3D打印聚乙二醇修饰木质素/聚乳酸生物复合材料的热性能与力学性能

鞠泽辉; 王志强; 张海洋; 郑维; 束必清

3D打印聚乙二醇修饰木质素/聚乳酸生物复合材料的热性能与力学性能

鞠泽辉^{1, 2, ,},
王志强^{1, 2},
张海洋¹,
郑维¹,
束必清³

1.
南京林业大学　材料科学与工程学院, 南京 210037
2.
江苏省林木资源高效利用协同创新中心, 南京 210037
3.
扬州工业职业技术学院土木工程学院, 扬州 225127

基金项目: 南京林业大学科研启动基金(163020342)；青蓝工程

详细信息

通讯作者:
鞠泽辉，博士，讲师，研究方向为生物质复合材料　E-mail: juzehui@njfu.edu.cn

中图分类号: TB332
计量
- 文章访问数: 60
- HTML全文浏览量: 37
- 被引次数: 0
出版历程
- 收稿日期: 2024-01-05
- 修回日期: 2024-01-29
- 录用日期: 2024-02-26
- 网络出版日期: 2024-03-22

Thermal and mechanical properties of polyethylene glycol modified lignin/polylactic acid biocomposites for 3D printing

JU Zehui^{1, 2
, ,},
WANG Zhiqiang^{1, 2},
ZHANG Haiyang¹,
ZHENG Wei¹,
SHU Biqing³

1.
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China
2.
Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing 210037, China
3.
College of Civil Engineering, Yangzhou Polytechnic Institute, Yangzhou 225127, China

Funds: Start-up Funds for Scientific Research at the Nanjing Forestry University (163020342); Qing Lan Project

摘要

摘要: 聚乳酸(PLA)是一种绿色可再生的、可降解的高分子材料，被认为是目前商业化程度最高的材料。然而，PLA材料主链结构的刚性决定了PLA的冲击强度弱、断裂伸长率低，限制了其在广泛领域的应用。本研究提出了一种双螺杆挤压法制备PLA和聚乙二醇(PEG)修饰木质素生物复合材料的方法，以期能够提升3D打印木质素/PLA复合材料的力学性能，拓展应用领域。对PEG修饰木质素的结构进行了初步研究。研究不同含量的碱木质素和PEG修饰木质素对PLA复合材料的物理力学性能、微观结构、热学性能和降解性能的影响。实验结果表明，采用酸催化PEG脱木质素的工艺能够将PEG接枝到木质素上，同时能够提高木质素的热性能。PEG修饰木质素的加入提高了聚乳酸复合材料的耐热性。与L30/PLA相比，PL30/PLA的拉伸应力和断裂伸长率分别提高了18.1%和81.9%。与纯聚乳酸相比，复合材料在水系统中具有更好的降解率，特别是在碱性介质中。因此，PEG修饰木质素不仅提高了木质素的附加值，而且为高性能PLA复合材料的生产提供了新的途径。
- 聚乳酸 /
- 碱木质素 /
- 聚乙二醇木质素 /
- 生物复合材料 /
- 性能分析
Abstract: Polylactic acid (PLA) was a green, renewable and degradable polymer material, which was considered to be the most commercially available material at present. However, the rigidity of the main chain structure of PLA material determined its weak impact strength and low elongation at break, which limited its application in a wide range of fields. In this study, a twin-screw extrusion method for preparing PLA and polyethylene glycol (PEG) modified lignin biocomposites was proposed, in order to improve the mechanical properties of 3D printed lignin / PLA composites and expand the application field. The structure of PEG modified lignin was studied. The effects of soda lignin and PEG modified lignin on the physical and mechanical properties, microstructure, thermal properties and degradation properties of PLA composites were studied. The experimental results showed that PEG can be grafted onto lignin and the thermal properties of lignin can be improved. The addition of PEG modified lignin increased the heat resistance of PLA composites. With the addition of 30% PEG modified lignin, the tensile properties of the composites did not decrease significantly. Compared with L30/PLA, the tensile stress and elongation at break of PL30/PLA were increased by 18.1% and 81.9%, respectively. Compared with pure PLA, the composite has a better degradation rate in water systems, especially in alkaline media. Therefore, PEG modified lignin not only improved the added value of lignin, but also provided a new way for the production of high-performance PLA composites.
- Polylactic acid (PLA) /
- soda lignin /
- polyethylene glycol (PEG) modified lignin /
- biocomposites /
- performance analysis

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图 1 不同木质素样品的FTIR光谱：(a) 4000 - 600 cm⁻¹；(b) 2000 - 600 cm⁻¹

Figure 1. FTIR spectra for different lignin samples：(a) lignins within 4000-400 cm⁻¹；(b) lignins within 2000-400 cm⁻¹

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图 2 不同木质素样品的分子分布色谱图

Figure 2. Molecular distribution chromatograms for different lignin samples

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图 3 不同样品的(a)TG和(b) DTG的(碱木质素、聚乳酸(PLA)修饰木质素、PLA、L30/PLA和PL30/PLA)曲线，(c)TG和(d) DTG的(L10/PLA、L20/PLA、PL10/PLA和PL20/PLA)曲线

Figure 3. (a) TG and (b) DTG curves of soda lignin, PEG-modified lignin, Polylactic acid (PLA), L30/PLA and PL30/PLA; (c) TG and (d) DTG curves of L10/PLA, L20/PLA, PL10/PLA and PL20/PLA

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图 4 PLA和木质素/PLA复合材料的DSC分析图

Figure 4. DSC thermograms of PLA and lignin/PLA composites

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图 5 PLA和木质素/PLA复合材料的力学性能

Figure 5. Mechanical properties of PLA and lignin/PLA composites

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图 6 (a) PLA, (b) L10/PLA, (c) L20/PLA, (d) L30/PLA, (e) PL10/PLA, (f) PL20/PLA和(g) PL30/PLA的SEM图像

Figure 6. SEM images of (a) PLA, (b) L10/PLA, (c) L20/PLA, (d) L30/PLA, (e) PL10/PLA, (f) PL20/PLA and (g) PL30/PLA0

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图 7 (a)不同木质素含量PLA在50天内的吸水率和(b)在不同溶剂介质中50天的降解率

Figure 7. (a)Water absorption of PLA with various lignin contents over 50 days and (b)degradation in different solvent media over 50 days

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表 1 生物复合材料的组成

Table 1. The composition of the biocomposites

Samples	PLA/wt%	Soda lignin /wt%	PEG-modified lignin /wt%
PLA	100
L10/PLA	90	10
L20/PLA	80	20
L30/PLA	70	30
PL10/PLA	90		10
PL20/PLA	80		20
PL30/PLA	70		30
Note: L-Soda lignin; PL- PEG-modified lignin

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表 2 木质素产率和木质素组分

Table 2. Lignin yield and carbohydrate compositions of the lignin fraction

Samples	Yield/wt%	Compositions/wt%
Samples	Yield/wt%	AIL	Glc	Xyl	Ara	Gal	Rha	GalA	GlcA	Total
Soda lignin	11.44 ± 1.49	96.14 ± 1.72	0.74 ± 0.11	0.09 ± 0.01	-	-	-	0.22 ± 0.02	0.16 ± 0.01	1.13 ± 0.06
PEG-modified lignin	10.08 ± 1.04	89.12 ± 1.48	0.47 ± 0.02	-	-	-	-	0.18 ± 0.01	0.12 ± 0.01	0.75 ± 0.01
Note: PEG is polyethylene glycol; AIL is acid insoluble lignin, Glc is glucose, Xyl is Xylose, Ara is arabinose, Gal is Galactose, Rha is Rhamnose, GalA is galacturonic acid, GlcA is glucuronic acid, - Not detected

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表 3 木质素的重量-平均分子量(M_w)、数量-平均分子量(M_n)和M_w/M_n

Table 3. Weight-Average Molecular Weight (M_w), Number-Average Molecular Weight (M_n), and M_w/M_n of Lignins

Samples	M_w	M_n	M_w/M_n
Soda lignin	712 ± 11	519 ± 7	1.37 ± 0.04
PEG-modified lignin	1184 ± 12	795 ± 8	1.49 ± 0.03

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表 4 不同样品的热性能

Table 4. Thermal properties of different samples

Samples	Soda lignin	PEG-modified lignin	PLA	L10/PLA	L20/PLA	L30/PLA	PL10/PLA	PL20/PLA	PL30/PLA
T_dst /°C	146.8	271.5	295.6	244.1	213.5	208.9	280.1	286.1	288.1
T_dmax /°C	336.7	393.4	357.8	314.6	293.1	289.1	336.4	340.1	342.1
Residue /%	42.55	34.03	-	3.39	7.58	9.71	0.15	5.92	3.61
Note: T_dst is the degradation starting temperature, T_dmax is the maximum weight loss temperature

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表 5 PLA和木质素/PLA复合材料的转变温度和焓

Table 5. Transition temperatures and enthalpies of PLA and lignin/PLA composites

Samples	T_g/°C	T_cc/°C	H_cc/(J·g⁻¹)	T_m/°C	H_m/(J·g⁻¹)	X_c/%
PLA	59.4	119.3	9.3	152.9	15.3	6.41
L10/PLA	61.3	116.9	24.8	156.5	33.6	9.39
L20/PLA	59.2	112.3	25.2	155.4	37.3	12.91
L30/PLA	58.8	109.4	18.8	151.1	24.3	5.87
PL10/PLA	62.3	122.5	12.5	153.6	18.4	6.30
PL20/PLA	62.6	121.6	15.2	154.1	19.2	4.27
PL30/PLA	61.6	118.0	16.9	155.3	20.8	4.16
Note: T_g is the glass transition temperature, T_cc is the cold crystallization temperature, H_cc is the recrystallization enthalpy, T_m is the melting temperature, H_m is the melting enthalpy, X_c is crystallinity

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表 6 本研究与相关文献的力学性能的对比分析

Table 6. Comparative analysis for mechanical properties of this study and previous studies

Sample	Tensile strength/MPa	Elongation at break/%	Tensile modulus/GPa	References
PLA : Soda lignin = 80wt% : 20wt%)	33.2	1.3	/	Ye, et al.^[10]
PLA : Soda lignin = 80wt% : 20wt%	39.4	/	2.5	Tanase-Opedal, et al.^[11]
PLA_L20_P2(PLA :Soda lignin : PEG= 78wt% : 20wt% : 2wt%)	50.84	≈4.1	≈2.1	Wasti, et al.^[16]
PLA_L20_P5(PLA : Soda lignin : PEG= 75wt% : 20wt% : 5wt%)	42.39	3.98	≈1.7	Wasti, et al.^[16]
PLA : Poplar powder = 90wt% : 10wt%	≈1.2	/	/	GE, et al.^[26]
PLA : Poplar powder = 80wt% : 20wt%	≈6.4	/	/
PLA : Poplar powder = 70wt% : 30wt%	≈4.9	/	/
PLA：nano-cellulose = 95wt% : 5wt%	≈55	/	3.9—4.1	Matea, et al.^[27]
PLA：jute fiber = 70wt% : 30wt%	51.35	/	2.25	Das, et al.^[28]
PLA：flax fiber = 70wt% : 30wt%	45.67	/	2.01	Das, et al.^[28]
PL10/PLA	61.55	6.72	3.67	In this study
PL20/PLA	57.84	5.71	3.75
PL30/PLA	50.31	3.94	3.97

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[1]	SWETHA TR, ANANTHI V, BORA A, et al. A review on biodegradable polylactic acid (PLA) production from fermentative food waste - Its applications and degradation[J]. International Journal of Biological Macromolecules, 2023, 234: 123703. doi: 10.1016/j.ijbiomac.2023.123703
[2]	WASTI S, ADHIKARI S. Use of biomaterials for 3D printing by fused deposition modeling technique: a review[J]. Frontiers in Chemistry, 2020, 8: 1-14. doi: 10.3389/fchem.2020.00001
[3]	BAJWA D-S, POURHASHEM G, ULLAH A-H, et al. A concise review of current lignin production, applications, products and their environmental impact[J]. Industrial Crops and Products, 2019, 139: 111526. doi: 10.1016/j.indcrop.2019.111526
[4]	黄宸超, 刘朝政, 杨蕊, 等. 熔融沉积打印微纳米生物质填料增强聚乳酸基复合材料的研究进展 [J/OL]. 复合材料学报, 2023, 1-19. HUANG chenchao, LIU chaozheng, YANG rui, et al. Research progress of biomass-based micro-nano filler reinforcing polylactic acid matrix composites printed by fused deposition modeling [J/OL]. Acta Materiae Compositae Sinica, 2023, 1-19(in Chinese).
[5]	WANG Y, HOU J, HUANG Y, et al. Structure-controlled lignin complex for PLA composites with outstanding antibacterial, fluorescent and photothermal conversion properties[J]. International Journal of Biological Macromolecules, 2022, 194: 1002-1009. doi: 10.1016/j.ijbiomac.2021.11.159
[6]	花蕾, 沈敏君. PLLA与sPCLPLLA星型嵌段共聚物结晶行为研究[J]. 现代塑料加工应用, 2016, 28(2): 20-24. HUA lei, SHEN minjun. Crystallization Behavior of Poly(L-lactide) and Star Shaped Poly(E-caprolactone-block-l-lactide) Blends[J]. Modern Plastics Processing and Applications, 2016, 28(2): 20-24(in Chinese).
[7]	闫承琳, 刘东, 刘子昕, 等. 基于木塑基耗材的增材制造技术研究进展[J]. 林业工程学报, 2022, 7(4): 22-30. YAN chenglin, LIU dong, LIU zixin, et al. Research progress of additive manufacturing technology and equipment for wood-plastic consumables[J]. Journal of Forestry Engineering, 2022, 7(4): 22-30(in Chinese).
[8]	刘杰, 赵雪松, 李奇, 等. 聚丁二酸丁二醇酯对聚乳酸基木塑复合材料性能的影响 [J/OL]. 复合材料学报, 2023, 1-10. LIU jie, ZHAO xuesong, LI qi, et al. Effect of polybutylene succinate on properties of polylactic acid-based wood-plastic composites [J/OL]. Acta Materiae Compositae Sinica, 2023, 1-10(in Chinese).
[9]	左迎峰, 李文豪, 李萍, 等. 竹纤维/聚乳酸可降解复合材料的增塑改性[J]. 林业工程学报, 2018, 3(01): 77-82. ZUO yingfeng, LI wenhao, LI ping, et al. Plasticization of bamboo fiber/polylactic acid degradable composite[J]. Journal of Forestry Engineering, 2022, 7(04): 22-30(in Chinese).
[10]	YE H, HE Y, LI H, et al. 3D-Printed Polylactic Acid/Lignin Films with Great Mechanical Properties and Tunable Functionalities towards Superior UV-Shielding, Haze, and Antioxidant Properties[J]. Polymers, 2023, 15: 2806. doi: 10.3390/polym15132806
[11]	TANASE-OPEDAL M, ESPINOSA E, RODRGUEZ A, et al. Lignin: a biopolymer from forestry biomass for biocomposites and 3D printing[J]. Materials, 2019, 12: 1-15.
[12]	李园媛. 聚乳酸/木质素复合材料的制备与性能研究[J]. 塑料科技, 2020, 48(6): 82-84. LI yuanyuan. Study on Preparation and Properties of Polylactic Acid/Lg Composites[J]. Plastics science and technology, 2020, 48(6): 82-84(in Chinese).
[13]	刘洋. 木质素含量对PLA基复合材料强韧性的影响[J]. 塑料科技, 2020, 48(4): 71-74. LIU yang. Effect of Lignin Content on Strength and Toughness of PLA-based Composites[J]. Plastics science and technology, 2020, 48(4): 71-74(in Chinese).
[14]	KIM Y, SUHR J, SEO HW, et al. All Biomass and UV Protective Composite Composed of Compatibilized Lignin and Poly (Lactic-acid)[J]. Scientific Reports, 2017, 7: 43596. doi: 10.1038/srep43596
[15]	GORDOBIL O, EGUES I, LABIDI J. Modification of Eucalyptus and Spruce organosolv lignins with fatty acids to use as filler in PLA[J]. Reactive and Functional Polymers, 2016, 104: 45-52. doi: 10.1016/j.reactfunctpolym.2016.05.002
[16]	WASTI S, TRIGGS E, FARAG R, et al. Influence of plasticizers on thermal and mechanical properties of biocomposite filaments made from lignin and polylactic acid for 3D printing[J]. Composites Part B:Engineering, 2021, 205: 108483. doi: 10.1016/j.compositesb.2020.108483
[17]	FENG Y, LAN J, MA P, et al. Chemical structure and thermal properties of lignin modified with polyethylene glycol during steam explosion[J]. Wood Science and Technology, 2017, 51: 135-150. doi: 10.1007/s00226-016-0870-9
[18]	NAKAGAME S, CHANDRA R-P, KADLA J-F, et al. The isolation, characterization and effect of lignin isolated from steam pretreated Douglas-fir on the enzymatic hydrolysis of cellulose[J]. Bioresource Technology, 2011, 102: 4507-4517. doi: 10.1016/j.biortech.2010.12.082
[19]	JU Z, ZIEGLER-DEVIN I, CHRUSCIEL L, et al. Efficient preparation of polyethylene glycol (PEG)-modified lignin from steam exploded hardwood biomass[J]. Industrial crops and products, 2023, 26: 117614.
[20]	MIGNEAULT S, KOUBAA A, ERCHIDUI F, et al. Effects of processing method and fiber size on the structure and properties of wood-plastic composites[J]. Composites Part A:Applied Science and Manufacturing, 2009, 40: 80-5. doi: 10.1016/j.compositesa.2008.10.004
[21]	HE Q, ZIEGLER-DEVIN I, CHRUSCIEL L, et al. Lignin-First Integrated Steam Explosion Process for Green Wood Adhesive Application[J]. ACS Sustainable Chemistry & Engineering, 2020, 8: 5380-5392.
[22]	左迎峰, 张彦华, 乔治邦, 等. 甘油用量对淀粉/聚乳酸复合材料热性能的影响[J]. 材料导报, 2014, 28(12): 63-65+69. ZUO yingfeng, ZHANG yanhua, QIAO zhibang, et al. Effects of Glycerol Amount on the Thermal Properties of Starch/Polylactic Acid Composites[J]. Materials Reports, 2014, 28(12): 63-65+69(in Chinese).
[23]	熊兴泉, 张辉, 高利柱. 木质素的功能化与应用研究进展[J]. 应用化学, 2023, 40(6): 806-819. XIONG xingquan, ZHANG hui, GAO lizhu. Progress in Chemical Modification and Application of Lignin[J]. Chinese Journal of Applied Chemistry, 2023, 40(6): 806-819(in Chinese).
[24]	欧阳琛, 沈人杰, 陈心茹, 等. 聚乳酸共混木质素静电纺丝特性与材料性能[J]. 纤维素科学与技术, 2022, 30(3): 1-10. OU yangchen, SHEN renjie, CHEN xinru, et al. Electrospinning Characteristics and Properties of Polylactic Acid Blended Lignin Composites[J]. Journal of Cellulose Science and Technology, 2022, 30(3): 1-10(in Chinese).
[25]	刘太闯, 宋修德, 姚亮, 等. 不同稳定剂和单体对PLA稳定性及力学性能的影响[J]. 上海塑料, 2022, 50(6): 31-35. LIU taichuang, SONG xiude, YAO liang, et al. Effect of Different Stabilizer and Monomer on the Stability and Mechanical Properties of PLA[J]. Shanghai Plastics, 2022, 50(6): 31-35(in Chinese).
[26]	葛正浩, 邹辛祺, 陈威, 等. PLA/杨木粉木塑复合材料的配方优化与力学性能研究[J]. 陕西科技大学学报, 2020, 38(1): 124-130+163. GE zhenghao, ZOU xinqi, CHEN wei, et al. Research on formula optimization and mechanical properties of PLA/Poplar Powder Wood-Plastic Composites[J]. Journal of Shaanxi University of Science & Technology, 2020, 38(1): 124-130+163(in Chinese).
[27]	MATEA P, ROBERT P, CHRISTIAN P. Influence of nanofibrillated cellulose on the mechanical and thermal properties of poly(lactic acid)[J]. European Polymer Journal, 2019, 114: 426-433. doi: 10.1016/j.eurpolymj.2019.03.014
[28]	DAS P P, CHAUDHARY V, AHMAD F, et al. Effect of nanotoxicity and enhancement in performance of polymer composites using nanofillers: A state-of-the-art review[J]. Polymer Composites, 2021, 42(5): 2152-2170. doi: 10.1002/pc.25968
[29]	徐佳, 李园, 冯昆鹏, 等. 聚乳酸/芦苇纤维复合材料降解性能研究[J]. 中国塑料, 2023, 37(4): 23-29. XU jia, LIyuan, FENG kunpeng, et al. Study on degradation properties of poly(lactic acid)/reed fiber composites[J]. China Plastics, 2023, 37(4): 23-29(in Chinese).
[30]	吕东阳, 陈利, 王静. 玻璃纤维及偶联剂对聚乳酸降解性能的影响 [J/OL]. 复合材料学报, 2024, 1-8. LYU Dongyang, CHEN Li, WANG Jing. Effect of glass fibers and coupling agents on the degradation properties of polylactic acid [J/OL]. Acta Materiae Compositae Sinica, 2024, 1-8(in Chinese).