纺织学报 ›› 2021, Vol. 42 ›› Issue (01): 16-21.doi: 10.13475/j.fzxb.20200504006

• 纤维材料 • 上一篇    下一篇

可降解聚羟基乙酸低聚物改性聚酯的合成及其性能

靳琳琳1, 田俊凯2, 李家炜1, 戚栋明1(), 沈晓炜2, 邬春涛3   

  1. 1.浙江理工大学 先进纺织材料与制备技术教育部重点实验室, 浙江 杭州 310018
    2.浙江卫星石化股份有限公司, 浙江 嘉兴 314000
    3.宁波市生态环境局, 浙江 宁波 315000
  • 收稿日期:2020-05-19 修回日期:2020-09-08 出版日期:2021-01-15 发布日期:2021-01-21
  • 通讯作者: 戚栋明
  • 作者简介:靳琳琳(1986—),女,博士生。主要研究方向为聚合物材料改性。
  • 基金资助:
    浙江省重点研发计划项目(2020C01148);浙江省基础公益研究计划项目(LGG20E030006);国家级大学生创新创业训练计划项目(201910338007);浙江理工大学基本科研业务费专项资金资助项目(2019Q021)

Synthesis and properties of biodegradable polyglycolic acid oligomer modified polyester

JIN Linlin1, TIAN Junkai2, LI Jiawei1, QI Dongming1(), SHEN Xiaowei2, WU Chuntao3   

  1. 1. Key Laboratory of Advanced Textile Materials & Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Satellite Petrochemical Co., Ltd., Jiaxing, Zhejiang 314000, China
    3. Ningbo Municipal Bureau of Ecology and Environment, Ningbo, Zhejiang 315000, China
  • Received:2020-05-19 Revised:2020-09-08 Online:2021-01-15 Published:2021-01-21
  • Contact: QI Dongming

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摘要：

为改善芳香族聚酯(PET)的降解性能,采用可降解的聚羟基乙酸(PGA)低聚物,利用熔融缩聚和固相缩聚联用的工艺路线,对聚酯进行共聚改性合成聚对苯二甲酸乙二醇酯-co-聚乙醇酸共聚酯(PET-co-PGA)。借助核磁共振波谱仪、差示扫描量热仪、拉伸试验机、扫描电子显微镜和荧光显微镜等对共聚酯的结构、特征黏度、结晶行为、力学性能及降解性能进行表征与分析。结果表明:与纯PET相比,共聚改性破坏了PET-co-PGA的结构规整性,随着PGA质量分数的增加,共聚酯的熔点下降,结晶温度降低,结晶能力逐渐降低;在低PGA添加量时共聚酯具有更好的韧性,当PGA质量分数为5%时,共聚酯的断裂伸长率从13.1%增加至15.0%;改性后聚酯降解速率随着PGA质量分数增加而逐渐提升。

关键词: 改性聚酯, 聚羟基乙酸, 聚对苯二甲酸乙二醇酯, 共聚改性, 熔融缩聚, 固相缩聚

Abstract:

In order to improve the degradation performance of aromatic poly (ethylene terephthalate) (PET), a novel polyethylene terephthalate-co-polyglycolic acid copolymer (PET-co-PGA) was synthesized by copolymerization modification of polyester with degradable polyglycolic acid (PGA) oligomer, through combining melt polycondensation and solid-phase polycondensation process. The structure, intrinsic viscosity, crytallization behavior and degradation property of the novel copolyester were characterized and analyzed by using nuclear magnetic resonance spectrometer, differential scanning calorimeter, tensile tester, scanning electron microscope and fluorescence microscope. The results show that the introduction of PGA damages the regularity of PET and results in the decrease of the melting point, crystallization temperature and crystallization ability. The tensile experiments show that the synthesized copolyester with the low volume of addition of PGA has better tenacity compared with pure PET. When 5% PGA is added,the elongation at the break of the copolyester is increased from 13.1% to 15.0%. The degradation rate of pre-modified PET gradually increases with the amount of PGA added.

Key words: modified polyester, polyglycolic acid, poly (ethylene terephthalate), modification by copolymerization, melt polycondensation, solid state polycondensation

中图分类号: 

  • TS193.5

图1

聚羟基乙酸低聚物改性聚酯的合成路线"

表1

聚羟基乙酸低聚物改性聚酯投料比"

样品
编号		 PTA的量/
mol		 EG的量/
mol		 PGA质量
分数/%
1# 0.9 1.2 0
2# 0.9 1.2 1
3# 0.9 1.2 5
4# 0.9 1.2 10
5# 0.9 1.2 15

图2

PET-co-PGA改性聚酯的化学结构式和核磁共振氢谱图"

图3

纯PET和PET-co-PGA共聚酯的DSC曲线"

表2

纯PET和PET-co-PGA共聚酯的DSC数据"

样品
编号		 Tg/
℃		 Tc/
℃		 Tc-Tg/
℃		 Tm/
℃		 ΔHc/
(J·g-1)		 ΔHm/
(J·g-1)
1# 81.94 180 98.06 248 47.32 67.57
2# 78.68 172 93.32 239 80.05 69.63
3# 75.23 140 64.77 218 17.50 57.10
4# 71.84 191 33.51
5# 67.21 173 8.41

表3

PET-co-PGA共聚酯的力学性能"

样品
编号		 拉伸断裂强度/
MPa		 弹性模量/
MPa		 断裂伸长率/
%
1# 67.67±0.4 589.03±2.5 13.09±0.20
2# 68.97±0.5 590.19±1.5 13.11±0.15
3# 69.68±0.4 600.32±2.0 15.28±0.22
4# 58.03±0.5 535.48±1.8 10.94±0.24
5# 55.47±0.4 523.33±1.7 9.64±0.28

图4

共聚酯碱性条件下的降解行为"

图5

共聚酯纤维降解过程的扫描电镜照片(×5 000)"

图6

共聚酯纤维在降解过程中结构形态变化的荧光照片"

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