[1]冯新军,任泓宇.热致形状记忆聚氨酯改性沥青的制备及微观机理研究[J].长安大学学报(自然科学版),2025,45(3):26-38.[doi:10.19721/j.cnki.1671-8879.2025.03.003]
　FENG Xin-jun,REN Hong-yu.Preparation and microscopic mechanism study of thermally induced shape memory polyurethane modified asphalt[J].Journal of Chang’an University (Natural Science Edition),2025,45(3):26-38.[doi:10.19721/j.cnki.1671-8879.2025.03.003]
点击复制

热致形状记忆聚氨酯改性沥青的制备及微观机理研究()
分享到：

长安大学学报（自然科学版）[ISSN:1006-6977/CN:61-1281/TN]

卷:
第45卷
期数:
2025年3期
页码:
26-38
栏目:
道路工程
出版日期:
2025-05-31

文章信息/Info

Title:
Preparation and microscopic mechanism study of thermally induced shape memory polyurethane modified asphalt
文章编号:
1671-8879(2025)03-0026-13
作者:
冯新军; 任泓宇
(长沙理工大学 交通运输工程学院,湖南 长沙 410114)
Author(s):
FENG Xin-jun;  REN Hong-yu
(Department of Traffic and Transportation Engineering, Changsha University of Science &Technology, Changsha 410114, Hunan, China)
关键词:
道路工程;  改性沥青;  正交试验;  热致形状记忆聚氨酯;  形状记忆性能;  微观机理
Keywords:
road engineering;  modified asphalt;  orthogonal experiment;  SMPU;  shape memory performance;  microscopic mechanism
分类号:
U414
DOI:
10.19721/j.cnki.1671-8879.2025.03.003
文献标志码:
A
摘要:
为研制适用于沥青路面工作温度且自愈合能力较强的热致形状记忆聚氨酯改性沥青(SMPU-MA),延长沥青路面的使用寿命,采用预聚体法,以聚己二酸-1,4-丁二醇酯(PBAG)为软段,甲苯-2,4-二异氰酸酯(TDI)为硬段,三羟甲基丙烷(TMP)为扩链剂,制备热致形状记忆聚氨酯(SMPU)预聚体对基质沥青改性。通过正交试验确定SMPU-MA最佳制备工艺参数; 采用软化点、针入度、延度、布氏黏度、离析试验及形状记忆性能试验评价改性沥青性能; 利用差示扫描量热试验和形状记忆性能试验探究SMPU-MA玻璃化转变温度和形状恢复原理及过程; 结合红外光谱试验和凝胶渗透色谱试验分析改性机理。研究结果表明:SMPU-MA最佳制备参数 PBAG、TDI、TMP摩尔比为1:8:14/3,PBAG分子量为3 000,SMPU制备反应温度为80 ℃,SMPU制备反应时间为120 min; SMPU-MA较基质沥青软化点提升8.7 ℃,25 ℃针入度为87.1(0.1 mm),5 ℃延度为12.6 cm,135 ℃黏度为623 mPa·s,离析软化点差为0.2 ℃,玻璃化转变温度为31.4 ℃,形状恢复率为53.3%; 添加SMPU使SMPU-MA依靠软段的玻璃态-橡胶态的转变表现出形状记忆聚合物特有的形状恢复能力,减小了自愈合性能指标,从而提升了沥青的自愈合能力; SMPU预聚物中的-NCO与沥青中多种活泼含氢官能团和扩链剂TMP中的-OH发生了化学反应生成氨基甲酸酯基团,因此,SMPU的加入使沥青中大分子物质比例增加,小分子物质比例减少,从而提高了改性沥青的储存稳定性和高温性能。
Abstract:
A thermally induced shape memory polyurethane modified asphalt(SMPU-MA)with enhanced self-healing capacity suitable for asphalt pavement service temperatures was developed to prolong pavement service life. The SMPU prepolymer was synthesized by using prepolymer method with polyethylene adipate-1,4-butanediol ester(PBAG)as soft segment, toluene-2,4-diisocyanate(TDI)as hard segment, and trimethylolpropane(TMP)as chain extender for matrix asphalt modification. The optimal preparation parameters for SMPU-MA were determined through orthogonal experiments; modified asphalt properties were evaluated by softening point, penetration, ductility, Brookfield viscosity, segregation tests, and shape memory performance evaluation; the glass transition temperature and shape recovery mechanism of SMPU-MA were investigated through differential scanning calorimetry and shape memory performance tests; modification mechanisms were analyzed by using Fourier transform infrared spectroscopy and gel permeation chromatography. The results shows that themolor ratio of PBAG, TDI, and TMP for the optimal preparation parameters of SMPU-MA is 1:8:14/3, PBAG molecular weight is 3 000, reaction temperature of SMPU is 80 ℃, and reaction duration of SMPU is 120 min; compared with base asphalt, SMPU-MA exhibits8.7 ℃ higher softening point, 87.1(0.1mm)penetration at 25 ℃, 12.6 cm ductility at5 ℃, 623 mPa·s viscosity at 135 ℃, 0.2 ℃ segregation softening point difference,31.4 ℃ glass transition temperature, and 53.3% shape recovery rate; the incorporation of SMPU enables SMPU-MA to demonstrate characteristic shape recovery capability through glass-to-rubber transition of soft segments, which reduces the self-healing index and consequently enhances asphalt's self-healing capacity; chemical reactions between -NCO groups in SMPU prepolymer and active hydrogen-containing functional groups in asphalt as well as -OH in TMP chain extender form urethane linkages, so the addition of SMPU increases the proportion of macromolecules while decreasing small molecules, thereby improving storage stability and high-temperature performance of modified asphalt.12 tabs, 9 figs, 34 refs.

参考文献/References:

[1] 林博煌,石立万,王悦婵,等.沥青路面裂缝的数字图像测量与细观结构特征研究[J].公路,2022,67(7):33-40.
LIN Bo-huang, SHI Li-wan, WANG Yue-chan, et al. Digital image measurement of asphalt pavement cracks and study on microstructure characteristics[J]. Highway, 2022, 67(7): 33-40.
[2]侯 越,陈逸涵,顾兴宇,等.基于卷积自编码的沥青路面目标与裂缝智能识别[J].中国公路学报,2020,33(10):288-303.
HOU Yue, CHEN Yi-han, GU Xing-yu, et al. Automatic identification of pavement objects and cracks using the convolutional auto-encoder[J]. China Journal of Highway and Transport, 2020, 33(10): 288-303.
[3]HAFEZZADEH R, AUTELITANO F, GIULIANI F. Asphalt-based cold patches for repairing road potholes-an overview[J]. Construction and Building Materials, 2021(306): 124870.
[4]FANG, Y F, M A, B A, WEI K, et al. Orthogonal experimental analysis of the material ratio and preparation technology of single-component epoxy resin for asphalt pavement crack repair[J]. Construction and Building Materials, 2021(288): 123074.
[5]SUN D Q, YU F, LI L H, et al. Effect of chemical composition and structure of asphalt binders on self-healing[J]. Construction and Building Materials, 2017, 133: 495-501.
[6]向 浩,何兆益,陈柳晓,等.再生沥青自愈合影响因素及疲劳性能分析[J].建筑材料学报,2019,22(2):292-298.
XIANG Hao, HE Zhao-yi, CHEN Liu-xiao, et al. Influential factors and fatigue performance analysis of recycled asphalt self-ranging[J]. Journal of Building Materials, 2019, 22(2): 292-298.
[7]STASTNA J, ZANZOTTO L, VACIN O J. Viscosity function polymer-modified asphalts[J]. Journal of Colloid and Interface Science, 2003, 259: 200-207.
[8]梁 明.聚合物改性沥青多相体系的流变学和形态学研究[D].青岛:中国石油大学(华东),2020.
LIANG Ming. Rheology and morphology for the heterogeneous system of polymer modified asphalt[D]. Qingdao: China University of Petroleum(East China), 2020.
[9]CHAN B Q Y, LOW, Z W K, HENG, SJW et al. Recent advances in shape memory soft materials for biomedical applications[J]. Acs Applied Materials & Interfaces, 2016, 8: 10070-10087.
[10]WANG Y Z, YU X, LIU R L et al. Shape memory active thermal-moisture management textiles[J]. Composites Part A-Applied Science and Manufacturing, 2022(160): 107037.
[11]WISCHKE C, NEFFE A T, STEUER S, et al. Evaluation of a degradable shape-memory polymer network as matrix for controlled drug release[J]. Journal of Controlled Release, 2009, 138: 243-250.
[12]COSTANZA G, TATA M E. Shape memory alloys for aerospace, recent developments, and new applications: A short review[J]. Materials, 2020(13): 1856.
[13]ZHOU X X, ZHU M, MA B, et al. Shape optimization of thermal shape memory epoxy resin and its mechanism for improving the self-healing of asphalt mixtures[J]. Construction and Building Materials, 2023(401): 132863.
[14]ZHANG R R, GUO X G, LIU Y J, et al. Theoretical analysis and experiments of a space deployable truss structure[J]. Composite Structures, 2014(112): 226-230.
[15]ZHANG F L, HUANG W, ZHANG L et al. Preparation and properties evaluation of shape memory epoxy asphalt composites with high toughness and damping[J]. Journal of Applied Polymer Science, 2022,45(139):e53117.
[16]LUO L, ZHANG F H, PAN W, et al. Shape memory polymer foam: Active deformation, simulation and validation of space environment[J]. Smart Materials and Structures, 2022(31): 035008.
[17]金 鑫,郭乃胜,尤占平,等.聚氨酯改性沥青研究现状及发展趋势[J].材料导报,2019,33(11):3686-3694.
JIN Xin, GUO Nai-sheng, YOU Zhan-ping, et al. Research and development trends of polyurethane modified asphalt[J]. Materials Reports, 2019, 33(11): 3686-3694.
[18]金 鑫,郭乃胜,闫思檬,等.聚氨酯复合改性沥青的制备与性能研究[J].中国公路学报,2021,34(3):80-94.
JIN Xin, GUO Nai-sheng, YAN Si-meng, et al. Preparation and performance evaluation on polyurethane composite modified asphalt[J]. China Journal of Highway and Transport, 2021, 34(3): 80-94.
[19]LI Z L, YANG F, YUAN J J, et al. Study on preparation and pavement performance of polyurethane modified asphalt based on in-situ synthesis method[J]. Construction and Building Materials, 2021(309): 125196.
[20]LIU H, ZHANG Z P, ZHU Y X, et al. Modification of asphalt using polyurethanes synthesized with different isocyanates[J]. Construction and Building Materials, 2022(327): 126959.
[21]崔 航,王 锋,胡剑青,等.形状记忆聚氨酯材料的研究进展[J].材料导报,2017,31(2):1-6.
CUI Hang, WANG Feng, HU Jian-qing, et al. Research progress of shape memory polyurethane material[J]. Materials Reports, 2017, 31(2): 1-6.
[22]李凤奎,张 贤,侯建安,等.具有热致形状记忆功能的热塑性多嵌段聚氨酯[J].高分子学报,1996,8(4):462-467.
LI Feng-kui, ZHANG Xian, HOU Jian-an, et al. Thermoplastic multiblock polyurethane with thermoinduced shape memory function[J]. Acta Polymerica Sinica, 1996, 8(4): 462-467.
[23]吴官正.多重刺激响应形状记忆聚氨酯复合材料的制备及性能研究[D].无锡:江南大学,2022.
WU Guan-zheng. Preparation and properties of multi-stimuli responsive shape memory polyurethane composites[D]. Wuxi: Jiangnan University, 2022.
[24]MA B, ZHOU X Y, BO Y Z, et al. Analysis of preparationand properties on shape memory hydrogenated epoxy resin used for asphalt mixtures[J]. Applied Sciences, 2017(7): 529.
[25]刘厚均.聚氨酯弹性体手册[M].2版.北京:化学工业出版社,2012.
LIU Hou-jun. Polyurethane elastomers handbook[M]. 2th ed. Beijing: Chemical Industry Press, 2012.
[26]严 冰.智能型形状记忆聚氨酯的合成与性能研究[D].长沙:湖南大学,2003.
YAN Bing. Synthesis and properties of intelligent shape memory polyurethane[D]. Changsha: Hunan University, 2003.
[27]XIA W J, CHEN X, XU T. Development of shape memory polyurethane/SBS compositely modified asphalt and synergistic modification mechanism[J]. Construction and Building Materials, 2023(360): 129936.
[28]罗 蓉,石晨光,冯光乐.沥青自愈合性能评价指标修正及应用[J].中国公路学报,2019,32(11):103-108.
LUO Rong, SHI Chen-guang, FENG Guang-le. Correction and application of self-healing performance index of asphalt binder[J]. China Journal of Highway and Transport, 2019, 32(11): 103-108.
[29]冯新军,梁 辉,彭 程.湿热地区沥青路面高性能灌缝胶的研制与性能[J].长安大学学报(自然科学版),2023,43(5):11-19.
FENG Xin-jun, LIANG Hui, PENG Cheng. Preparation and performance of high performance grouting sealant for asphalt pavement in humid and hot areas[J]. Journal of Chang'an University(Natural Science Edition), 2023, 43(5): 11-19.
[30]华幼卿,金日光.高分子物理[M].北京:化学工业出版社,2014.
HUA You-qin, JIN Ri-guang. Polymer physics[M]. Beijing: Chemical Industry Press, 2014.
[31]夏 磊.聚氨酯改性沥青的性能研究[D].青岛:中国石油大学(华东),2016.
XIA Lei. Study on properties of polyurethane modified asphalt[D]. Qingdao: China University of Petroleum(East China), 2016.
[32]赵永尚.煤直接液化残渣改性沥青及其胶浆的性能研究[D].北京:北京建筑大学,2015.
ZHAO Yong-shang. Study on the performances of DCLR modified asphalt and asphalt mortar[D]. Beijing: Beijing University of Civil Engineering and Architecture, 2015.
[33]MENG F, MA S Y, YASEEN M et al. Analysis of virgin asphalt brands via the integrated application of FTIR and gel permeation chromatography[J]. Arabian Journal for Science and Engineering, 2020, 45(10): 1-11.
[34]LEI Z, BAHIA H, TAN Y Q, et al. Mechanism of low and intermediate-temperature performance improvement of reclaimed oil-modified asphalt[J]. Road Materials and Pavement Desgin, 2018, 19(6): 1301-1313.

相似文献/References:

[1]武建民,祝伟,马士让,等.应用加权密切值法评价基质沥青抗老化性能[J].长安大学学报(自然科学版),2012,32(01):0.
[2]张宜洛,袁中山.SMA混合料结构参数的影响因素[J].长安大学学报(自然科学版),2012,32(01):0.
[3]陈璟,袁万杰,郝培文,等.微观指标对沥青热稳定性能的影响[J].长安大学学报(自然科学版),2012,32(01):0.
[4]周兴业,刘小滔,王旭东,等.基于轴载谱的沥青路面累计当量轴次换算[J].长安大学学报(自然科学版),2012,32(01):0.
[5]李祖仲,王伯禹,陈拴发,等.轴载对复合式路面应力吸收层荷载应力的影响[J].长安大学学报(自然科学版),2012,32(01):0.
[6]关博文,刘开平,陈拴发,等.水镁石纤维路面混凝土路用性能[J].长安大学学报(自然科学版),2012,32(01):0.
[7]翁效林,王玮,张留俊,等.拓宽路基荷载下管桩复合地基沉降变形模式[J].长安大学学报(自然科学版),2012,32(01):0.
[8]穆柯,王选仓,柳志军,等.基于非饱和渗流原理的路基含水率预估[J].长安大学学报(自然科学版),2012,32(01):0.
[9]李振霞,陈渊召.不同类型半刚性基层材料性能的试验与分析[J].长安大学学报(自然科学版),2012,32(01):0.
[10]马 骉,马 晋,周宇鹏.沥青混合料降温收缩断裂特性[J].长安大学学报(自然科学版),2012,32(03):1.
　MA Biao,MA Jin,ZHOU Yu-peng.Cooling shrinkage fracture characteristic of asphalt mixture[J].Journal of Chang’an University (Natural Science Edition),2012,32(3):1.
[11]周 燕,张 凯,陈拴发,等.改性沥青测力延度试验[J].长安大学学报(自然科学版),2012,32(03):30.
　ZHOU Yan,ZHANG Kai,CHEN Shuan-fa,et al.Research on force ductility test of modified asphalt[J].Journal of Chang’an University (Natural Science Edition),2012,32(3):30.
[12]孙晓龙,张奕康,彭钦源,等.高弹嵌段共聚物功能性微结构与沥青改性效应[J].长安大学学报(自然科学版),2022,42(3):112.[doi:10.19721/j.cnki.1671-8879.2022.03.011]
　SUN Xiao-long,ZHANG Yi-kang,PENG Qin-yuan,et al.Functional microstructure of high elastic block copolymer and modification effect on asphalt[J].Journal of Chang’an University (Natural Science Edition),2022,42(3):112.[doi:10.19721/j.cnki.1671-8879.2022.03.011]

备注/Memo

备注/Memo:
收稿日期:2025-01-15
基金项目:湖南省自然科学基金项目(2021JJ30709); 长沙理工大学研究生科研创新项目(CXCLY2022010);
河南省交通运输学会科研项目(YJXHZD202401)
作者简介:冯新军(1971-),男,江西宜春人,教授,工学博士,E-mail:fxjasphalt@aliyun.com。
更新日期/Last Update: 2025-05-30