聚乳酸／聚（3⁃羟基丁酸⁃co⁃3⁃羟基戊酸酯）共混材料3D打印线材改性研究

doi:10.19491/j.issn.1001-9278.2020.07.006

中国塑料 ›› 2020, Vol. 34 ›› Issue (7): 36-43.DOI: 10.19491/j.issn.1001-9278.2020.07.006

聚乳酸／聚（3⁃羟基丁酸⁃co⁃3⁃羟基戊酸酯）共混材料3D打印线材改性研究

祖钰, 任亚男, 胡晶()

北京工商大学材料与机械工程学院，塑料卫生与安全质量评价技术北京市重点实验室，北京 100048

收稿日期:2019-10-22 出版日期:2020-07-26 发布日期:2020-07-26
基金资助:
国家自然科学基金(51601002)

Study on Modification of Polylactic Acid/Poly(3⁃Hydroxybutyric Acid⁃co⁃3⁃Hydroxyvalate) Blends as 3D⁃Printing Filament

Yu ZU, Yanan REN, Jing HU()

School of Materials and Mechanical Engineering，Beijing Technology and Business University，Beijing Key Laboratory of Quality Evaluation Technology for Hygiene and Safety of Plastics，Beijing 100048，China

Received:2019-10-22 Online:2020-07-26 Published:2020-07-26
Contact: Jing HU E-mail:hujing@th.btbu.edu.cn

摘要/Abstract

摘要：

采用熔融共混法制备聚乳酸／聚（3?羟基丁酸?co?3?羟基戊酸酯）（PLA/PHBV），以及分别添加苯乙烯?甲基丙烯酸缩水甘油酯共聚物（ADR）、柠檬酸三丁酯（TBC）的共混物PLA/PHBV/ADR和PLA/PHBV/TBC，通过注塑和熔融沉积成型（FDM）技术制备了标准测试样条，研究了添加ADR和TBC后对PLA/ PHBV共混材料及三维（3D）打印样品热学性能和力学性能的影响。结果表明，PHBV结晶度均降低，加入ADR的注塑样品断裂伸长率最大提高到32 %，加入TBC的注塑样品拉伸强度和冲击强度提高，断裂伸长率提高到2.8 %；加入ADR的3D打印制品拉伸强度降低，断裂伸长率提高，添加TBC的3D打印制品相容性得到了明显的提升，通过扫描电子显微镜（SEM）观察无明显的颗粒相，拉伸强度在改性前后无明显变化。

关键词: 聚乳酸, 聚（3?羟基丁酸?co?3?羟基戊酸酯）, 扩链剂, 增塑剂, 三维打印

Abstract:

A series of polylactic acid (PLA)/poly(3?hydroxybutyric acid?co?3?hydroxyvalate) (PHBV), PLA/PHBV/styrene?methacrylate glycidyl copolymer (ADR) and PLA/PHBV/tributyl citrate (TBC) blends were prepared by a melt blending method, and the standard test bars were prepared by injection molding and fused deposition molding (FDM) techniques. The effects of ADR and TBC as modifiers on the thermal and mechanical properties of PLA/PHBV blends and 3D?printed specimens were investigated. The results indicated that the crystallinity of PHBV was decreased, and the injection?molded sample with ADR exhibited the maximum elongation at break with an increment rate of 32 %. Moreover, the incorporation of TBC also improved the tensile strength and impact strength of the injection?molded sample, and its elongation at break increased by 2.8 %. The 3D?printed specimens presented a decrease in tensile strength but an increase in elongation at break due to the introduction of ADR. Meanwhile, the compatibility of 3D?printed specimens was improved significantly in the presence of TBC. There was no obvious particle phase observed from SEM, and the tensile strength of blends did not change significantly after the modification.

Key words: polylactic acid, poly (3?hydroxybutyric acid?co?3?hydroxyvalate), chain extender, plasticizer, three?dimensional printing

中图分类号:

TQ 321

祖钰, 任亚男, 胡晶. 聚乳酸／聚（3⁃羟基丁酸⁃co⁃3⁃羟基戊酸酯）共混材料3D打印线材改性研究[J]. 中国塑料, 2020, 34(7): 36-43.

Yu ZU, Yanan REN, Jing HU. Study on Modification of Polylactic Acid/Poly(3⁃Hydroxybutyric Acid⁃co⁃3⁃Hydroxyvalate) Blends as 3D⁃Printing Filament[J]. China Plastics, 2020, 34(7): 36-43.

图/表 10

图1 PLA/PHBV添加ADR和TBC的共混材料DSC曲线

Fig.1 DSC curves of the PLA/PHBV blends with ADR and TBC

PLA/PHBV /ADR/TBC	T_g,PLA/℃	T_g,PHBV/℃	T_cc/℃	?H_cc，PHBV/ J·g^-1	T_m,PLA/℃	T_m,PHBV/℃	?H_m，PHBV/ J·g^-1	Χ_PHBV/%
85/15/0/0	55.22	-1.76	114.59	9.25	149.22	168.50	10.86	11.72
80/20/0/0	55.52	-1.20	114.09	10.95	149.68	168.35	13.86	15.89
75/25/0/0	55.56	-0.78	104.57	12.30	149.33	171.83	17.08	20.89
70/30/0/0	55.62	-1.27	108.15	14.23	148.97	171.67	22.23	29.13
60/35/0/0	55.44	-0.43	105.24	11.53	149.21	171.80	21.04	29.69
85/15/0.3/0	59.13	2.37	136.32	3.15	152.01	173.88	3.697	3.99
80/20/0.3/0	60.8	2.67	131.35	2.97	152.44	173.32	3.764	4.32
75/25/0.3/0	59.07	2.23	132.84	4.70	151.22	172.65	6.525	7.98
70/30/0.3/0	59.88	1.90	130.57	3.94	150.21	170.33	6.586	9.63
65/35/0.3/0	59.35	1.88	121.88	7.99	151.37	170.66	14.58	20.58
85/15/0/2	51.8	-1.32	130.08	1.10	151.68	172.90	2.94	13.37
80/20/0/2	53.29	-2.23	132.54	2.94	150.00	171.54	7.83	26.71
75/25/0/2	54.14	-2.14	128.89	4.24	148.62	169.42	11.29	30.80
70/30/0/2	53.96	-3.23	113.93	6.62	148.58	167.00	17.60	40.01
65/35/0/2	53.99	-3.81	118.48	6.03	148.40	166.81	16.04	31.26

表1 PLA/PHBV/ADR（TBC）共混材料DSC热性能数据

Tab.1 Thermal properties of PLA/PHBV/ADR(TBC) blends from DSC

图2 PLA/PHBV加入添加剂前后的共混材料熔体质量流动速率对比图

Fig.2 Comparison of melt mass flow rates of PLA / PHBV blends after adding additives

图3 加入ADR前后共混材料注塑样品力学性能对比图

Fig.3 Comparison of mechanical properties of injection samples after adding ADR

图4 加入TBC前后共混材料注塑样品力学性能对比图

Fig.4 Comparison of mechanical properties of injection samples of blends after adding TBC

图5 加入ADR前后共混材料打印样品力学性能对比图

Fig.5 Comparison of mechanical properties of printing samples of the blends after adding ADR

图6 加入TBC前后共混材料打印样品力学性能对比图

Fig.6 Comparison of mechanical properties of printing samples of the blends after adding TBC

图7 加入改性剂后共混材料注塑样品SEM照片（×5 000）

Fig.7 SEM pictures of injection samples of the blends after adding the modifier(×5 000)

图8 加入改性剂后共混材料打印样品SEM照片（×5 000）

Fig.8 SEM pictures of the samples printed by the blends with modifier（×5 000）

图9 加入改性剂后共混材料打印样品SEM照片（×200）

Fig.9 SEM pictures of the samples printed by the blends with modifier(×200)

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聚乳酸／聚（3⁃羟基丁酸⁃co⁃3⁃羟基戊酸酯）共混材料3D打印线材改性研究

Study on Modification of Polylactic Acid/Poly(3⁃Hydroxybutyric Acid⁃co⁃3⁃Hydroxyvalate) Blends as 3D⁃Printing Filament

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