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Ring-opening Polymerization of
ω -Pentadecalactone Catalyzed by Organobases toward Degradable Polyethylene-like Plastics- Acta Polymerica Sinica Vol. 55, Issue 8, Pages: 976-985(2024)
- 作者机构：
1.青岛科技大学，化工学院，青岛 266042
2.青岛科技大学，高分子科学与工程学院，青岛 266042
- 作者简介：
Zhi-bo Li, E-mail: zbli@qust.edu.cn
- 基金信息：
DOI：10.11777/j.issn1000-3304.2024.24067
CLC：Published：20 August 2024，
Published Online：03 June 2024，
Received：03 March 2024，
Accepted：12 April 2024
- 稿件说明：
移动端阅览
黄炳政, 韩瑞, 李峥, 李志波. 有机碱催化ω‑十五内酯开环聚合制备类聚乙烯性质的可降解塑料. 高分子学报, 2024, 55(8), 976-985
Huang, B. Z.; Han, R.; Li, Z.; Li, Z. B. Ring-opening polymerization of ω-pentadecalactone catalyzed by organobases toward degradable polyethylene-like plastics. Acta Polymerica Sinica, 2024, 55(8), 976-985
黄炳政, 韩瑞, 李峥, 李志波. 有机碱催化ω‑十五内酯开环聚合制备类聚乙烯性质的可降解塑料. 高分子学报, 2024, 55(8), 976-985 DOI： 10.11777/j.issn1000-3304.2024.24067.
Huang, B. Z.; Han, R.; Li, Z.; Li, Z. B. Ring-opening polymerization of ω-pentadecalactone catalyzed by organobases toward degradable polyethylene-like plastics. Acta Polymerica Sinica, 2024, 55(8), 976-985 DOI： 10.11777/j.issn1000-3304.2024.24067.
摘要
以环三磷腈碱(CTPB)为催化剂，以苄醇(BnOH)为引发剂，实现了
ω
-十五内酯(PDL)的高效可控开环聚合. 通过优化实验条件，得到了高分子量的聚
ω
-十五内酯(PPDL). 示差扫描量热法(DSC)表征证明了PPDL聚酯材料较好的结晶性. 高分子量的PPDL不仅有与聚乙烯相似的力学性质、结晶性和高熔点(
T
m
=95.5 ℃)，而且还具有聚酯类材料的降解性. 合成了PDL与
ε
-己内酯(
ε
-CL)的无规共聚物，证明可以通过改变
ε
-CL的含量实现共聚物的熔点、力学性质和降解性可控调节. 进一步通过双官能团引发剂合成中低分子量的双羟基端PPDL，证明可以通过与二异氰酸酯进行扩链反应制备高分子量PPDL (PPDL-E)，力学性能能够得到有效提升. 最后在碱性条件下实现了PPDL共聚酯的水解，验证了PPDL及其与
ε
-CL共聚物的水解性能.
Abstract
This study reported that an efficient and controllable
ring-opening polymerization of
ω
‑pentadecalactone (PDL) by using cyclic trimeric phosphazene base (CTPB) as a catalyst and benzyl alcohol (BnOH) as an initiator. High molecular weight PPDL was obtained after optimizing the experimental conditions. The PPDL film with high molecular weight not only showed similar mechanical properties
crystallinity and high melting point (
T
m
=95.5 ℃) as polyethylene
but also exhibited the degradability of aliphatic polyesters. Differential scanning calorimetry (DSC) tests proved that PPDL had good crystallinity. Wide-angle X-ray scattering (WAXS) showed that PPDL had a unit cell structure similar to that of commercial high-density polyethylene (HDPE). Moreover
bishydroxyl-end-capped PPDL (PPDL-diol) can be easily prepared
via
ring opening polymerization (ROP) of PDL with 1
4-benzenedimethanol (BDM) as initiator. Then the PPDLs with high molecular weights were obtained by chain extension reactions with diisocyanates and showed enhanced mechanical properties. In addition
we synthesized a variety of random copolymers with different ratios of PDL to
ε
-caprolactone (
ε
-CL). The melting points and hydrolysis of the copolymers could be adjusted by changing the ratio of
ε
-CL. The melting points of the obtained random copolymers could be adjusted in the range of 53.0-95.5 ℃ by changing the ratio of
ε
-CL. Finally
the hydrolysis of PPDL copolyester was achieved under alkaline conditions. Compared with PPDL homopolymer
the hydrolysis of random copolymers showed faster hydrolysis rate and adjustability.
关键词
开环聚合有机碱类聚乙烯高分子可降解聚酯
Keywords
Ring-opening polymerizationOrganobasePolyethylene-like polymersDegradable polyester
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