亚磷酸三苯酯调控聚乳酸<strong>/</strong>氯化铁共混体系的降解行为和性能

doi:10.11901/1005.3093.2020.300

材料研究学报

2021, Vol. 35

Issue (8): 632-640 DOI: 10.11901/1005.3093.2020.300

研究论文

本期目录 | 过刊浏览

亚磷酸三苯酯调控聚乳酸/氯化铁共混体系的降解行为和性能

令狐昌开¹, 李小龙¹, 罗筑¹(

), 杨乐², 夏啸松¹

^1.贵州大学材料与冶金学院高分子材料工程系贵阳 550025
^2.贵州理工学院材料与能源工程学院贵阳 550003

Triphenyl Phosphite Regulates Degradation Behavior and Properties of Polylactic Acid/Ferric Chloride Blend

LINGHU Changkai¹, LI Xiaolong¹, LUO Zhu¹(

), YANG Le², XIA Xiaosong¹

^1.Department of Polymer Materials Engineering, College of Materials and Metallurgy, Guizhou University, Guiyang 550025, China
^2.School of Materials and Energy Engineering, Guizhou Institute of Technology, Guiyang 550003, China

引用本文:

令狐昌开, 李小龙, 罗筑, 杨乐, 夏啸松. 亚磷酸三苯酯调控聚乳酸/氯化铁共混体系的降解行为和性能[J]. 材料研究学报, 2021, 35(8): 632-640.
Changkai LINGHU, Xiaolong LI, Zhu LUO, Le YANG, Xiaosong XIA. Triphenyl Phosphite Regulates Degradation Behavior and Properties of Polylactic Acid/Ferric Chloride Blend[J]. Chinese Journal of Materials Research, 2021, 35(8): 632-640.

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摘要:

用熔融共混法制备了氯化铁(FeCl₃)催化聚乳酸(PLA)快速降解材料。PLA材料降解的速率提高了10倍，但是PLA/FeCl₃在加工过程中分子量大幅度减小，使力学性能和可加工性能降低。为了减小PLA/FeCl₃在熔融加工中的过度降解，将有优良扩链和增塑效果的亚磷酸三苯酯(TPPi)引入PLA/FeCl₃体系中，用熔融共混制备TPPi改性PLA/FeCl₃材料，使其具有一定的综合力学性能。通过碱溶液降解实验和多种测试研究了样品的降解速率和综合性能。结果表明，TPPi和FeCl₃的添加量之比为3∶1的P3-1样品性能最优，拉伸强度和弯曲强度分别达到43.78 MPa和99.04 MPa，在碱液中降解8d其质量损失率为65.76%，远大于纯聚乳酸的4.67%。含2.95 phr FeCl₃的样品能在碱液中产生高降解速率，加工时不发生过度降解，由此制备出一种可快速降解并保持良好力学性能的聚乳酸改性材料。

关键词 ：复合材料, 聚乳酸, 氯化铁, 亚磷酸三苯酯, 降解行为, 力学性能

Abstract：

A rapid degradation material, ferric chloride (FeCl₃) catalyzed polylactic acid (PLA) PLA/FeCl₃ was prepared by the melt blending method, which presents degradation rate of 10 times higher than that of bare PLA. However, the molecular weight of PLA/FeCl₃ is greatly reduced during the processing, which results in decrease in mechanical properties and processability. In order to reduce the over-degradation of PLA/FeCl₃ in melt processing, triphenyl phosphite (TPPi), which has excellent chain extension and plasticizing effect, was introduced into the PLA/FeCl₃ system and melt blended to improve its comprehensive mechanical properties. The degradation rate and comprehensive performance of the prepared samples were investigated via alkaline solution degradation test and various test methods. The results show that the sample P3-1 had the best performance when the ratio of TPPi to FeCl₃ was 3∶1, namely, the tensile strength and flexural strength reached 43.78 MPa and 99.04 MPa, respectively. The mass loss rate of degradation for 8d in alkaline solution is 65.76%, which was much higher than that of 4.67% for bare PLA. The sample containing 2.95 phr FeCl₃ has been able to produce a high degradation rate in the alkaline solution without over-degradation during the processing, thereby obtaining a modified PLA material that can quickly degrade and maintain good mechanical properties.

Key words： composite polylactic acid ferric chloride triphenyl phosphite degradation behavior mechanical property

收稿日期: 2020-07-20

ZTFLH:

TQ323

基金资助:贵州省科学技术基金(20195607)

作者简介: 令狐昌开，男，1998年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2020.300 或 https://www.cjmr.org/CN/Y2021/V35/I8/632

表1 样品的配方表

图1 纯聚乳酸和TPPi改性PLA/FeCl3材料的反应加工过程中的扭矩曲线

图 2 PLA、TPPi、FeCl3以及纯化TPPi改性PLA/FeCl3材料的红外谱

图3 TPPi抑制FeCl3/PLA改性材料过度降解的机理图

图4 纯PLA和TPPi改性PLA/FeCl3样品在10%(质量分数)NaOH溶液中降解行为的变化过程

图5 纯PLA以及TPPi改性PLA/FeCl3样品在NaOH溶液中质量损失率

图6 纯PLA和TPPi改性PLA/FeCl3样品的TG/DTG曲线

表2 图6中样品的热重数据

图7 纯PLA和TPPi改性PLA/FeCl3材料170℃时的储能模量随角频率的变化

图8 纯PLA和TPPi改性PLA/FeCl3材料的复数粘度随角频率的变化

图9 纯PLA和纯化的TPPi改性PLA/FeCl3材料的分子量及其分布

表3 图9中用折光指数检测器所得的参数

图10 纯PLA和TPPi改性PLA/FeCl3样品的拉伸强度和弯曲强度

1	Alippilakkotte S, Sreejith L. Benign route for the modification and characterization of poly(lactic acid) (PLA) scaffolds for medicinal application [J]. J. Appl. Polym. Sci., 2018, 135(13): 46056
2	Marra A, Silvestre C, Duraccio D, et al. Polylactic acid/zinc oxide biocomposite films for food packaging application [J]. Int. J. Biol. Macromol., 2016, 88: 254
3	Li M Z, Hu X Y, Yu J, et al. Structure and properties of epoxy modified PLA/low melting point PA6 composites [J]. Chin. J. Mater. Res., 2019,33(4):261
3	李明专, 胡孝迎, 何敏等.环氧树脂改性聚乳酸/低熔点尼龙6复合材料的结构和性能 [J].材料研究学报,2019,33(4):261
4	Arnau Carné Sánchez, Collinson S R. The selective recycling of mixed plastic waste of polylactic acid and polyethylene terephthalate by control of process conditions [J]. Eur. Polym. J., 2011, 47(10): 1970
5	Zhu D Y, Gu T, Yu J, et al. Dynamic rheological characterization of PLA/PBS blends compatibilized by epoxy furan resin [J]. Chin. J. Mater. Res., 2018,32(7):547
5	朱大勇, 辜婷, 于杰等. 环氧呋喃树脂反应性增容PLA/PBS共混体系的动态流变学表征 [J]. 材料研究学报, 2018, 32(7): 547
6	Zuo Y F, Gu J, Qiao Z, et al. Effects of dry method esterification of starch on the degradation characteristics of starch/polylactic acid composites. [J]. Int. J. Biol. Macromol., 2015, 72: 391
7	Ramlee N A, Tominaga Y. Mechanical and degradation properties in alkaline solution of poly(ethylene carbonate)/poly(lactic acid) blends [J]. Polymer, 2019, 166: 44
8	Felfel R M, Hossain K M Z, Parsons A J, et al. Accelerated in vitro degradation properties of polylactic acid/phosphate glass fibre composites [J]. J. Mater. Sci., 2015, 50(11): 3942
9	Yang C H, Ma F C, Gao C G, et al. Degradation properties of polylactic acid and its copolymer monofilaments in vitro [J]. Polym. Mater. Sci. Eng., 2019, 35(11): 101
9	杨彩红, 马凤仓, 高晨光等. 聚乳酸及其共聚物单丝的体外降解性能 [J]. 高分子材料科学与工程, 2019, 35(11): 101
10	And T M O, Coates G W. Stereoselective ring-opening polymerization of meso-lactide: synthesis of syndiotactic poly(lactic acid) [J]. J. Chem. Soc., 2000, 121(16): 4072
11	Orozco V H, Kozlovskaya V, Kharlampieva E, et al. Biodegradable self-reporting nanocomposite films of poly(lactic acid) nano-particles engineered by layer-by-layer assembly [J]. Polymer, 2010, 51(18): 4127
12	Li X L, Gong S, Yang L, et al. Study on the degradation behavior and mechanism of poly(lactic acid) modification by ferric chloride [J]. Polymer, 2019, 188: 121991
13	Zhou F, Lu Q, Zhang Y H, et al. Effect of chain extender triphenyl phosphite on the structure and properties of r-PETG [J]. Polym. Mater. Sci. Eng., 2017, 33(2): 78
13	周峰, 吕奇, 张月航等. 扩链剂亚磷酸三苯酯对r-PETG结构与性能的影响 [J]. 高分子材料科学与工程, 2017, 33(2): 78
14	Aharoni, Shaul M. Physics of injection-moldable PET [J]. Int. J. Polym. Mater., 2001, 50(3-4): 301
15	Ma M, Xu L, Liu K, et al. Effect of triphenyl phosphite as a reactive compatibilizer on the propertiesof poly (lactic acid)/poly (butylene succinate) blends [J]. J. Appl. Polym. Sci., 2019, 137(355): 48646
16	Dias M L, Silva A P F. Transesterification reactions in triphenyl phosphite additivated‐poly(ethylene terephthalate)/poly(ethylene naphthalate) blends [J]. Polym. Eng. Sci., 2000, 40(8): 1777
17	Xie J X, Yang R J. Preparation and characterization of high-molecular-weight poly(L-lactic acid) by chain-extending reaction with phosphites [J]. J. Appl. Polym. Sci., 2012, 124(5): 3963
18	Tang G, Wang X, Xing W, et al. Thermal degradation and flame retardance of biobased polylactide composites based on aluminum hypophosphite [J]. Ind. Eng. Chem. Res., 2012, 51(37): 12009
19	Wang Y, Steinhoff B, Brinkmann C, et al. In-line monitoring of the thermal degradation of poly(l-lactic acid) during melt extrusion by UV-vis spectroscopy [J]. Polymer, 2008, 49(5): 1257

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