Poly (lactic acid)-based thermoplastic elastomer with dynamic vulcanization of epoxidized rubber in-situ induced by a zinc ionomer

CHEN Yufei; GENG Biyao; RU Jing; TONG Congcong; ZHANG Lihao; LIU Hongzhi

doi:10.11833/j.issn.2095-0756.2017.03.019

Volume 34 Issue 3

May 2017

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CHEN Yufei, GENG Biyao, RU Jing, TONG Congcong, ZHANG Lihao, LIU Hongzhi. Poly (lactic acid)-based thermoplastic elastomer with dynamic vulcanization of epoxidized rubber in-situ induced by a zinc ionomer[J]. Journal of Zhejiang A&F University, 2017, 34(3): 528-533. doi: 10.11833/j.issn.2095-0756.2017.03.019

Citation:

CHEN Yufei, GENG Biyao, RU Jing, TONG Congcong, ZHANG Lihao, LIU Hongzhi. Poly (lactic acid)-based thermoplastic elastomer with dynamic vulcanization of epoxidized rubber in-situ induced by a zinc ionomer[J]. Journal of Zhejiang A&F University, 2017, 34(3): 528-533. doi: 10.11833/j.issn.2095-0756.2017.03.019

Poly (lactic acid)-based thermoplastic elastomer with dynamic vulcanization of epoxidized rubber in-situ induced by a zinc ionomer

doi: 10.11833/j.issn.2095-0756.2017.03.019

1.
School of Engineering, Zhejiang A & F University, Lin'an 311300, Zhejiang, China
2.
National Engineering and Technology Research Center of Wood-based Resources Comprehensive Utilization, Zhejiang A & F University, Lin'an 311300, Zhejiang, China

Received Date: 2016-06-12
Rev Recd Date: 2016-08-04
Publish Date: 2017-06-20

Abstract

Poly (lactic acid)(PLA), a biodegradable polyester material which is derived from renewable resources and has broad development prospects, as well as thermoplastic vulcanizates (TPV) that use PLA as a matrice material, could help meet the demands of sustainable development. The objectives of this study were to prepare a novel biobased TPVs together with determine the influences of temperature and the content of a zinc ionomer of (ethylene-acrylic acid) copolymer (EMAA-Zn) on the mechanical properties as well as the microstructure of the PLA-based TPVs. In this work, using a PLA as the plastic phase and an epoxidized rubber of (ethylene-butyl acrylate-glycidyl methacrylate) terpolymer (EBA-GMA) as the rubber phase along with an EMAA-Zn as a vulcanizing agent, PLA-based TPVs with different ratio of rubber and plastics were prepared using the dynamic vulcanization method. Results revealed that in a certain temperature range (185-210℃), increasing the temperature was conducive to the crosslinking of ENA-GMA with the best compounding temperature being 210℃. Data from mechanical properties showed that when the PLA/EBA-GMA/EMAA-Zn ratio was 30:70:7.5, the sample had the best mechanical properties with a tensile strength of 14.2 MPa and an elongation up to 500%. However, when the content of EMAA-Zn was higher (more than 7.5%), surface hardness of the samples gradually increased, but the elongation at break of the samples gradually decreased. Finally, scanning electron microscope (SEM) and transmission electron microscope (TEM) images showed that the PLA-based TPV samples exhibited the unique "sea-island" microstructure characteristic of TPV materials (that is the continuous PLA phase and dispersed rubber phase) appeared as well. This indicates that the phase inversion has been happened.
- PLA,
- epoxidized rubber,
- ionomer,
- thermoplastic vulcanizates,
- sea-island micro-structure

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References

[1]	CHEN Erfan, HAN Yunfeng, DENG Wenwen, et al. The development of dynamically vulcanized thermoplastic[J]. Polym Mater Sci Eng, 2011, 27(3):171-174.
[2]	LIU Congcong, WU Shemao, ZHANG Liqun. Recent developments for thermoplastic elastomer[J]. China Rubber, 2009, 25(8):17-21.
[3]	LIANG Cheng. The production situation and developing trend of thermoplastic elastomers[J]. Techno-Econ Petrochem, 2005, 21(1):35-40.
[4]	MITCHELL D M R, AURAS R, SINGH S P. Performance evaluation of PLA against existing PET and PS containers[J]. J Test Eval, 2006, 34(6):1-7.
[5]	WANG Hualin, DAI Jing, ZHAI Linfeng, et al. Preparation and degradat ion of poly lactic acid/bone dust hybrid material[J]. Polym Mater Sci Eng, 2007, 23(3):167-170.
[6]	CHEN Yufei, LIU Hongzhi, WEI Jinguang, et al. Research progress of poly (lactic acid) thermoplastic elastomer[J]. Polym Bull, 2015(5):21-35.
[7]	RYTLEWSKI P, ŻENKIEWICZ M, MALINOWSKI R. Influence of dicumyl peroxide content on thermal and mechanical properties of polylactide[J]. Int Polym Proc Soc, 2011, 26(5):580-586.
[8]	THONGPIN C, KUTTANATE N, KAMPUANG K, et al. Study of dynamic vulcanized PLA/ENR TPV filled with various organic modified MMT (OMMT)[J]. J Metals Mater Miner, 2012, 22(2):105-117.
[9]	THONGPIN C, KLATSUWAN S, BORKCHAIYAPOOM P, et al. Crystallization behavior of PLA in PLA/NR compared with dynamic vulcanized PLA/NR[J]. J Metals Mater Miner, 2013, 23(1):53-59.
[10]	CHEN Yukun, YUAN Daosheng, XU Changhui. Dynamically vulcanized biobased polylactide/natural rubber blend material with continuous cross-linked rubber phase[J]. ACS Appl Mater Interfaces, 2014, 6(6):3811-3816.
[11]	LIU Hongzhi, CHEN Feng, LIU Bo, et al. Super toughened poly (lactic acid) ternary blends by simultaneous dynamic vulcanization and interfacial compatibilization[J]. Macromolecules, 2010, 43(14):6058-6066.
[12]	LIU Hongzhi, SONG Wenjia, CHEN Feng, et al. Interaction of microstructure and interfacial adhesion on impact performance of polylactide (PLA) ternary blends[J]. Macromolecules, 2011, 44(6):1513-1522.
[13]	MAY C A, TANAKA Y. Epoxy Resins:Chemistry and Technology[M]. New York:Marcel Dekker, 1973.

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沈阳化工大学材料科学与工程学院沈阳 110142

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Poly (lactic acid)-based thermoplastic elastomer with dynamic vulcanization of epoxidized rubber in-situ induced by a zinc ionomer

1. School of Engineering, Zhejiang A & F University, Lin'an 311300, Zhejiang, China

2. National Engineering and Technology Research Center of Wood-based Resources Comprehensive Utilization, Zhejiang A & F University, Lin'an 311300, Zhejiang, China

Received Date: 2016-06-12

Rev Recd Date: 2016-08-04

Publish Date: 2017-06-20

Key words:

Abstract: Poly (lactic acid)(PLA), a biodegradable polyester material which is derived from renewable resources and has broad development prospects, as well as thermoplastic vulcanizates (TPV) that use PLA as a matrice material, could help meet the demands of sustainable development. The objectives of this study were to prepare a novel biobased TPVs together with determine the influences of temperature and the content of a zinc ionomer of (ethylene-acrylic acid) copolymer (EMAA-Zn) on the mechanical properties as well as the microstructure of the PLA-based TPVs. In this work, using a PLA as the plastic phase and an epoxidized rubber of (ethylene-butyl acrylate-glycidyl methacrylate) terpolymer (EBA-GMA) as the rubber phase along with an EMAA-Zn as a vulcanizing agent, PLA-based TPVs with different ratio of rubber and plastics were prepared using the dynamic vulcanization method. Results revealed that in a certain temperature range (185-210℃), increasing the temperature was conducive to the crosslinking of ENA-GMA with the best compounding temperature being 210℃. Data from mechanical properties showed that when the PLA/EBA-GMA/EMAA-Zn ratio was 30:70:7.5, the sample had the best mechanical properties with a tensile strength of 14.2 MPa and an elongation up to 500%. However, when the content of EMAA-Zn was higher (more than 7.5%), surface hardness of the samples gradually increased, but the elongation at break of the samples gradually decreased. Finally, scanning electron microscope (SEM) and transmission electron microscope (TEM) images showed that the PLA-based TPV samples exhibited the unique "sea-island" microstructure characteristic of TPV materials (that is the continuous PLA phase and dispersed rubber phase) appeared as well. This indicates that the phase inversion has been happened.

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动态硫化热塑性弹性体（thermoplastic vulcanizate, TPV）是一类采用动态硫化^[1-2]技术制备的共混型热塑性弹性体（TPE）。其独特的“海-岛”相态结构中，交联的橡胶微区提供材料高弹性，热塑性树脂基体赋予TPV加工流动性。由于其分散橡胶相已硫化成具有稳定微区形态的交联颗粒，TPV的某些性能（如高温下使用性能、耐油性、压缩永久变形、尺寸稳定性等）甚至优于嵌段共聚物型TPE^[2]。因此，TPV已成为增长最快的TPE品种^[3]。然而，商业化TPV基材仍以不可再生石油基塑料为主，如聚丙烯和尼龙。聚乳酸（PLA）是一种以玉米Zea mays或甘蔗Saccharum officinarum等农产品发酵制备的乳酸单体为原料聚合得到的热塑性生物降解脂肪族聚酯。因优异的性能^[4]，PLA被公认为是一种最有前途取代传统石油基塑料的“绿色”生物基塑料^[5]。随着石油等不可再生资源的逐渐枯竭，人们对保护环境及可持续发展的日益重视，若能以PLA替代传统PP或尼龙塑料制备出生物基的新型TPV材料，有望解决TPV产业长期受不可再生石油资源制约的问题，具有重要的研究意义和广阔的市场前景。合适的硫化剂体系是制备相形态和性能都优异的TPV材料的关键^[6]。目前，国内外学者在PLA基TPV方面已进行诸多有益的探索^[7-11]。然而，目前适用于聚丙烯基TPV常用的有机过氧化物硫化体系很容易诱发PLA基体交联或热降解^[7]，对TPV材料的性能不利。此外，大多数聚烯烃橡胶与PLA的相容性不佳^[8-10]，直接进行动态硫化无法获得满意性能的TPV材料。前期研究中，LIU等^[11]首次报道了一种含PLA，聚（乙烯-丙烯酸丁酯-甲基丙烯酸环氧甘油酯）三元环氧橡胶（简称EBA-GMA）及部分中和聚（乙烯-丙烯酸）锌离聚物（简称EMAA-Zn）的新型、超韧PLA反应性三元共混体系^[11]。该共混物在熔融共混过程中，EMAA-Zn不仅促进PLA与EBA-GMA之间两相界面的相容化反应，而且还引发了环氧橡胶中的环氧基团发生有效交联。另外，GPC测试结果表明，PLA基体在高温熔融加工过程中未发生显著降解。基于前期的研究基础，本研究拟选用EMAA-Zn作为PLA/EBA-GMA共混体系的硫化剂，在Haake密炼机动态硫化制备了PLA基TPV，考察了EMAA-Zn的用量对EBA-GMA橡胶相的交联反应、TPV材料的表面硬度、力学性能及微观结构的影响，并优化得到了最佳硫化工艺条件和组分配比，从而为生物基TPV的设计、硫化工艺的选择及材料性能的优化提供新的思路和指导。

1. 实验设计

1.1. 原料

聚乳酸（PLA，牌号4032D），熔融指数为0.5~1.0 g·min^-1（210 ℃，2.16 kg），美国NatureWorks LLC生产；聚（乙烯-丙烯酸丁酯-甲基丙烯酸环氧甘油酯）三元环氧橡胶（EBA-GMA，牌号Elvaloy^®PTW），熔融指数为1.2 g·min^-1（210 ℃，2.16 kg），美国杜邦公司产品；部分中和聚（乙烯-丙烯酸）锌离聚物组分（EMAA-Zn，牌号Surlyn^® 9945），熔融指数为0.4 g·min^-1（210 ℃，2.16 kg），美国杜邦公司产品；抗氧剂1010为市售产品。

1.2. 试样制备

混炼前，PLA和EMAA-Zn 2种粒料在85 ℃鼓风烘箱下干燥12 h，EBA-GMA在60 ℃下干燥12 h。密炼过程中，螺杆转速保持在100 r·min^-1，具体密炼过程如下：先将一定质量比的PLA/EBA-GMA（添加质量分数为0.2%抗氧剂1010）粒料加入到预热到一定温度的密炼机（中国上海科创橡塑机械设备有限公司）中，混炼大约2 min后，迅速加入硫化剂EMAA-Zn，并继续混炼8 min后，取出物料，在平板硫化机上热压成大约1 mm厚的薄片，然后裁剪成ASTM D412标准中Die-C型哑铃状拉伸样条。混炼温度设置为185 ℃和210 ℃；硫化剂EMAA-Zn质量分数设置为0，5.0%，7.5%，10.0%；m（PLA）:m（EBA-GMA）设为30.0:70.0，40.0:60.0。

1.3. 透射电镜（TEM）分析

将样品冷冻切片，用透射电镜（JEM-1230，日本电子）观察其微观相结构，加速电压80 kV。

1.4. 扫描电镜（SEM）分析

将液氮中脆断的样品断面喷金后，用扫描电镜（JSM-7610F，日本电子）对其脆断面进行微观形貌观察，加速电压为12 kV。

1.5. 表面硬度

表面硬度用LAC-J邵氏硬度仪（中国上海伦捷机电仪表有限公司）室温下进行测量。

1.6. 拉伸性能

采用CMT 4304电子万能试验机（中国深圳新三思），按照ASTM D412标测，拉伸速度为500 mm·min^-1，室温下测定哑铃型试样的拉伸强度。测试试样5组·配方^-1，计算平均值和标准偏差。

3. 结论

综上所述，锌离聚物EMAA-Zn作为PLA/EBA-GMA共混体系的硫化剂成功制备出具有较好机械性能的PLA基TPV。当混炼温度为210 ℃以及PLA/EBA-GMA/EMAA-Zn共混体系m（PLA）:m（EBA-GMA）:m（EMAA-Zn）=30.0:70.0:7.5时，所制备的TPV材料的力学性能和表面硬度最佳，拉伸强度为14 MPa，断裂伸长率可达500%，邵氏A表面硬度达到88。此外，在橡塑比不变的情况下，随着锌离聚物的增多，TPV的微观相结构从交联的EBA-GMA为基体相演变成以PLA为基体相的“海-岛”相结构。

Reference (13)

[1]	陈尔凡, 韩云凤, 邓雯雯. 动态硫化热塑性弹性体的研究进展[J]. 高分子材料科学与工程, 2011, 27(3): 171-174.	CHEN Erfan, HAN Yunfeng, DENG Wenwen. The development of dynamically vulcanized thermoplastic[J]. Polym Mater Sci Eng, 2011, 27(3): 171-174.
[2]	刘丛丛, 伍社毛, 张立群. 热塑性弹性体的研究进展[J]. 中国橡胶, 2009, 25(8): 17-21.	LIU Congcong, WU Shemao, ZHANG Liqun. Recent developments for thermoplastic elastomer[J]. China Rubber, 2009, 25(8): 17-21.
[3]	梁诚. 热塑性弹性体生产现状与发展趋势[J]. 石油化工技术与经济, 2005, 21(1): 35-40.	LIANG Cheng. The production situation and developing trend of thermoplastic elastomers[J]. Techno-Econ Petrochem, 2005, 21(1): 35-40.
[4]	MITCHELL D M R, AURAS R, SINGH S P. Performance evaluation of PLA against existing PET and PS containers[J]. J Test Eval, 2006, 34(6): 1-7.
[5]	王华林, 戴静, 翟林峰. 可降解聚乳酸/骨粉杂化材料的制备与降解性能[J]. 高分子材料科学与工程, 2007, 23(3): 167-170.	WANG Hualin, DAI Jing, ZHAI Linfeng. Preparation and degradat ion of poly lactic acid/bone dust hybrid material[J]. Polym Mater Sci Eng, 2007, 23(3): 167-170.
[6]	陈宇飞, 刘宏治, 魏金光. 聚乳酸热塑性弹性体的研究进展[J]. 高分子通报, 2015, (5): 21-35.	CHEN Yufei, LIU Hongzhi, WEI Jinguang. Research progress of poly (lactic acid) thermoplastic elastomer[J]. Polym Bull, 2015, (5): 21-35.
[7]	RYTLEWSKI P, ŻENKIEWICZ M, MALINOWSKI R. Influence of dicumyl peroxide content on thermal and mechanical properties of polylactide[J]. Int Polym Proc Soc, 2011, 26(5): 580-586. doi: 10.3139/217.2521
[8]	THONGPIN C, KUTTANATE N, KAMPUANG K. Study of dynamic vulcanized PLA/ENR TPV filled with various organic modified MMT (OMMT)[J]. J Metals Mater Miner, 2012, 22(2): 105-117.
[9]	THONGPIN C, KLATSUWAN S, BORKCHAIYAPOOM P. Crystallization behavior of PLA in PLA/NR compared with dynamic vulcanized PLA/NR[J]. J Metals Mater Miner, 2013, 23(1): 53-59.
[10]	CHEN Yukun, YUAN Daosheng, XU Changhui. Dynamically vulcanized biobased polylactide/natural rubber blend material with continuous cross-linked rubber phase[J]. ACS Appl Mater Interfaces, 2014, 6(6): 3811-3816. doi: 10.1021/am5004766
[11]	LIU Hongzhi, CHEN Feng, LIU Bo. Super toughened poly (lactic acid) ternary blends by simultaneous dynamic vulcanization and interfacial compatibilization[J]. Macromolecules, 2010, 43(14): 6058-6066. doi: 10.1021/ma101108g
[12]	LIU Hongzhi, SONG Wenjia, CHEN Feng. Interaction of microstructure and interfacial adhesion on impact performance of polylactide (PLA) ternary blends[J]. Macromolecules, 2011, 44(6): 1513-1522. doi: 10.1021/ma1026934
[13]	MAY C A, TANAKA Y. Epoxy Resins:Chemistry and Technology[M]. New York:Marcel Dekker, 1973.

m(PLA):m(EBA-GMA):m(EMAA-Zn)	拉伸强度/MPa	断裂伸长率/%	100%定伸应力/MPa	邵氏A硬度
30.0:70.0:0	4.3 ± 0.2	268.0 ± 58.1	4.0 ± 0.2	73.0 ± 0.5
30.0:70.0:5.0	9.2 ±0.3	298.0 ± 15.3	7.3 ± 0.2	83.0 ± 0.7
30.0:70.0:7.5	14.2 ±0.4	501.0 ± 37.0	9.4 ± 0.4	88.0 ± 0.5
30.0:70.0:10.0	14.2 ±0.8	325.0 ± 9.3	9.3 ± 0.2	92.0 ± 0.6
40.0:60.0:7.5	15.8 ± 0.4	373.0 ± 9.3	11.1 ± 0.2	91.0 ± 0.6

Poly (lactic acid)-based thermoplastic elastomer with dynamic vulcanization of epoxidized rubber in-situ induced by a zinc ionomer

doi: 10.11833/j.issn.2095-0756.2017.03.019