Effect of soft segment structure on properties of polyurethane elastomers

ZHANG Congcong; ZHENG Mengkai; LI Bo-Geng

doi:10.11949/0438-1157.20190477

您当前的位置：

首页 >

文章列表页 >

Effect of soft segment structure on properties of polyurethane elastomers

Material science and engineering\, nanotechnology | 更新时间：2026-07-24

- Effect of soft segment structure on properties of polyurethane elastomers
- CIESC Journal Vol. 70, Issue 10, Pages: 4043-4051(2019)
- 作者机构：
  
  化学工程联合国家重点实验室，浙江大学化学工程与生物工程学院，浙江杭州 310027
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20190477
  CLC： TQ 323.8;TQ 328.3;TQ 334.1
- Received：07 May 2019，
  
  Revised：2019-07-08，
  
  Online First：24 July 2026，
  
  Published：05 October 2019
- 稿件说明：
移动端阅览
张聪聪, 郑梦凯, 李伯耿. 软段结构对聚氨酯弹性体性能的影响[J]. 化工学报, 2019, 70(10): 4043-4051

ZHANG Congcong, ZHENG Mengkai, LI Bo-Geng. Effect of soft segment structure on properties of polyurethane elastomers[J]. CIESC Journal, 2019, 70(10): 4043-4051
张聪聪, 郑梦凯, 李伯耿. 软段结构对聚氨酯弹性体性能的影响[J]. 化工学报, 2019, 70(10): 4043-4051 DOI： 10.11949/0438-1157.20190477.

ZHANG Congcong, ZHENG Mengkai, LI Bo-Geng. Effect of soft segment structure on properties of polyurethane elastomers[J]. CIESC Journal, 2019, 70(10): 4043-4051 DOI： 10.11949/0438-1157.20190477.

摘要

分别以聚四氢呋喃二醇(PTMG)、聚己内酯二醇(PCL)、高顺式端羟基聚丁二烯(HTPB)和自由基聚合制得的端羟基聚丁二烯(FHTPB)为软段，采用溶液聚合两步法制得了四种聚氨酯弹性体(PUE)。通过拉伸试验、动态力学性能分析(DMA)、差示扫描量热(DSC)和热重分析等手段，考察了软段结构对它们室温及低温下力学性能、热性能等的影响。结果表明，四种PUE低温(-30℃)下的拉伸强度和断裂伸长率均大于室温下的对应值。这不仅与低温下软段诱导结晶所产生的自增强效应有关，也与软、硬两段的微相分离程度增大有关。相较于其他三种PUE，HTPB-PUE软段不仅玻璃化温度(

)最低，而且极性也最弱，因而微相分离程度高，具有优异的柔性，-30℃下其断裂伸长率仍达660%以上。PCL-PUE和PTMG-PUE因软段易结晶，且软段与硬段的微相分离程度低，则刚性强。低温循环拉伸试验表明，-30℃下HTPB-PUE和FHTPB-PUE有较强的弹性恢复能力，而PCL-PUE和PTMG-PUE则相对较差。DSC和DMA结果显示HTPB-PUE的

远低于其他三种PUE，其

(DSC)低至-103℃。此外，四种PUE的初始分解温度十分相近，均在270℃左右。

Abstract

Using four different soft segments

i.e

. polyterahydrofuran diol (PTMG)

polycaprolactone diol (PCL)

hydroxyl-terminated polybutadiene with high

cis

-1

4 content (HTPB)

and commercial hydroxyl-terminated polybutadiene produced by free radical polymerization (FHTPB)

four kinds of polyurethane elastomers (PUE) were prepared by a two-step solution polymerization. The effects of soft segment structure on mechanical properties and thermal properties at room temperature and low temperature were investigated by tensile test

dynamic mechanical property analysis (DMA)

differential scanning calorimetry (DSC) and thermogravimetric analysis. It has been found that the tensile strength and elongation at break of the four PUEs at low temperature (-30℃) are superior to those at room temperature. This is not only related to the autofrettage effect i

nduced by crystallization of soft segment at low temperature

but also to the increase of the degree of micro-phase separation between the soft and hard segments. Compared with the other three kinds of PUE

the soft segment in HTPB-PUE has lowest polarity and glass transition temperature (

)

so the micro-phase separation is in highest degree

and the elastomer has the most excellent flexibility. Even at -30℃

elongation at break of the HTPB-PUE is up to 660%. PCL-PUE and PTMG-PUE are rigid because their soft segments are easy to crystallize and their degree of micro-phase separation between soft and hard segment is low. The cyclic tensile testing indicated that HTPB-PUE and FHTPB-PUE still have excellent elasticity at -30℃. The results from DSC and DMA showed that the

of HTPB-PUE is much lower than the other three PUEs

and the value from DSC is about -103℃. The initial thermal decomposition temperatures of the four PUEs are very similar

and are all around 270℃.

关键词

Keywords

references

山西省化工研究所 . 聚氨酯弹性体手册 [M ] . 北京 : 化学工业出版社 , 2001 : 7 .

Shanxi Provincial Institute of Chemical Industry . Polyurethane Elastomers Manual [M ] . Beijing : Chemical Industry Press , 2001 : 7 .

刘菁 , 李汾 . 聚氨酯弹性体新进展 [J ] . 化学推进剂与高分子材料 , 2018 , 16 ( 5 ): 26 - 31, 43 .

Liu J , Li F . New progress of polyurethane elastomer [J ] . Chemical Propellants & Polymeric Materials , 2018 , 16 ( 5 ): 26 - 31, 43 .

李绍雄 , 刘益军 . 聚氨酯树脂及其应用 [M ] . 北京 : 化学工业出版社 , 2002 : 45 - 47 .

Li S X , Liu Y J . Polyurethane Resin and Application [M ] . Beijing : Chemical Industry Press , 2002 : 45 - 47 .

孟凡宁 , 胡开放 . 丁羟型聚氨酯弹性体力学性能研究 [J ] . 粘接 , 2010 , 31 ( 9 ): 71 - 74 .

Meng F N , Hu K F . Study on mechanical properties of HTPB type PU elastomers [J ] . Adhesion , 2010 , 31 ( 9 ): 71 - 74 .

向平 , 张成彬 , 张均 , 等 . 不同异氰酸酯型聚氨酯弹性体的合成与性能研究 [J ] . 化工新型材料 , 2017 , ( 4 ): 70 - 72 .

Xiang P , Zhang C B , Zhang J , et al . Synthesis and property of polyurethane elastomer with different isocyanate [J ] . New Chemical Materials , 2017 , ( 4 ): 70 - 72 .

刘听 , 马猛 , 罗骁 , 等 . 聚己内酯二醇及其聚氨酯弹性体的合成和性能研究 [J ] . 聚氨酯工业 , 2015 , ( 5 ): 10 - 13 .

Liu T , Ma M , Luo X , et al . The synthesis and property research of polycaprolactone diol and the polyurethane elastomer [J ] . Polyurethane Industry , 2015 , ( 5 ): 10 - 13 .

张晓远 , 刘锦春 . 聚己内酯型聚氨酯弹性体的合成与性能研究 [J ] . 特种橡胶制品 , 2012 , 33 ( 1 ): 27 - 30 .

Zhang X Y , Liu J C . Study on synthesis and properties of polycaprolactone polyurethane elastomer [J ] . Special Purpose Rubber Products , 2012 , 33 ( 1 ): 27 - 30 .

Bagdi K , Molnár K , Pukánszky B , et al . Thermal analysis of the structure of segmented polyurethane elastomers [J ] . Journal of Thermal Analysis and Calorimetry , 2009 , 98 ( 3 ): 825 - 832 .

Eceiza A , Larrañaga M , de la Caba K , et al . Structure–property relationships of thermoplastic polyurethane elastomers based on polycarbonate diols [J ] . Journal of Applied Polymer Science , 2008 , 108 ( 5 ): 3092 - 3103 .

李健 , 陈淑海 , 宋小娜 , 等 . 聚酯分子量对热塑性聚氨酯弹性体性能影响的研究 [C ] // 中国聚氨酯工业协会弹性体专业委员会2015年年会论文集 . 太原 : 山西省化工研究院 , 2015 : 176 - 181 .

Li J , Chen S H , Song X N , et al . Performance effect study on thermoplastic polyurethane elastomer with polyester molecular weight [C ] // Proceedings of the 2015 Annual Meeting of the Elastomer Professional Committee of China Polyurethane Industry Association . Taiyuan : Shanxi Provincial Institute of Chemical Industry , 2015 : 176 - 181 .

Klinedinst D B , Yilgör I , Yilgör E , et al . The effect of varying soft and hard segment length on the structure-property relationships of segmented polyurethanes based on a linear symmetric diisocyanate, 1,4-butanediol and PTMO soft segments [J ] . Polymer , 2012 , 53 ( 23 ): 5358 - 5366 .

刘凉冰 , 刘红梅 , 贾林才 . 聚酯软段对聚氨酯弹性体力学性能影响的研究 [J ] . 聚氨酯工业 , 2007 , ( 4 ): 20 - 23 .

Liu L B , Liu H M , Jia L C . Effect of soft-segment of polyester on mechanical properties of polyurethane elastomer [J ] . Polyurethane Industry , 2007 , ( 4 ): 20 - 23 .

Mao K , Xia M , Luo Y . Thermal and mechanical properties of two kinds of hydroxyl-terminated polyether prepolymers and the corresponding polyurethane elastomers [J ] . Journal of Elastomers & Plastics , 2016 , 48 ( 6 ): 546 - 560 .

Kébir N , Campistron I , Laguerre A , et al . Use of hydroxytelechelic cis -1,4-polyisoprene (HTPI) in the synthesis of polyurethanes (PUs)（Ⅰ）： Influence of molecular weight and chemical modification of HTPI on the mechanical and thermal properties of PUs [J ] . Polymer , 2005 , 46 ( 18 ): 6869 - 6877 .

温勇 , 王海芳 , 刘春艳 , 等 . H-HTPB型和HTPB型聚氨酯弹性体的力学和耐水解性能比较 [J ] . 聚氨酯工业 , 2018 , 33 ( 1 ): 31 - 33 .

Wen Y , Wang H F , Liu C Y , et al . Mechanical properties and hydrolysis resistance comparison of H-HTPB and HTPB based polyurethane elastomer [J ] . Polyurethane Industry , 2018 , 33 ( 1 ): 31 - 33 .

曹哲 , 介素云 , 李伯耿 . 环氧丁羟型聚氨酯弹性体的制备与性能 [J ] . 高分子学报 , 2017 , ( 8 ): 1350 - 1357 .

Cao Z , Jie S Y , Li B G . Preparation and properties of epoxided hydroxyl-terminated polybutadiene based polyurethane elastomers [J ] . Acta Polymerica Sinica , 2017 , ( 8 ): 1350 - 1357 .

易建军 . 聚丁二烯型聚氨酯弹性体的合成及性能研究 [D ] . 济南 : 山东大学 , 2014 .

Yi J J . Synthesis and property investigation of polybutadiene-based polyurethane elastomer [D ] . Jinan : Shandong University , 2014 .

Cao Z , Zhou Q Z , Jie S Y , et al . High cis- 1,4 hydroxyl- terminated polybutadiene-based polyurethanes with extremely low glass transition temperature and excellent mechanical properties [J ] . Industrial & Engineering Chemistry Research , 2016 , 55 ( 6 ): 1582 - 1589 .

Wingborg N . Increasing the tensile strength of HTPB with different isocyanates and chain extenders [J ] . Polymer Testing , 2002 , 21 ( 3 ): 283 - 287 .

Sekkar V , Gopalakrisham S , Devi K A . Studies on allophanate-urethane networks based on hydroxyl terminated polybutadiene: effect of isocyanate type on the network characteristics [J ] . European Polymer Journal , 2003 , 39 ( 6 ): 1281 - 1290 .

Kulkarni P , Ojha U , Wei X , et al . Thermal and mechanical properties of polyisobutylene-based thermoplastic polyurethanes [J ] . Journal of Applied Polymer Science , 2013 , 130 ( 2 ): 891 - 897 .

Ahmad N , Khan M B , Ma X , et al . The influence of cross-linking/chain extension structures on mechanical properties of HTPB-based polyurethane elastomers [J ] . Arabian Journal for Science and Engineering , 2014 , 39 ( 1 ): 43 - 51 .

易建军 , 李勇 , 陈继明 , 等 . 丁羟聚氨酯弹性体交联网络均匀性与其力学性能之间的关系 [J ] . 合成橡胶工业 , 2015 , 38 ( 4 ): 289 - 293 .

Yi J J , Li Y , Chen J M , et al . Relationships between crosslinked network homogeneity and mechanical properties of hydroxyl terminated polybutadiene based polyurethane elastomer [J ] . China Synthetic Rubber Industry , 2015 , 38 ( 4 ): 289 - 293 .

周勤灼 , 曹哲 , 介素云 , 等 . 胶液法制备高顺式端羟基聚丁二烯液体橡胶 [J ] . 高分子学报 , 2016 , ( 3 ): 293 - 299 .

Zhou Q Z , Cao Z , Jie S Y , et al . Synthesis of HTPB with high cis -1,4 content from PBD original solution [J ] . Acta Polymerica Sinica , 2016 , ( 3 ): 293 - 299 .

艾青松 , 许冬梅 , 方心灵 , 等 . 利用红外光谱和核磁共振氢谱分析聚氨酯弹性体的原料及配比 [J ] . 塑料科技 , 2016 , 44 ( 1 ): 39 - 43 .

Ai Q S , Xu D M , Fang X L , et al . Analysis on formula raw materials and their proportions of polyurethane elastomer by IR and 1 H-NMR [J ] . Plastic Science and Technology , 2016 , 44 ( 1 ): 39 - 43 .

刘听 . 聚己内酯型聚氨酯弹性体的合成改性及其性能研究 [D ] . 杭州 : 浙江工业大学 , 2015 .

Liu T . Synthesis, modifined and property research of polycaprolactone polyurethane elastomer [D ] . Hangzhou : Zhejiang University of Technology , 2015 .

周勤灼 . 基于顺丁橡胶氧化裂解的端(多)羟基聚丁二烯液体橡胶的可控制备 [D ] . 杭州 : 浙江大学 , 2016 .

Zhou Q Z . Controllable synthesis of hydroxyl functional polybutadiene liquid rubber via oxidolysis of butadiene rubber [D ] . Hangzhou : Zhejiang University , 2016 .

李再峰 , 李德和 , 杨光华 . FTIR 在聚氨酯弹性体化学中的应用 [J ] . 弹性体 , 1997 , ( 4 ): 30 - 35 .

Li Z F , Li D H , Yang G H . The application of FTIR in polyurethane chemistry [J ] . China Elastomerics , 1997 , ( 4 ): 30 - 35 .

Zhou Q Z , Jie S Y , Li B G . Preparation of hydroxyl-terminated polybutadiene with high cis -1,4 content [J ] . Industrial & Engineering Chemistry Research , 2014 , 53 ( 46 ): 17884 - 17893 .

Zhou Q Z , Jie S Y , Li B G . Facile synthesis of novel HTPBs and EHTPBs with high cis- 1,4 content and extremely low glass transition temperature [J ] . Polymer , 2015 , 67 : 208 - 215 .

霍尔登 , 莱格 , 夸克 , 等 . 热塑性弹性体 [M ] . 傅志峰, 译. 北京 : 化学工业出版社 , 2000 : 21 - 22 .

Holden G , Legge N R , Quirk R P , et al . Thermoplastic Elastomers [M ] . Fu Z F, trans. Beijing : Chemical Industry Press , 2000 : 21 - 22 .

邹业成 , 张永丽 , 翟进贤 , 等 . 序列结构与结晶行为对聚氨酯弹性体力学性能的影响 [J ] . 高分子材料科学与工程 , 2018 , 34 ( 3 ): 22 - 29 .

Zou Y C , Zhang Y L , Zhai J X , et al . Effect of sequence structure and crystallization behavior of the prepolymer on mechanical properties of the polyurethane elastomers [J ] . Polymer Materials Science and Engineering , 2018 , 34 ( 3 ): 22 - 29 .

庞爱民 . HTPB聚氨酯弹性体的动态力学性能研究 [J ] . 固体火箭技术 , 1999 , ( 1 ): 42 - 45 .

Pang A M . Investigation on the dynamic mechanical property of HTPB polyurethane elastomer [J ] . Journal of solid rocket Technology , 1999 , ( 1 ): 42 - 45 .

Rocco J A F F , Lima J E S , Lourenço V L , et al . Dynamic mechanical properties for polyurethane elastomers applied in elastomeric mortar [J ] . Journal of Applied Polymer Science , 2012 , 126 ( 4 ): 1461 - 1467 .

李娟 , 王景存 , 韩艳 , 等 . H 12 MDI聚氨酯弹性体微相分离研究 [J ] . 塑料工业 , 2010 , 38 ( 6 ): 47 - 51 .

Li J , Wang J C , Han Y , et al . Study on microphase separation of H 12 MDI based polyurethane elastomers [J ] . China Plastics Industry , 2010 , 38 ( 6 ): 47 - 51 .

刘凉冰 . 化学结构对聚氨酯弹性体热分解的影响 [C ] // 中国聚氨酯工业协会第十四次年会论文集 . 上海 : 中国聚氨酯工业协会 , 2008 : 257 - 261 .

Liu L B . Effects of chemical structure on thermal degradation of polyurethane elastomer [C ] // Proceedings of the 14th Annual Meeting of China Polyurethane Industry Association . Shanghai : China Polyurethane Industry Association , 2008 : 257 - 261 .

崔喜 , 刘冰灵 , 赫崇衡 , 等 . 脂肪族聚醚型聚氨酯弹性体热降解机理及热稳定性 [J ] . 化工进展 , 2016 , 35 ( 11 ): 3585 - 3589 .

Cui X , Liu B L , He C H , et al . Research on thermal degradation mechanism and thermal stability of aliphatic polyether-polyurethane elastomer [J ] . Chemical Industry and Engineering Progress , 2016 , 35 ( 11 ): 3585 - 3589 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Research progress on high and low temperature performance and influencing factors of polyurethane modified asphalt

Characteristic, structure, preparation and applications of soft and hard carbons

Low modulus, high elasticity and high peel adhesion acrylate pressure sensitive adhesives

Preparation and adsorption properties of crude glycerol bio-based polyurethane material

Engineering verification and NO emission control of rare earth Y2O3-based catalytic coatings on a metal fiber surface burner

Related Author

GUO Naisheng

ZHU Xiaobo

WANG Shuang

CHEN Ping

CHU Zhaoyang

WANG Zhichen

GUO Naisheng

WANG Shuang

Related Institution

College of Transportation Engineering, Dalian Maritime University

School of Computer Science and Engineering, Hunan University of Information Technology

Intelligent Engineering Technology Research Center, Harbin Cambridge University

The Key Laboratory of Hubei Province for Coal Conversion and New Carbon Materials, Wuhan University of Science and Technology

The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology

⁰