羧基化多壁碳纳米管对PBAT/PLA反应性增容体系界面状态及性能的影响

王平; 宋杰; 刘佳佳; 田洪瑜; 陆海冰; 朱露芳; 杨利; 仕敏; 曹田

doi:10.13801/j.cnki.fhclxb.20230110.002

羧基化多壁碳纳米管对PBAT/PLA反应性增容体系界面状态及性能的影响

doi: 10.13801/j.cnki.fhclxb.20230110.002

王平^{1, 3, 4, ,},
宋杰^{1, 4},
刘佳佳^{1, 4},
田洪瑜^{1, 4},
陆海冰^{1, 4},
朱露芳^{1, 4},
杨利^{1, 4},
仕敏^{2, 4},
曹田^{1, 4}

1.
安徽建筑大学　材料与化学工程学院，合肥 230601
2.
安徽建筑大学　数理学院，合肥 230601
3.
安徽建筑大学　安徽省先进建筑材料国际联合研究中心，合肥 230601
4.
特种电线电缆国家地方联合工程研究中心安徽建筑大学分中心，合肥 230601

基金项目: 国家自然科学基金(51903002)；安徽省科技重大专项项目(202103a05020031)；安徽省高校自然科学杰出青年科研项目(2022AH020024)；安徽省高校哲学社会科学重大研究项目(2022AH040047)；安徽建筑大学博士启动基金(2019QDZ22)；安徽省自然科学基金优青项目(2308085Y34)；安徽省博士后研究人员科研活动经费资助项目(2020B413)；安徽省高校省级自然科学研究项目(YJS20210509)

详细信息

通讯作者:
王平，博士，副教授，硕士生导师，研究方向为精细与功能高分子的合成与应用、高分子材料共混与复合　E-mail: anjzwp@ahjzu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-11-08
- 修回日期: 2022-12-14
- 录用日期: 2022-12-25
- 网络出版日期: 2023-01-10
- 刊出日期: 2023-10-15

Influence of carboxylic multi-walled carbon nanotubes on the interface state and properties of PBAT/PLA reactive compatibilization system

WANG Ping^{1, 3, 4
, ,},
SONG Jie^{1, 4},
LIU Jiajia^{1, 4},
TIAN Hongyu^{1, 4},
LU Haibing^{1, 4},
ZHU Lufang^{1, 4},
YANG Li^{1, 4},
SHI Min^{2, 4},
CAO Tian^{1, 4}

1.
School of Materials and Chemical Engineering, Anhui Jianzhu University, Hefei 230601, China
2.
School of Mathematics and Physics, Anhui Jianzhu University, Hefei 230601, China
3.
Anhui Province International Research Center on Advanced Building Materials, Anhui Jianzhu University, Hefei 230601, China
4.
Special Wire and Cable National Local Joint Engineering Research Center Anhui Jianzhu University Branch Center, Hefei 230601, China

Funds: National Natural Science Foundation of China (51903002); Major Science and Technology Projects of Anhui Province (202103a05020031); University Natural Science Outstanding Youth Research Projects of Anhui Province (2022AH020024); University Major Research Projects in Philosophy and Social Sciences of Anhui Province (2022AH040047); Anhui Jianzhu University PhD Startup Fund (2019QDZ22); Excellent Youth Projects of Anhui Provincal Natural Science Foundation (2308085Y34); Research Fund for Postdoctoral Researchers in Anhui Province (2020B413); University Provincial Natural Science Research Projects of Anhui Province (YJS20210509)

摘要

摘要: 聚乳酸(PLA)因其生物可降解及较高的强度在环保型介电材料制备上具有较大的潜力，但较低的介电常数限制了其在该领域的应用。通过熔融共混法将羧基化多壁碳纳米管(MWCNTs—COOH)、环氧扩链剂(ADR)及聚对苯二甲酸-己二酸丁二醇酯(PBAT)引入PLA中制备MWCNTs—COOH-ADR-PBAT/PLA复合材料。采用FTIR、转矩流变仪、DSC、DMA、电子万能试验机、SEM和LCR介电测量仪等研究MWCNTs—COOH对PBAT/PLA反应性增容体系的分子链间相互作用、加工性能、结晶性能、动态力学性能、力学性能及介电性能的影响。研究结果表明，共混过程中MWCNTs—COOH中羧基优先与反应增容剂反应，降低了反应增容剂对PLA与PBAT相界面的催化增容效率。MWCNTs—COOH在动力学和热力学的驱动下优先分散于两相界面处，赋予材料优异刚韧平衡性的同时，明显提高了材料的介电性能。当MWCNTs—COOH含量为4wt%时，在频率100 Hz下，MWCNTs—COOH-ADR-PBAT/PLA复合材料的介电常数为5.35、介电损耗为0.06，材料具有较好的综合性能。
- 聚乳酸 /
- 聚对苯二甲酸-己二酸丁二醇酯 /
- 羧基化多壁碳纳米管 /
- 熔融共混 /
- 介电性能
Abstract: The polylactic acid (PLA) has great potential in the preparation of environmentally friendly dielectric materials due to its biodegradability and high strength, but low dielectric constant limits its wide application in this field. The carboxylic multi-walled carbon nanotubes (MWCNTs—COOH), epoxy-based chain extender (ADR) and poly(butylene adipate-co-terephthalate) (PBAT) were introduced into PLA by melt blending to prepare MWCNTs—COOH-ADR-PBAT/PLA composites. The effects of MWCNTs—COOH on the inter-molecular chain interactions, processing, crystallization, dynamic mechanical, mechanical and dielectric properties of the PBAT/PLA reactive compatibilization system were studied by FTIR, Torque rheometer, DSC, DMA, electron universal testing machine, SEM and LCR dielectric measuring instrument, etc. The results show that the carboxyl group in MWCNTs—COOH preferentially reacts with the reactive compatibilizer during the blending process, which reduces the catalytic compatibilization efficiency of the reactive compatibilizer on the interface between PLA and PBAT. At the same time, MWCNTs—COOH preferentially disperse at the two-phase interface under the drive of dynamics and thermodynamics, giving the material a better rigid toughness balance, while significantly improving the dielectric properties of the material. When the MWCNTs—COOH content is 4wt%, the dielectric constant and dielectric loss of MWCNTs—COOH-ADR-PBAT/PLA composite at 100 Hz were 5.35 and 0.06 respectively, and the material had good comprehensive properties.
- poly(lactic acid) /
- poly(butylene adipate-co-terephthalate) /
- carboxylic multi-walled carbon nanotubes /
- melt blending /
- dielectric properties

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图 1 PLA及其共混复合材料的FTIR图谱

Figure 1. FTIR spectra of PLA and PLA blend composites

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图 2 PLA及其共混复合材料扭矩-时间关系曲线

Figure 2. Torque-time relationship curves of PLA and PLA blend composites

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图 3 PLA及其共混复合材料脆断面的SEM图像：(a) 1wt%MWCNTs—COOH-ADR-PBAT/PLA；(b) 2wt%MWCNTs—COOH-ADR-PBAT/PLA；(c) 3wt%MWCNTs—COOH-ADR-PBAT/PLA；(d) 4wt%MWCNTs—COOH-ADR-PBAT/PLA

Figure 3. SEM images of the brittle fracture surface of PLA blend composites: (a) 1wt%MWCNTs—COOH-ADR-PBAT/PLA; (b) 2wt%MWCNTs—COOH-ADR-PBAT/PLA; (c) 3wt%MWCNTs—COOH-ADR-PBAT/PLA; (d) 4wt%MWCNTs—COOH-ADR-PBAT/PLA

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图 4 PLA及其共混复合材料的DSC二次升温曲线

Figure 4. DSC secondary heating curves of PLA and PLA blend composites

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图 5 PLA及其共混复合材料的储能模量(E') (a) 和损耗模量(E'') (b) 曲线

Figure 5. Storage modulus (E') (a) and loss modulus (E'') (b) curves of PLA and PLA blend composites

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图 6 PLA及其共混复合材料的拉伸强度和断裂伸长率

Figure 6. Tensile strength and elongation at break of PLA and PLA blend composites

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图 7 PLA及其共混复合材料拉伸断面的SEM图像：(a) PLA；(b) PBAT/PLA；(c) ADR-PBAT/PLA；(d) 1wt%MWCNTs—COOH-ADR-PBAT/PLA；(e) 2wt%MWCNTs—COOH-ADR-PBAT/PLA；(f) 3wt%MWCNTs—COOH-ADR-PBAT/PLA；(g) 4wt%MWCNTs—COOH-ADR-PBAT/PLA

Figure 7. SEM images of tensile fracture surface of PLA and PLA blend composites: (a) PLA; (b) PBAT/PLA; (c) ADR-PBAT/PLA; (d) 1wt%MWCNTs—COOH-ADR-PBAT/PLA; (e) 2wt%MWCNTs—COOH-ADR-PBAT/PLA; (f) 3wt%MWCNTs—COOH-ADR-PBAT/PLA; (g) 4wt%MWCNTs— COOH-ADR-PBAT/PLA

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图 8 PLA及其共混复合材料的介电常数(ε') (a) 和介电损耗(tanδ) (b) 与频率的关系

Figure 8. Frequency dependence of dielectric constant (ε') (a) and dielectric loss (tanδ) (b) for PLA and PLA blend composites

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图 9 MWCNTs—COOH在复合材料内部分散状态及形成机制

Figure 9. Dispersion and formation mechanism of MWCNTs—COOH in composites

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表 1 聚乳酸(PLA)及其共混复合材料的组成与配比

Table 1. Composition of polylactic acid (PLA) and PLA blend composites

Sample	PLA/wt%	PBAT/wt%	ADR/wt%	MWCNTs—COOH/wt%
PLA	100.0	—	—	—
PBAT/PLA	60.0	40.0	—	—
ADR-PBAT/PLA	58.8	39.2	2.0	—
1wt%MWCNTs—COOH-ADR-PBAT/PLA	58.2	38.8	2.0	1.0
2wt%MWCNTs—COOH-ADR-PBAT/PLA	57.6	38.4	2.0	2.0
3wt%MWCNTs—COOH-ADR-PBAT/PLA	57.0	38.0	2.0	3.0
4wt%MWCNTs—COOH-ADR-PBAT/PLA	56.4	37.6	2.0	4.0
Notes: MWCNTs—COOH—Carboxylic multi-walled carbon nanotubes; ADR—Epoxy-based chain extender; PBAT—Poly(butylene adipate-co-terephthalate).

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表 2 PLA及其共混复合材料的扭矩

Table 2. Torque of PLA and PLA blend composites

Sample	Torque/(N·m)
PLA	9.9
PBAT/PLA	4.1
ADR-PBAT/PLA	9.8
1wt%MWCNTs—COOH-ADR-PBAT/PLA	8.6
2wt%MWCNTs—COOH-ADR-PBAT/PLA	9.3
3wt%MWCNTs—COOH-ADR-PBAT/PLA	9.6
4wt%MWCNTs—COOH-ADR-PBAT/PLA	9.3

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表 3 PLA及其共混复合材料热力学参数

Table 3. Thermodynamic parameters of PLA and PLA blend composites

Sample	T_g/℃	T_cc/℃	∆H_cc/(J∙g⁻¹)	T_m/℃	∆H_m/(J∙g⁻¹)	χ_c/%
PLA	60.5	108.5	31.9	170.2	36.2	4.6
PBAT	—	—	—	124.8	—	—
PBAT/PLA	60.9	101.1	17.5	169.2	19.9	4.4
ADR-PBAT/PLA	61.6	118.7	17.2	164.3	17.4	0.4
1wt%MWCNTs—COOH-ADR-PBAT/PLA	61.7	114.5	15.7	164.4	17.2	2.8
2wt%MWCNTs—COOH-ADR-PBAT/PLA	64.0	115.6	15.0	166.0	15.3	0.6
3wt%MWCNTs—COOH-ADR-PBAT/PLA	62.3	116.2	14.2	166.1	14.4	0.4
4wt%MWCNTs—COOH-ADR-PBAT/PLA	61.0	114.0	14.2	163.8	15.0	1.5
Notes: T_g—Glass transition temperature; T_cc—Cold crystallization temperature; ∆H_cc—Cold crystallization enthalpy; T_m—Melting temperature; ∆H_m— Melting enthalpy; χ_c—Crystallinity.

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表 4 PLA及其共混复合材料拉伸测试参数

Table 4. Tensile test parameters of PLA and PLA blend composites

Sample	Tensile strength/MPa	Elongation at break/%
PLA	61.8	4.1
PBAT/PLA	26.9	28.5
ADR-PBAT/PLA	31.8	287.5
1wt%MWCNTs—COOH- ADR-PBAT/PLA	22.0	57.9
2wt%MWCNTs—COOH- ADR-PBAT/PLA	24.3	61.7
3wt%MWCNTs—COOH- ADR-PBAT/PLA	23.7	40.5
4wt%MWCNTs—COOH- ADR-PBAT/PLA	23.0	18.0

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羧基化多壁碳纳米管对PBAT/PLA反应性增容体系界面状态及性能的影响

doi: 10.13801/j.cnki.fhclxb.20230110.002

通讯作者:
王平，博士，副教授，硕士生导师，研究方向为精细与功能高分子的合成与应用、高分子材料共混与复合　E-mail: anjzwp@ahjzu.edu.cn

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Influence of carboxylic multi-walled carbon nanotubes on the interface state and properties of PBAT/PLA reactive compatibilization system

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留言板

羧基化多壁碳纳米管对PBAT/PLA反应性增容体系界面状态及性能的影响

doi: 10.13801/j.cnki.fhclxb.20230110.002

通讯作者: 王平，博士，副教授，硕士生导师，研究方向为精细与功能高分子的合成与应用、高分子材料共混与复合 E-mail: anjzwp@ahjzu.edu.cn

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Influence of carboxylic multi-walled carbon nanotubes on the interface state and properties of PBAT/PLA reactive compatibilization system

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出版历程

目录

通讯作者:
王平，博士，副教授，硕士生导师，研究方向为精细与功能高分子的合成与应用、高分子材料共混与复合　E-mail: anjzwp@ahjzu.edu.cn