脂环族/直链脂肪族硬段复配对聚氨酯共混材料结构与性能的影响

王玉杰; 刘家甜; 荆友麒; 王非; 陈春东; 胡亚勇

doi:10.11777/j.issn1000-3304.2026.26113

您当前的位置：

首页 >

文章列表页 >

脂环族/直链脂肪族硬段复配对聚氨酯共混材料结构与性能的影响

研究论文 | 更新时间：2026-07-24

- 脂环族/直链脂肪族硬段复配对聚氨酯共混材料结构与性能的影响
- Effect of Alicyclic/Aliphatic Hard Segment on the Structure and Properties of Polyurethane Blends
- 高分子学报 2026年57卷第8期页码：1834-1844
- 作者机构：
  
  1.河南工程学院化工与印染工程学院郑州 450007
  2.兰考县鼎丰木业有限公司开封 475399
- 作者简介：
  
  E-mail: wf2003@haue.edu.cn
- 基金信息：
  
  河南省科技攻关项目(262102320178;252102321152);河南省大学生创新创业训练计划(202511517002);河南工程学院教育教学改革研究项目(2025JYYB45);河南工程学院开放实验室重点项目
- DOI：10.11777/j.issn1000-3304.2026.26113
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7631
- 收稿：2026-04-21，
  
  录用：2026-05-28，
  
  网络首发：2026-07-13，
  
  纸质出版：2026-08-20
- 稿件说明：
移动端阅览
王玉杰, 刘家甜, 荆友麒, 王非, 陈春东, 胡亚勇. 脂环族/直链脂肪族硬段复配对聚氨酯共混材料结构与性能的影响. 高分子学报, 2026, 57(8), 1834-1844.

Wang, Y. J.; Liu, J, T.; Jing, Y. Q.; Wang, F.; Chen, C. D.; Hu, Y. Y. Effect of alicyclic/aliphatic hard segment on the structure and properties of polyurethane blends. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1834-1844.
王玉杰, 刘家甜, 荆友麒, 王非, 陈春东, 胡亚勇. 脂环族/直链脂肪族硬段复配对聚氨酯共混材料结构与性能的影响. 高分子学报, 2026, 57(8), 1834-1844. DOI： 10.11777/j.issn1000-3304.2026.26113. CSTR： 32057.14.GFZXB.2026.7631.

Wang, Y. J.; Liu, J, T.; Jing, Y. Q.; Wang, F.; Chen, C. D.; Hu, Y. Y. Effect of alicyclic/aliphatic hard segment on the structure and properties of polyurethane blends. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1834-1844. DOI： 10.11777/j.issn1000-3304.2026.26113. CSTR： 32057.14.GFZXB.2026.7631.

摘要

以聚碳酸酯二元醇为软段、1

4-丁二醇为扩链剂，分别采用异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)合成了具有脂环族硬段的聚氨酯(R-PCPU)与直链脂肪族硬段的聚氨酯(L-PCPU)，并通过溶液共混制备了不同质量比的R-PCPU/L-PCPU共混材料(PUB). 采用傅里叶变换红外光谱(FTIR)、热失重分析(TGA)、X射线衍射光谱(XRD)、示差扫描量热分析(DSC)及万能试验机等对PUB的结构与性能进行表征. 结果表明：受硬段空间位阻影响，L-PCPU中的氢键作用及微相分离程度均高于R-PCPU，而两者在PUB中均随L-PCPU含量的增加而增强. R-PCPU以软段结晶为主(熔融温度约43.26 ℃)，L-PCPU以硬段结晶为主(熔融温度约168.66 ℃)，PUB则同时呈现软、硬段结晶，其软段结晶能力随L-PCPU含量增加而减弱，硬段结晶能力则随之增强. 得益于环型与线型硬段的协同效应，PUB实现了力学性能的可控调节，兼具优于R-PCPU的断裂伸长率(最高达900%)和优于L-PCPU的拉伸强度(最高达75.62 MPa). 此外，软硬段的同时结晶赋予PUB优异的形状记忆性能，使其具备远高于R-PCPU或L-PCPU的应用价值. 基于综合性能优势，PUB在正畸弓丝、自收缩缝合线等智能医用器械领域展现出广阔的应用前景，本工作同时为形状记忆聚氨酯的结构设计与简便制备提供了新策略.

Abstract

Using polycarbonate diol as the soft segment and 1

4-butanediol as the chain extender

polyurethanes with alicyclic hard segments (R-PCPU) and aliphatic hard segments (L-PCPU) were synthesized using isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI)

respectively. A series of R-PCPU/L-PCPU blends (PUB) with different mass ratios were prepared

via

solution blending. The structure and properties of PUB were characterized using Fourier transform infrared spectroscopy (FTIR)

thermogravimetric analyze (TGA)

X-ray diffraction (XRD)

differential scanning calorimetry (DSC)

and a universal testing machine. The results showed that

owing to the steric hindrance of the hard segments

hydrogen bonding and microphase separation were stronger in L-PCPU than in R-PCPU

and both properties in PUB increase with increasing L-PCPU content. R-PCPU primarily exhibited soft-segment crystallization (melting temperature of approximately 43.26 ℃)

whereas L-PCPU exhibited hard-segment crystallization (approximately 168.66 ℃). PUB exhibited crystallization behavior in both soft and hard segments. As the L-PCPU content increased

the crystallinity of the soft segment decreased

whereas that of the hard segment increased. Benefiting from the synergistic effects of the ring-shaped and linear hard segments

PUB exhibited controllable mechanical properties

with an elongatio

n at break (up to 900%) higher than that of R-PCPU and a tensile strength (up to 75.62 MPa) higher than that of L-PCPU. Furthermore

the synchronized crystallization behavior of the soft and hard segments endowed PUB with excellent shape memory properties

making it significantly more valuable than R-PCPU or L-PCPU. Owing to its comprehensive performance advantages

PUB showed great potential for application in the field of smart medical devices

such as orthodontic wires and self-contracting sutures. This study also provides a novel strategy for the structural design and simple preparation of shape memory polyurethane.

关键词

Keywords

references

Lu X. Y. ; Wei H. Q. ; Zhang P. ; Wei A. ; Zhao S. Y. ; Wang Q. ; Liu J. P. ; Yu Y. Designing strong yet tough, multifunctional and printable dynamic cross-linking waterborne polyurethane for customizable smart soft devices . Adv. Funct. Mater. , 2025 , 35 ( 36 ), 2502720 . doi: 10.1002/adfm.202502720 http://dx.doi.org/10.1002/adfm.202502720

Yao W. J. ; Huang J. ; Liu W. ; Ma J. H. ; Li J. Y. ; Liu D. S. ; Yang Y. M. ; Liu X. Y. ; Tian Q. Y. ; Liu W. T. Thermal/NIR activated self-healing polyurethane with shape memory toward multi-level encryption . Chem. Eng. J. , 2025 , 522 , 167643 . doi: 10.1016/j.cej.2025.167643 http://dx.doi.org/10.1016/j.cej.2025.167643

Mirasadi K. ; Yousefi M. A. ; Jin L. C. ; Rahmatabadi D. ; Baniassadi M. ; Liao W. H. ; Bodaghi M. ; Baghani M. 4D printing of magnetically responsive shape memory polymers: toward sustainable solutions in soft robotics, wearables, and biomedical devices . Adv. Sci. , 2026 , 13 ( 15 ), e 13091 . doi: 10.1002/advs.202513091 http://dx.doi.org/10.1002/advs.202513091

Zhang Y. C. ; Hu Q. Q. ; Yang S. R. ; Wang T. ; Sun W. X. ; Tong Z. Unique self-reinforcing and rapid self-healing polyampholyte hydrogels with a pH-induced shape memory effect . Macromolecules , 2021 , 54 ( 11 ), 5218 - 5228 . doi: 10.1021/acs.macromol.0c02657 http://dx.doi.org/10.1021/acs.macromol.0c02657

Liu W. K. ; Wang A. ; Yang R. B. ; Wu H. C. ; Shao S. R. ; Chen J. L. ; Ma Y. ; Li Z. ; Wang Y. C. ; He X. L. ; Li J. H. ; Tan H. ; Fu Q. Water-triggered stiffening of shape-memory polyurethanes composed of hard backbone dangling PEG soft segments . Adv. Mater. , 2022 , 34 ( 46 ), 2201914 . doi: 10.1002/adma.202201914 http://dx.doi.org/10.1002/adma.202201914

Lin C. ; Yang M. J. ; Zhang F. H. ; Liu Y. J. ; Leng J. S. Stimuli-responsive smart materials for biomedical applications . Mater. Sci. Eng. R Rep. , 2026 , 167 , 101126 . doi: 10.1016/j.mser.2025.101126 http://dx.doi.org/10.1016/j.mser.2025.101126

You D. Q. ; Lin L. N. ; Dong M. Y. ; Wu Y. H. ; Hu Y. J. ; Hu X. Y. ; Shao Y. J. ; Xie Y. ; Xu M. H. ; Chen G. C. ; Lan R. ; Ma H. Y. ; Zhou Y. T. ; Wang H. M. ; Jin B. J. ; Yu M. F. Recent advances in shape memory polymers for biomedical applications: bridging macro- and micro-scale effects . Smart Mater. Med. , 2025 , 6 ( 2 ), 240 - 269 . doi: 10.1016/j.smaim.2025.06.001 http://dx.doi.org/10.1016/j.smaim.2025.06.001

王有朋 . 具有多重响应形状记忆和自修复两性离子聚合物的制备研究 . 高分子通报 , 2020 , ( 6 ), 43 - 49 .

Zheng W. ; Wang Y. L. ; Zhang F. H. ; Li C. Y. ; Liu Y. J. ; Leng J. S. Development of shape memory polymers micro/nanofiber membranes in biomedical applications . Sci. Sin.-Tech. , 2018 , 48 ( 8 ), 811 - 826 . doi: 10.1360/n092018-00126 http://dx.doi.org/10.1360/n092018-00126

朱光明 , 魏堃 , 王坤 . 形状记忆聚合物及其在航空航天领域中的应用 . 高分子材料科学与工程 , 2010 , 26 ( 8 ), 168 - 171 .

Liu C. ; Xue T. T. ; Yang Y. J. ; Mu X. S. ; Wan X. ; Fan W. ; Liu T. X. Shape memory polyimide aerogel fabrics with high-thermal-switching-ratio enabled by synergistic micro- and macro-deformation . Adv. Funct. Mater. , 2026 , 36 ( 35 ), e 30874 . doi: 10.1002/adfm.202530874 http://dx.doi.org/10.1002/adfm.202530874

Chen T. Z. ; Xu J. ; Wang C. Y. ; Zhang X. R. ; Pei X. Q. ; Wang T. M. ; Wang Q. H. Shape-memory polyurethanes for polar wearables with ultrasensitive multi-monitoring . Nat. Commun. , 2025 , 16 , 11329 . doi: 10.1038/s41467-025-66422-3 http://dx.doi.org/10.1038/s41467-025-66422-3

邵建铭 , 仇超 , 董侠 , 王笃金 . 反式-1,4-聚异戊二烯(杜仲胶)改性方法与形状记忆应用进展 . 高分子学报 , 2025 , 56 ( 5 ), 734 - 753 .

冯茹 , 许雅惠 , 韩慧 , 黄文峻 , 王延斌 , 李兴建 . 4D打印形状记忆高分子的打印方法、驱动原理、变形模式和应用 . 材料导报 , 2021 , 35 ( 5 ), 5147 - 5157 . doi: 10.11896/cldb.20020012 http://dx.doi.org/10.11896/cldb.20020012

Lin C. ; Xin X. Z. ; Tian L. F. ; Zhang D. ; Liu L. W. ; Liu Y. J. ; Leng J. S. Thermal-, magnetic-, and light-responsive 4D printed SMP composites with multiple shape memory effects and their promising applications . Compos. Part B Eng. , 2024 , 274 , 111257 . doi: 10.1016/j.compositesb.2024.111257 http://dx.doi.org/10.1016/j.compositesb.2024.111257

李兴建 , 白宝仕 , 刘升 , 苗玉杰 , 郑朝晖 , 丁小斌 . 具有相分离结构的PMMA/PEG半互穿网络形状记忆高分子 . 材料导报 , 2020 , 34 ( 1 ), 2142 - 2146 .

王玉杰 , 陈科宇 , 程国栋 , 荆友麒 , 刘家甜 , 聂慧芳 , 王世民 , 王非 . 羟基磷灰石的异氰酸酯改性及其对热塑性聚氨酯性能的影响 . 高分子学报 , 2025 , 56 ( 6 ), 992 - 1001 .

王瑞 , 轩慧霞 , 陈海良 , 刘广臣 , 李英乾 , 管永 , 管清宝 , 游正伟 . 多重动态杂化交联构建聚肟氨酯弹性体及其自愈合与可回收再加工性能 . 高分子学报 , 2025 , 56 ( 11 ), 1976 - 1986 .

熊勇 , 姜昀良 , 董育民 , 邓景月 , 周建萍 , 周炳华 , 梁红波 . 基于分级氢键的自修复聚氨酯弹性体的微相分离结构与性能研究 . 高分子学报 , 2025 , 56 ( 3 ), 487 - 500 .

Shi J. X. ; Xia F. ; Tu Q. C. ; Wang C. ; Wang Z. Q. ; Li B. ; Guo B. H. ; Qiu C. ; Xu J. Damage-resistant and body-temperature shape memory skin-mimic elastomer for biomedical applications . Sci. Adv. , 2025 , 11 ( 24 ), eadv 4646 . doi: 10.1126/sciadv.adv4646 http://dx.doi.org/10.1126/sciadv.adv4646

史家昕 , 郭宝华 , 徐军 . 调控嵌段序列长度提升热塑性聚氨酯的力学性能 . 高分子学报 , 2025 , 56 ( 9 ), 1537 - 1545 .

Ur Rehman H. ; Chen Y. J. ; Hedenqvist M. S. ; Li H. ; Xue W. C. ; Guo Y. L. ; Guo Y. P. ; Duan H. N. ; Liu H. Z. Self-healing shape memory PUPCL copolymer with high cycle life . Adv. Funct. Mater. , 2018 , 28 ( 7 ), 1704109 . doi: 10.1002/adfm.201704109 http://dx.doi.org/10.1002/adfm.201704109

Guo Y. T. ; Chen Y. J. ; Yu Q. L. ; Liu H. Z. ; Li H. ; Yu Y. X. Ultra-tough and stress-free two-way shape memory polyurethane induced by polymer segment "spring" . Chem. Eng. J. , 2023 , 470 , 144212 . doi: 10.1016/j.cej.2023.144212 http://dx.doi.org/10.1016/j.cej.2023.144212

Wang Y. J. ; Wang L. L. ; Liu H. ; He S. Q. ; Liu X. Y. ; Liu W. T. ; Huang M. M. ; Zhu C. S. Polyurethane as smart biocoatings: effects of hard segments on phase structures and properties . Prog. Org. Coat. , 2021 , 150 , 106000 . doi: 10.1016/j.porgcoat.2020.106000 http://dx.doi.org/10.1016/j.porgcoat.2020.106000

Wang Y. J. ; Zhu M. ; Hao C. B. ; Dai R. X. ; Huang M. M. ; Liu H. ; He S. Q. ; Liu W. T. Development of semi-crystalline polyurethane with self-healing and body temperature-responsive shape memory properties . Eur. Polym. J. , 2022 , 167 , 111060 . doi: 10.1016/j.eurpolymj.2022.111060 http://dx.doi.org/10.1016/j.eurpolymj.2022.111060

袁开军 , 江治 , 李疏芬 , 周允基 . 聚氨酯的热分解研究进展 . 高分子通报 , 2005 , ( 4 ), 22 - 26 . doi: 10.3969/j.issn.1003-3726.2005.06.004 http://dx.doi.org/10.3969/j.issn.1003-3726.2005.06.004

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

兼具高柔韧、高隔热的可编织核壳气凝胶纤维

高强度、耐低温压缩的聚氨酯弹性体的设计与性能

二乙二醇改性聚对苯二甲酸丁二醇酯的结晶行为与性能

耐低温水性聚氨酯胶黏剂的分子设计及性能研究

非对称喹噁啉诱导主链扭曲制备高频低损耗聚芳醚