软段结构对聚氨酯弹性体性能的影响

张聪聪1 郑梦凯1 李伯耿1

(1.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)

【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(Tg)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Tg远低于其他三种PUE,其Tg(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。

【关键词】 聚氨酯; 弹性体; 软段; 结构; 性能;

【DOI】

Download this article

    References

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

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

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

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

    [5]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.

    [6]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.

    [7]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.

    [8]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.

    [9]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.

    [10]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.

    [11]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.

    [12]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.

    [13]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.

    [14]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.

    [15]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.

    [16]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.

    [17]Yi J J.Synthesis and property investigation of polybutadienebased polyurethane elastomer[D].Jinan:Shandong University,2014.

    [18]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.

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

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

    [21]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.

    [22]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.

    [23]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.

    [24]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.

    [25]Ai Q S,Xu D M,Fang X L,et al.Analysis on formula raw materials and their proportions of polyurethane elastomer by IRand1H-NMR[J].Plastic Science and Technology,2016,44(1):39-43.

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

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

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

    [29]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.

    [30]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.

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

    [32]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.

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

    [34]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.

    [35]Li J,Wang J C,Han Y,et al.Study on microphase separation of H12MDI based polyurethane elastomers[J].China Plastics Industry,2010,38(6):47-51.

    [36]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.

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

This Article

ISSN:0438-1157

CN: 11-1946/TQ

Vol 70, No. 10, Pages 4043-4051

October 2019

Downloads:0

Share
Article Outline

摘要

  • 引言
  • 1 试验材料和方法
  • 2 结果与讨论
  • 3 结论
  • 参考文献