下SiO₂-甲基乙烯基硅橡胶分子界面的粘结性[J]. 复合材料学报, 2020, 37(12):3079-3090. WANG Chengjiang, FAN Zhengyang, ZHAO Ning, et al. Adhesion of SiO₂-methyl vinyl silicone rubber molecular interface modified by silane coupling agents[J]. Acta Materiae Compositae Sinica,2020,37(12):3079-3090(in Chinese).
[20]	刘钰馨, 盛家荣, 莫羡忠, 等. 二氧化硅粒子对热塑性木薯淀粉稳定性能的影响[J]. 弹性体, 2014(6):55-58. doi: 10.3969/j.issn.1005-3174.2014.06.011 LIU Yuxin, SHENG Jiarong, MO Xianzhong, et al. Effect of silica particle on stability of thermoplastic cassava starch[J]. China Elastomerics,2014(6):55-58(in Chinese). doi: 10.3969/j.issn.1005-3174.2014.06.011
[21]	刘钰馨, 盛家荣, 莫羡忠, 等. 二氧化硅对热塑性木薯淀粉力学性能及加工行为的影响[J]. 高分子材料科学与工程, 2015(7):81-86. LIU Yuxin, SHENG Jiarong, MO Xianzhong, et al. Effect of silica on mechanical properties and processing behavior of thermoplastic cassava starch[J]. Polymer Materials Science & Engineering,2015(7):81-86(in Chinese).
[22]	郭斌, 韩梓军, 薛灿, 等. 注塑工艺制备二氧化硅/热塑性淀粉复合材料[J]. 塑料, 2017, 46(4):23-25. GUO Bin, HAN Zijun, XUE Can, et al. Preparation of SiO₂ reinforced thermoplastic starch composite by injection molding[J]. Plastics,2017,46(4):23-25(in Chinese).
[23]	中国国家标准化管理委员会. 塑料拉伸性能的测定第1部分: 总则: GB/T 1040.1—2018 [S]. 北京: 中国标准出版社, 2018. Standardization Administration of the People’s Republic of China. Plastics determination of tensile properties part 1: General principles: GB/T 1040.1—2018 [S]. Beijing: China Standards Press, 2018 (in Chinese).
[24]	田庆丰, 唐源, 刘亚兰, 等. 表面功能化纳米SiO₂的制备及其在溶液聚合丁苯橡胶-顺丁橡胶中的应用[J]. 复合材料学报, 2020, 37(7):1703-1712. TIAN Qingfeng, TANG Yuan, LIU Yalan, et al. Preparation of surface functionalized nano SiO₂ and its application in solution polymerized styrene butadiene rubber-polybutadiene rubber[J]. Acta Materiae Compositae Sinica,2020,37(7):1703-1712(in Chinese).
[25]	GUO B, ZHA D D, LI B G, et al. Polyvinyl alcohol microspheres reinforced thermoplastic starch composites[J]. Materials,2018,11(4):640. doi: 10.3390/ma11040640