聚己内酯/聚丁内酰胺电纺纤维的制备及性能

明远; 陈涛; 赵黎明; 邱勇隽

doi:10.14133/j.cnki.1008-9357.20220520001

聚己内酯/聚丁内酰胺电纺纤维的制备及性能

doi: 10.14133/j.cnki.1008-9357.20220520001

明远^1,,
陈涛^{1, 3, ,},
赵黎明^{2, 3, ,},
邱勇隽^{2, 3}

1.
材料科学与工程学院, 上海市先进聚合物材料重点实验室华东理工大学
2.
生物工程学院, 生物反应器工程国家重点实验室, 发酵工业分离提取技术研发中心华东理工大学
3.
中国轻工业生物基材料工程重点实验室,上海 200237 华东理工大学

基金项目: 上海市自然科学基金 (21ZR1416000)；上海市“科技创新行动计划” 技术标准项目（21DZ2205900）

详细信息

作者简介:
明远：明　远（1997—），女，山东潍坊人，硕士，主要研究方向为静电纺丝。E-mail：1059807411@qq.com

通讯作者:
陈　涛，E-mail：tchen@ecust.edu.cn

赵黎明，E-mail：zhaoliming@ecust.edu.cn

中图分类号: TQ340
计量
- 文章访问数: 105
- HTML全文浏览量: 98
- PDF下载量: 130
- 被引次数: 0
出版历程
- 收稿日期: 2022-05-20
- 录用日期: 2022-11-29
- 网络出版日期: 2022-12-01
- 刊出日期: 2023-04-01

Preparation and Properties of PCL/PBL Electrospun Fibers

MING Yuan^1
,,
CHEN Tao^{1, 3
, ,},
ZHAO Liming^{2, 3
, ,},
QIU Yongjun^{2, 3}

1.
Shanghai Key Laboratory of Advanced Polymer Materials, School of Materials Science and Engineering
2.
State Key Laboratory of Bioreactor Engineering, The R&D Center of Separation and Extraction Technology in Fermentation Industry, School of Biotechnology
3.
Key Laboratory of Bio-based Material Engineering of China National Light Industry Council, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 通过溶液静电纺丝法制备了聚己内酯/聚丁内酰胺（PCL/PBL）电纺纤维膜。采用扫描电子显微镜（SEM）、水相接触角测量仪、原子力显微镜（AFM）、能谱仪（EDS）、透射电子显微镜（TEM）、X射线衍射仪（XRD）、热重分析仪（TGA）、差示扫描量热仪（DSC）、电子万能拉力机对PCL/PBL电纺纤维的形貌、亲疏水性、结晶性能、热性能及力学性能进行了研究。结果表明，随着PBL含量的增加，纤维直径增大、分布变窄，且纤维膜的亲水性明显改善；PCL与PBL有一定相容性，PCL/PBL电纺纤维膜的结晶度高于PCL或PBL均聚物电纺纤维膜，并随PBL含量增加而提高；PCL/PBL电纺纤维膜中PCL熔点随PBL含量增加而略有增加，PBL组分的熔点则基本不变。两组分的结晶温度和纤维膜热稳定性均随PBL含量增加而降低。PBL的加入使电纺纤维膜的力学性能明显提高。
- 聚己内酯 /
- 聚丁内酰胺 /
- 静电纺丝 /
- 亲水性 /
- 相容性 /
- 力学性能
Abstract: Electrospun polycaprolactone (PCL) nanofibers are often used as biomedical materials for drug release systems and tissue engineering scaffolds due to their biodegradability, but the hydrophobicity and mechanical defects limit the wider applications. Here, polybutyrolactam (PBL), a biodegradable polyamide with excellent mechanical properties and high moisture regain, was blended with PCL in co-solvent to electrospin fiber membranes with improved mechanical properties and the hydrophilicity. Scanning electron microscope (SEM), water contact angle measuring instrument, atomic force microscope (AFM), energy dispersive spectroscopy (EDS), transmission electron microscope (TEM), X-ray diffraction (XRD), thermogravimetric analyzer (TGA), differential scanning calorimetry (DSC), electronic universal tension machine were used to investigate the morphology, diameter and distribution of fibers, the hydrophilicity, crystallinity, thermal and mechanical properties of the fiber membranes. It was found that increasing the PBL content increased the fiber diameter, narrowed the diameter distribution, and significantly improved the hydrophilicity of the fiber membrane. PBL had been shown to be compatible with PCL, and the crystallinity of PCL/PBL electrospun fiber membranes with increasing PBL content was higher than that of monocomponent fiber membranes. Increasing the PBL content also slightly raised the melting point of the PCL component in the fiber membranes, while that of PBL remained unchanged. The crystallization temperatures of PBL and PCL, as well as the thermal stability of the fiber membranes decreased with increasing PBL content. The addition of PBL significantly improved the mechanical properties of electrospun fiber membranes. The greater PBL content was, the better the mechanical properties of the fiber membrane were.
- polycaprolactone /
- polybutyrolactam /
- electrospinning /
- hydrophilicity /
- compatibility /
- mechanical property

HTML全文

图 1 PCL/PBL电纺纤维的SEM图像及纤维直径分布

Figure 1. SEM images and fiber diameter distributions of PCL/PBL electrospun fibers

下载: 全尺寸图片幻灯片

图 2 PCL/PBL电纺纤维膜水相接触角

Figure 2. Water contact angles of PCL/PBL electrospun fiber membranes

下载: 全尺寸图片幻灯片

图 3 PCL/PBL电纺纤维膜的AFM图像

Figure 3. AFM images of PCL/PBL electrospun fiber membranes

下载: 全尺寸图片幻灯片

图 4 PCL/PBL电纺纤维的TEM图像

Figure 4. TEM images of PCL/PBL electrospun fibers

下载: 全尺寸图片幻灯片

图 5 PCL/PBL电纺纤维膜的红外谱图

Figure 5. FT-IR spectra of PCL/PBL electrospun fiber membranes

下载: 全尺寸图片幻灯片

图 6 PCL/PBL电纺纤维膜的XRD曲线

Figure 6. XRD patterns of PCL/PBL electrospun fiber membranes

下载: 全尺寸图片幻灯片

图 7 PCL/PBL电纺纤维膜的（a）TGA曲线和（b）DTG曲线

Figure 7. (a) TGA and (b) DTG curves of PCL/PBL electrospun fiber membranes

下载: 全尺寸图片幻灯片

图 8 PCL/PBL电纺纤维膜的DSC曲线

Figure 8. DSC curves of PCL/PBL electrospun fiber membranes

下载: 全尺寸图片幻灯片

图 9 PCL/PBL电纺纤维膜的低温DSC曲线

Figure 9. Low temperature DSC curves of PCL/PBL electrospun fiber membranes

下载: 全尺寸图片幻灯片

表 1 PCL/PBL电纺纤维特性

Table 1. Characters of PCL/PBL electrospun fibers

Sample	D/μm	C_V	X_c/%	ρ/%
PCL	—	—	35	—
PCL/PBL(95/5)	0.841 ± 0.238	0.283	36	34.6 ± 1.5
PCL/PBL(90/10)	0.583 ± 0.078	0.134	42	27.9 ± 0.4
PCL/PBL(85/15)	1.088 ± 0.142	0.131	47	22.8 ± 0.5
PCL/PBL(80/20)	1.010 ± 0.095	0.094	52	18.0 ± 0.6
PBL	0.125 ± 0.030	0.240	29	-

下载: 导出CSV

表 2 PCL/PBL电纺纤维膜表面元素分布

Table 2. Element distribution on PCL/PBL electrospun fiber membranes surface

Sample	w_t/%			w_p/%
Sample	N	O	C	N	O	C
PCL/PBL(95/5)	0.9	30.3	68.8	4.4	17.5	78.1
PCL/PBL(90/10)	1.8	29.7	68.5	5.9	20.2	73.9
PCL/PBL(85/15)	2.7	29.2	68.1	6.9	21.1	72.0
PCL/PBL(80/20)	3.6	28.7	67.7	7.7	21.6	70.7

下载: 导出CSV

表 3 PCL/PBL电纺纤维膜的力学性能

Table 3. Mechanical properties of PCL/PBL electrospun fiber membranes

Sample	Young’s modulus/MPa	Tensile strength/MPa	Elongation at break/%
PCL/PBL(95/5)	26.01 ± 10.97	1.41 ± 0.33	5.9 ± 3.8
PCL/PBL(90/10)	34.29 ± 5.87	1.65 ± 0.35	5.9 ± 3.2
PCL/PBL(85/15)	27.67 ± 6.40	1.81 ± 0.10	38.4 ± 18.1
PCL/PBL(80/20)	45.90 ± 8.30	3.16 ± 0.99	37.8 ± 6.9

下载: 导出CSV

参考文献(27)

[1]	CHEN S X, LI R Q, LI X R, XIE J W. Electrospinning: An enabling nanotechnology platform for drug delivery and regenerative medicine [J]. Advanced Drug Delivery Reviews,2018,132(6):188-213.
[2]	LI J J, YANG Y Y, YU D G, DU Q, YANG X L. Fast dissolving drug delivery membrane based on the ultra-thin shell of electrospun core-shell nanofibers [J]. European Journal of Pharmaceutical Sciences,2018,122(10):195-204.
[3]	HIVECHI A, BAHRAMI S H, SIEGEL R A. Drug release and biodegradability of electrospun cellulose nanocrystal reinforced polycaprolactone [J]. Materials Science & Engineering C: Materials for Biological Applications,2019,94(10):929-937.
[4]	HOUSHYAR S, KUMAR G S, RIFAI A, TRAN N, NAYAK R, SHANKS R A, PADHYE R, FOX K, BHATTACHARYYA A. Nanodiamond/poly-ε-caprolactone nanofibrous scaffold for wound management [J]. Materials Science and Engineering:C,2019,100(7):378-387.
[5]	HOMAEIGOHAR S, BOCCACCINI A R. Nature-derived and synthetic additives to poly(ɛ-caprolactone) nanofibrous systems for biomedicine: An updated overview [J]. Frontiers in Chemistry,2022,9:809676. doi: 10.3389/fchem.2021.809676
[6]	CHANDRA R, RUSTGI R. Biodegradable polymers [J]. Progress in Polymer Science,1998,23(7):1273-1335. doi: 10.1016/S0079-6700(97)00039-7
[7]	OKADA M. Chemical syntheses of biodegradable polymers [J]. Progress in Polymer Science,2002,27(1):87-133. doi: 10.1016/S0079-6700(01)00039-9
[8]	NAIR L S, LAURENCIN C T. Biodegradable polymers as biomaterials [J]. Progress in Polymer Science,2007,32(8):762-798.
[9]	LI P F, RUAN L M, WANG R F, LIU T Q, SONG G, GAO X F, JIANG G H, LIU X Y. Electrospun scaffold of collagen and polycaprolactone containing ZnO quantum dots for skin wound regeneration [J]. Journal of Bionic Engineering,2021,18(6):1378-1390. doi: 10.1007/s42235-021-00115-7
[10]	陈晨, 陈涛, 赵黎明, 邱永隽. CO₂对酰基化合物引发2-吡咯烷酮聚合的影响 [J]. 功能高分子学报,2020,33(3):290-296. CHEN C, CHEN T, ZHAO L M, QIU Y J. Influence of CO₂ on acyl compound initiated polymerization of 2-pyrrolidone [J]. Journal of Functional Polymers,2020,33(3):290-296.
[11]	BACSKAI R. Synthesis and thermal stability evaluation of end-capped nylon 4 oligomers [J]. Polymer Bulletin,1984,11(3):229-236.
[12]	HASHIMOTO K, HAMANO T, OKADA M. Degradation of several polyamides in soils [J]. Journal of Applied Polymer Science,1994,54(10):1579-1583. doi: 10.1002/app.1994.070541023
[13]	FUKUDA Y, SASANUMA Y. Computational characterization of nylon 4, a biobased and biodegradable polyamide superior to nylon 6 [J]. ACS Omega,2018,3(8):9544-9555. doi: 10.1021/acsomega.8b00915
[14]	TACHIBANA K, URANO Y, NUMATA K. Biodegradability of nylon 4 film in a marine environment [J]. Polymer Degradation and Stability,2013,98(9):1847-1851. doi: 10.1016/j.polymdegradstab.2013.05.007
[15]	YAMANO N, KAWASAKI N, IDA S, NAKAYAMA Y, NAKAYAMA A. Biodegradation of polyamide 4 in vivo [J]. Polymer Degradation and Stability,2017,137(6):281-288.
[16]	NAKAYAMA A, YAMANO N, KAWASAKI N, NAKAYAMA Y. Synthesis and biodegradation of poly(2-pyrrolidone-co-ε-caprolactone)s [J]. Polymer Degradation and Stability,2013,98(9):1882-1888. doi: 10.1016/j.polymdegradstab.2013.04.011
[17]	CHEN T, WANG C, ZHAO L, WANG L, QIU Y. Suspension polymerization of 2-pyrrolidone in the presence of CO₂ and organic promoters [J]. Journal of Applied Polymer Science,2021,138(4):49736. doi: 10.1002/app.49736
[18]	BLAZKOVA L, MALINOVA L, BENESOVA V, RODA J, BROZEK J. Nanofibers prepared by electrospinning from solutions of biobased polyamide 4 [J]. Journal of Polymer Science Part A:Polymer Chemistry,2017,55(13):2203-2210. doi: 10.1002/pola.28605
[19]	GHASEMI-MOBARAKEH L, PRABHAKARAN M P, MORSHED M, NASR-ESFAHANI M H, RAMAKRISHNA S. Electrospun poly(ε-caprolactone)/gelatin nanofibrous scaffolds for nerve tissue engineering [J]. Biomaterials,2008,29(34):4532-4539. doi: 10.1016/j.biomaterials.2008.08.007
[20]	张媛婷, 明远, 陈涛, 赵黎明, 邱永隽. 聚乳酸/聚丁内酰胺电纺核-壳结构纤维的制备及性能 [J]. 功能高分子学报,2022,35(2):137-145. doi: 10.14133/j.cnki.1008-9357.20210531001 ZHANG Y T, MING Y, CHEN T, ZHAO L M, QIU Y J. Preparation and properties of PLLA/PBL electrospun fibers with core-sheath structure [J]. Journal of Functional Polymers,2022,35(2):137-145. doi: 10.14133/j.cnki.1008-9357.20210531001
[21]	祝振鑫. 膜材料的亲水性、膜表面对水的湿润性和水接触角的关系 [J]. 膜科学与技术,2014,34(2):1-4. doi: 10.3969/j.issn.1007-8924.2014.02.001 ZHU Z X. Hydrophilicity, wettability and contact angle [J]. Membrane Science and Technology,2014,34(2):1-4. doi: 10.3969/j.issn.1007-8924.2014.02.001
[22]	CHEN T, ZHONG G C, ZHANG Y T, ZHAO L M, QIU Y J. Bio-based and biodegradable electrospun fibers composed of poly(L-lactide) and polyamide 4 [J]. Chinese Journal of Polymer Science,2020,38(1):53-62. doi: 10.1007/s10118-019-2299-8
[23]	MARTINS-FRANCHETTI S M, EGERTON T A, WHITE J R. Morphological changes in poly(caprolactone)/poly(vinyl chloride) blends caused by biodegradation [J]. Journal of Polymers and the Environment,2010,18(1):79-83. doi: 10.1007/s10924-009-0158-3
[24]	WAN Y, LU X L, DALAI S Q, ZHANG J. Thermophysical properties of polycaprolactone/chitosan blend membranes [J]. Thermochimica Acta,2009,487(1-2):33-38. doi: 10.1016/j.tca.2009.01.007
[25]	ALI S, KHATRI Z, OH K W, KIM I S, KIM S H. Preparation and characterization of hybrid polycaprolactone/cellulose ultrafine fibers via electrospinning [J]. Macromolecular Research,2014,22(5):562-568. doi: 10.1007/s13233-014-2078-x
[26]	ZHONG Z, GUO Q. Miscibility and morphology of thermosetting polymer blends of novolac resin with poly(ethylene oxide) [J]. Polymer,1998,39(3):517-523. doi: 10.1016/S0032-3861(97)00309-1
[27]	ZHENG H, ZHENG S, GUO Q. Thermosetting polymer blends of unsaturated polyester resin and poly(ethylene oxide): I. Miscibility and thermal properties [J]. Journal of Polymer Science Part A:Polymer Chemistry,1997,35(15):3161-3168. doi: 10.1002/(SICI)1099-0518(19971115)35:15<3161::AID-POLA9>3.0.CO;2-Z