聚氨酯改性沥青高低温性能及影响因素的研究进展

doi:10.11949/0438-1157.20241243

化工学报 ›› 2025, Vol. 76 ›› Issue (6): 2505-2523.DOI: 10.11949/0438-1157.20241243

聚氨酯改性沥青高低温性能及影响因素的研究进展

郭乃胜¹(), 朱小波¹, 王双²^,³(), 陈平³, 褚召阳¹, 王志臣²^,³

^1.大连海事大学交通运输工程学院，辽宁大连 116026
^2.湖南信息学院计算机科学与工程学院，湖南长沙 410151
^3.哈尔滨剑桥学院智能工程技术研究中心，黑龙江哈尔滨 150069

收稿日期:2024-11-02 修回日期:2024-12-10 出版日期:2025-06-25 发布日期:2025-07-09
通讯作者: 王双
作者简介:郭乃胜（1978—），男，博士，教授，naishengguo@126.com
基金资助:
大连市重点科技研发计划项目(2023YF22SN043);黑龙江省自然科学基金项目(LH2023E026);湖南省教育厅科学研究项目重点项目(24A0752);湖南省教育厅科学研究项目优秀青年项目(24B1069)

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

Naisheng GUO¹(), Xiaobo ZHU¹, Shuang WANG²^,³(), Ping CHEN³, Zhaoyang CHU¹, Zhichen WANG²^,³

^1.College of Transportation Engineering, Dalian Maritime University, Dalian 116026, Liaoning, China
^2.School of Computer Science and Engineering, Hunan University of Information Technology, Changsha 410151, Hunan, China
^3.Intelligent Engineering Technology Research Center, Harbin Cambridge University, Harbin 150069, Heilongjiang, China

Received:2024-11-02 Revised:2024-12-10 Online:2025-06-25 Published:2025-07-09
Contact: Shuang WANG

摘要/Abstract

摘要：

聚氨酯（PU）因其性能调整自由度高而受到广泛关注。然而，其多样的性质导致学者在PU改性沥青的高低温流变性能改性效果上存在分歧。因此深入了解不同PU原料特性、合成工艺、成品结构与改性沥青高低温性能间的联系至关重要。基于PU的化学改性机理，结合分子形成过程与聚合物改性沥青的性能评价标准，系统探讨了不同种类软硬段的性质以及不同合成方法制备的PU改性剂的结构对于改性沥青的影响。研究表明，PU分子在沥青内部的物理交联与化学交联程度是性能改善的关键因素：软硬段性质及分子结构主要影响物理交联的微观结构稳定性，而异氰酸酯基团的含量直接决定了化学交联的强度和复杂性。进一步分析了PU与聚合物及其他改性剂的复合体系在沥青中的作用机理。外加改性剂通过改变沥青的内部组分与PU的结构分布来提升性能。然而，目前研究尚难通过微观结构精准量化PU的交联程度，这限制了合成参数与工艺的精确调控，进而导致改性效果的可预测性较低。此外，复合体系结构不稳定、改性剂间化学作用微弱等问题往往引发储存稳定性下降或某些性能劣化。最后，提出了PU及其复合改性沥青研究的发展趋势与展望。

关键词: 聚氨酯, 改性沥青, 流变性能, 聚合物, 弹性体, 复合材料, 合成

Abstract:

Polyurethane (PU) has received a lot of attention due to its high degree of freedom in performance adaptation. However, its diverse properties have led researchers to disagree on the effects of modifying the high and low temperature rheological properties of PU-modified asphalt. Therefore, it is crucial to gain a deeper understanding of the connection between different PU raw material properties, synthesis processes, product structures and the high and low temperature properties of modified asphalt. Based on the chemical modification mechanism of PU, combined with the molecular formation process and the performance evaluation criteria of polymer modified asphalt, this paper systematically explores the properties of different types of soft and hard segments and the structure of PU modifiers prepared by different synthesis methods on modified asphalt. It was shown that the degree of physical and chemical cross-linking of PU molecules within the asphalt is a key factor in the improvement of performance: the nature of the soft and hard segments and the molecular structure mainly affects the microstructural stability of the physical cross-linking, while the content of the isocyanate group directly determines the strength and complexity of the chemical cross-linking. The composite system of PU with polymers and other modifiers in asphalt was further analyzed for the modified mechanism. The addition of modifiers enhances the performance by changing the structural distribution of the internal components of asphalt with PU. However, it is difficult to accurately quantify the degree of cross-linking of PU through the microstructure in the current study, which restricts the precise tuning of the synthesis parameters and processes, which in turn leads to a low predictability of the modification effect. In addition, the structural instability of the composite system and the weak chemical interaction between modifiers often triggered the decrease of storage stability or the deterioration of certain properties. Finally, the development trend and outlook of the research on PU and its composite modified asphalt are proposed.

Key words: polyurethane, modified asphalt, rheological properties, polymers, elastomer, composites, synthesis

中图分类号:

U 414

郭乃胜, 朱小波, 王双, 陈平, 褚召阳, 王志臣. 聚氨酯改性沥青高低温性能及影响因素的研究进展[J]. 化工学报, 2025, 76(6): 2505-2523.

Naisheng GUO, Xiaobo ZHU, Shuang WANG, Ping CHEN, Zhaoyang CHU, Zhichen WANG. Research progress on high and low temperature performance and influencing factors of polyurethane modified asphalt[J]. CIESC Journal, 2025, 76(6): 2505-2523.

图/表 20

图1 聚氨酯反应式

Fig.1 Reaction formula of PU

图2 聚氨酯的不同合成方法

Fig.2 Various synthesis methods of PU

图3 MDI、TDI、HDI及IPDI的分子结构

Fig.3 Molecular structures of MDI, TDI, HDI, IPDI

图4 PRM改性沥青四大组分质量分数的变化

Fig.4 Changes in mass fractions of the components of PRM-modified asphalt

图5 低聚物多元醇的分子结构

Fig.5 Molecular structures of oligomeric polyols

图6 不同硬段含量下TPU改性沥青的荧光显微镜图像[37]

Fig.6 Fluorescence microscopy images of bitumen-TPU blends with various HS contents[37]

图7 不同原料种类对PU改性沥青的影响

Fig.7 Effect of different raw material types on PU-modified asphalt

图8 PRM改性沥青的微观结构示意图[45]

Fig.8 Microstructure diagram of PRM-modified bitumen[45]

图9 PUP与SBS改性沥青高低温性能对比[58]

Fig.9 Comparison of high and low temperature performance of PUP and SBS modified asphalt[58]

图10 不同掺量下TS-PU与PUP的高低温流变性能[59, 61]

Fig.10 High and low temperature rheological properties of binders involved various TS-PU and PUP contents[59, 61]

图11 不同硬段含量下热塑性聚氨酯的高低温流变性能[11]

Fig.11 High and low temperature rheological properties of TPU asphalt with various HS contents[11]

图12 TSPU与TPU改性沥青的结构模型

Fig.12 Structure model of TSPU and TPU modified asphalt

图13 不同分子结构下PU改性沥青的高低温性能的改性效果对比

Fig.13 Comparison of modification effects on high and low temperature properties of PU-modified asphalt with different molecular structures

图14 不同合成制备方法、分子结构下PU改性沥青的性能对比

Fig.14 Comparison of the performance of PUMA with different synthetic methods and various molecular structure

表1 聚氨酯的聚合物复合体系及其改性效果

Table 1 Polymer composite modifiers and their modification effects

复合改性剂	基质沥青	制备条件	参考样本	沥青改性效果
复合改性剂	基质沥青	制备条件	参考样本	高温流变性能	低温流变性能	抗永久变形能力	储存稳定性
EP+TSPU^[68]	70#	60℃搅拌3 min；60℃固化4 d	SBSMA	+	-	+	+
EP+TSPU^[69]	70#	150℃、500 r/min搅拌30 min；150℃、500 r/min搅拌3 min；150℃固化3 h；60℃养护4 d	SBSMA	+	+	+	+
EP+PUP^[70]	80/100pen grade	3000 r/min、(130±10)℃剪切2 h；同温度剪切40、5 min；120℃固化4 h	EPMA/PUMA	*	*	*	+
SBS+PUP^[71]	60/80pen grade	160℃、1500 r/min剪切10 min+15 min；5000 r/min剪切30 min，180℃养护2 h；120℃、1000 r/min剪切60 min+5 min+5 min；3000 r/min剪切20 min，固化2 h	SBSMA	*	*	+	+
CRM+TPU^[72]	PG64-22	177℃、700 r/min剪切30 min+60 min	CRMA/TPUMA	+	+	+	*
SBS+WTPU^[73]	60/80pen grade	175℃、3000 r/min剪切1 h；180℃、3000 r/min剪切1 h	SBSMA	-	+	+	-
APAO+WTPU^[74]	60/80pen grade	190℃、2000 r/min剪切30 min+20 min	BA/TPUMA	+	+	+	+
RET+PUP^[75]	70#	170～180℃、5000 r/min剪切2 h+1 h	RETMA	+	+	+	*

图15 环氧树脂/聚氨酯复合改性沥青在60℃下固化不同时间的FM结果[68]

Fig.15 FM images of PEA-0.65 in different curing time at 60℃[68]

图16 环氧树脂/聚氨酯复合改性沥青在不同掺量下的LSCM结果[70]

Fig.16 LSCM images of the EPU modified asphalt binders[70]

表2 聚氨酯的其他复合体系及其改性效果

Table 2 Other composite modifiers and their modification effects

复合改性剂	基质沥青	制备条件	参考样本	沥青改性效果
复合改性剂	基质沥青	制备条件	参考样本	高温流变性能	低温流变性能	抗永久变形能力	储存稳定性
VO+COPU^[19]	70#	130~140℃、3000 r/min剪切30 min+45 min	VA	+	+	+	*
WO+MDI(Liquefied)^[80]	PG 64-22	140℃、3500 r/min剪切20 min+30 min；140℃、800 r/min剪切5 min+5 min；90℃固化1 h	WBBA	+	+	+	*
IS+COPU^[81]	60/70pen grade	125℃、2000 r/min剪切10 min	BA	+	+	+	+
GO+SBS+TPU^{[14, 82-83]}	90#	160℃、300 r/min搅拌30 min；160℃、3000 r/min剪切45 min	TPU-SBSMA	+	+	*	*
Nano TiO₂+TPU^[84]	90#	160℃、5000 r/min剪切0.5 h；130℃搅拌0.5 h；170℃、5000 r/min剪切0.5 h	BA	+	+	*	*
OMMT+TPU^[85]	90#	(135±5)℃、2000 r/min剪切0.5 h+0.5 h；135℃固化1 h	BA	+	+	*	+
OATT+PUP^[13]	60/80pen grade	135℃、3000 r/min剪切15 min+30 min+1 h；125℃固化2 h	BA	+	+	*	-
BG+TPU^[86]	70#	135℃搅拌10 min；145℃、3000 r/min剪切40 min	BA/SBSMA	*	-	+	*
RA+TPU^[87]	90#	150℃、3000 r/min剪切0.5 h；150℃、5000 r/min剪切0.5 h	BA/PUMA/RAMA	+	+	+	*

图17 不同沥青样品的SEM测试结果[24]

Fig.17 SEM of different asphalts[24]

图18 OATT/PU复合改性沥青体系示意图[13]

Fig.18 Schematic diagram of OATT/PU combined modified asphalt system[13]

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聚氨酯改性沥青高低温性能及影响因素的研究进展

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

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