Journal of Road Engineering 3 (2023) 16–34

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Journal of Road Engineering

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Review Article

Materials, preparation, performances and mechanism of polyurethane

modified asphalt and its mixture: A systematic review
Chaohui Wang *, Shuai Huang, Qian Chen **, Xiaoping Ji, Kaixi Duan
School of Highway, Chang'an University, Xi'an 710064, China

H I G H L I G H T S

Summarize the material ratio and preparation process of polyurethane-modified asphalt.

Compare and evaluate the road performances of polyurethane-modified asphalt and its mixtures.

Discuss the modification mechanism of polyurethane-modified asphalts.

A R T I C L E I N F O A B S T R A C T

Keywords: With the rapid development of asphalt pavement technology, it has attracted considerable attention to improving
Road materials the durability of asphalt pavement. An effective action is to use modified asphalt with high performance and
Polyurethane durability. Polyurethane (PU) has been used in asphalt pavement engineering to enhance the durability and
Modified asphalt
service life of asphalt pavement because of its excellent high-temperature performance, toughness, wear resis-
Preparation process
Modification mechanism
tance, aging resistance and oil resistance. However, PU modified asphalt technology is still in the exploratory
stage. The preparation, modification mechanism and working performances of PU modified asphalt need to be
further clarified. Therefore, this paper summarized the research progress of PU modified asphalt and its mixture.
The composition of PU modified asphalt was introduced. The addition methods of PU materials and preparation
process parameters of the PU modified asphalt were determined. The modification mechanism of PU on asphalt
was discussed. The effects of polyurethane on asphalt were analyzed and the road performances of its mixture
were evaluated. Finally, the development tendency towards PU modified asphalt and its mixture were forecasted.

1. Introduction Department of China Journal of Highway and Transport, 2020). Asphalt

As the important mainstay of economic development, transportation
is an important factor affecting global sustainable development. In recent
years, sustainable transportation is actively developed in many countries,
focusing on improving the service life and durability of highway infra-
structure (Bazmara et al., 2018; Chen et al., 2022, 2023; Wang et al.,
2023; Xu et al., 2020). Asphalt mixture were widely used in high-grade
pavement because of the feature of low noise, smooth surface, seam-
less, comfortable driving and short construction period (Sun et al., 2020).
However, as asphalt mixture directly contact with atmospheric and
traffic loads, asphalt pavement often suffers from cracking, rutting,
aggregate spalling, and other diseases (Cong et al, 2019; Editorial
materials with excellent performance play a positive role in improving
the performance of asphalt pavement (Song et al., 2021; Zhang et al.,
2021c). The performances of conventional asphalt materials are difficult
to meet the requirements of pavement, so polymer materials are used to
enhance the performances of asphalt (Sun et al., 2018). The commonly
used polymers are styrene-butadiene-styrene (SBS), crumb rubber pow-
der, styrene-butadiene rubber (SBR), polyethylene (PE), ethylene-vinyl
acetate (EVA) (Cao et al., 2021; Cuadri et al., 2014a). These polymer
modified asphalt are often physically modified (Cong et al, 2019).
Asphalt by chemical modification has also been employed to enhance
performance, which can produce new functional groups and alter struc-
tures of asphalt (Sun et al., 2018). Compared to physically modified

* Corresponding author.
** Corresponding author.
E-mail addresses: wchh0205@chd.edu.cn (C. Wang), 18291831269@163.com (S. Huang), 2016121160@chd.edu.cn (Q. Chen), jixp82@163.com (X. Ji),
378100710@qq.com (K. Duan).
Peer review under responsibility of Chang’an University.

https://doi.org/10.1016/j.jreng.2023.01.002
Received 16 September 2022; Received in revised form 12 January 2023; Accepted 12 January 2023
Available online 2 March 2023
2097-0498/© 2023 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
C. Wang et al.
Fig. 1. The flow chart of the overall structure.
asphalt, it has better compatibility stability (Li et al., 2021a). In addition,
the above polymer-modified asphalt mixture are prepared at 150  C–170

C. At this temperature, a large amount of volatile organic compounds
(VOCs) and smog will be generated, which will increase the consumption
of fuel resources and CO2 emissions (Chen et al., 2020; Kok et al., 2021;
Wang et al., 2020, 2021, 2022). Therefore, a number of researchers
groups have focused on the development of high-performance and
environmental-friendly asphalt.
Polyurethane has attracted extensive attention to pavement engineers
and researchers due to its superior high-temperature performance,
toughness, wear resistance, aging resistance, oil resistance (Jin et al.,
2019; Li et al., 2021b). Polyurethane is a kind of polymer with urethane
groups (–NHCOO–), which is formed by the reaction of isocyanate and
polyol. Isocyanates and polyols exist in liquid form at normal tempera-
ture, so they can be mixed with asphalt at lower temperature (Sun et al.,
2020). Lower production temperature saves energy, reduces CO2 and
volatile organic compound (VOCs) emissions, and delays asphalt oxida-
tion. Compared with other modified asphalt, polyurethane modified as-
phalts is cleaner and more environment-friendly (Sun et al., 2021).
Numerous studies have been carried out on PU modified asphalt and
its mixture mainly for the preparation optimization, asphalt perfor-
mances, modification mechanism, mixture performances. Regarding the
preparation optimization, He et al. (2020) studied the influence of
preparation parameters on asphalt performance by the variance analysis,
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Journal of Road Engineering 3 (2023) 16–34
and optimized the preparation process of the PU modified asphalt. Jin
et al. (2021) determined the optimal preparation process parameters of
asphalt with the modification of thermoplastic polyurethane elastomer
(TPU) by the grey correlation analysis. Zeng et al. (2017) optimized the
preparation process parameters of the PU modified asphalt based on the
range and the significance analysis. Regarding the asphalt performances,
Zhang et al. (2020b) prepared a thermosetting polyurethane modified
asphalt used for bridge deck pavement. It was found that PU was bene-
ficial to the high-temperature and mechanical performance of asphalt,
but was unfavourable for low-temperature performance of asphalt. Yu
et al. (2018a) reported that PU materials could enhance the aging
resistance, thermal performance and high-temperature storage stability
of asphalt. Fang and Tu (2019) reported that polyurethane clearly
strengthened the ultraviolet aging resistance of asphalt according to the
short-term aging test and long-term aging test. Lu et al. (2021) studied
the mechanical properties of the PU modified asphalt by the molecular
dynamics method, and the Young's modulus, bulk modulus and shear
modulus of asphalt were explicitly increased with the addition of poly-
urethane. Regarding the modification mechanism, Sun et al. (2019)
investigated the modification mechanism of PU on asphalt by Fourier
transform infrared (FTIR), dynamic mechanical analysis (DMA) and
differential scanning calorimeter (DSC). Zhang et al. (2021a) explored
the microscopic mechanism of PU with different soft segment structures
on asphalt. Regarding the mixture performance, Lyu et al. (2020)
C. Wang et al.
Fig. 2. The chemical synthesis reaction and the molecular structure model of polyurethane. (a) Unimolecular reaction. (b) Chemical synthesis reaction. (c) Molecular
structure model.
believed that the high-temperature stability and low-temperature crack
resistance of the PU modified asphalt mixture were better than SBS
modified asphalt mixture, and their water stability were basically the
same. Sun et al. (2021) reported that the PU modified asphalt mixture
had higher water stability and mechanical properties and lower the
low-temperature crack resistance than SBS modified asphalt mixture. Li
(2017) reported that the PU modified asphalt mixture had obvious high-
and low-temperature performance when the curing temperature and
time were 120  C and 48 h, respectively. In addition, extensive studies
had been carried out on composite modified asphalt, such as the PU/e-
poxy resin, PU/SBS, PU/rubber powder, PU/rock asphalt and so on (Jin
et al., 2020; Yan et al., 2019; Zhang et al., 2020d). However, the research
results are complex, and a relatively complete system has not been
formed. The preparation process of PU modified asphalt had significant
differences. The modification mechanism of PU on asphalt still needs to
be fully combed. The influence of polyurethane on asphalt performance
and pavement performance of asphalt mixture is still lack of systematic
research.
Therefore, this paper reviewed the research status and future pros-
pects for PU modified asphalt and its mixture. The paper structure was
shown in Fig. 1, which was composed of five sections: 1) the background
knowledge of PU, including the synthesis, structure, properties and
content in asphalt, was introduced; 2) the preparation methods of the PU
modified asphalt were analyzed and the optimal preparation method was
selected; 3) basic properties and rheological properties of PU modified
asphalt were discussed; 4) the modification mechanism of PU in asphalt
was analyzed; 5) the performances of PU modified asphalt mixture were
evaluated.
2. Raw materials
2.1. Polyurethane
Polyurethane is mainly formed by the reaction of isocyanates and
polyols in the presence of chain extenders, crosslinkers, catalysts and
other additives. PU is a block polymer, and the main chain consists of soft
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Fig. 3. The chemical structures of polyols. (a) Polyether polyols. (b) Poly-
ester polyols.
segments and hard segments. The chemical synthesis reaction and the
molecular structure model of polyurethane were shown in Fig. 2. The
hard segments usually consist of isocyanates and chain extenders, and the
soft segments are generally composed of polyols (Lyu et al., 2022; Wei
et al., 2019a, 2019b). PU molecular structure determines its perfor-
mances. Different polyurethane materials can be prepared by adjusting
the types, structures and ratios of polyols and isocyanates.
The synthesis of polyurethane mainly includes one-step method and
two-step method (Cong et al., 2019; Li et al., 2021a, 2021b). For one-step
method, PU is directly prepared by the reaction of isocyanate, polyol,
chain extender, crosslinker, and other additives. For two-step method,
firstly prepolymer with isocyanate group at both ends of the molecule is
produced by the reaction of polyol and excessive isocyanate. These
prepolymers can react with active hydridea (e.g., amines, carboxylic
acid) and produce substituted ureas containing –NHCONH– groups. After
that, it occurs the curing reaction that excessive –NCO groups react with
active hydrogen in the reaction –NHCOO– and –NHCONH– groups in
presence of chain extenders or crosslinkers. Polyurethane will be added
to asphalt in the form of liquid, powder and particle when PU modified
asphalt is prepared (Jia et al., 2021; Wei et al., 2019a, b).
Polyols mainly affect the low-temperature performance and elastic
performance of PU modified asphalt. Polyols are divided into polyethers
and polyesters, and their structures were shown in Fig. 3. Polyethers
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Fig. 4. The chemical structures of isocyanates. (a) MDI. (b) TDI. (c) IPDI. (d) PADI.

Fig. 5. The chemical structures of some additives. (a) MAH. (b) MOCA. (c) 1,4-butanediol.

polyols are the most widely used, and the reasons are as follows. Poly-
esters polyols have high strength and low flexibility because the ester
group with large polarity is easy to form strong hydrogen bonds, but the
ester group is easy to hydrolyze. The polyethers with non-polar and
rotatable ether bonds increase the flexibility of polyurethane (Jia et al.,
2021; Li et al., 2021b). Especially, hydroxyl-containing materials are
used to replace polyols in the preparation of polyurethane, such as lignin,
castor oil and palm oil (He et al., 2020; Peng et al., 2020; Xia et al.,
2016a).
Isocyanates mainly affect the high-temperature performance and
mechanical performance of PU modified asphalt. Isocyanates for modi-
fied asphalt are mainly divided into four categories, methylene diphenyl
diisocyanates (MDI), toluene diisocyanate (TDI), isophorone diisocya-
nate (IPDI) and polyaryl polymethylene isocyanate (PADI), as shown in
Fig. 4. Each isocyanate molecule usually contains two or more unsatu-
rated isocyanate groups (–N¼C¼O), which is chemically active (Jia et al.,
2021). The MDI is commonly used because a MDI molecule contains two
benzene rings to provide PU higher strength, and symmetrical molecular
configuration is easy to form a linear structure with polyols to enhance
the ductility of polyurethane (Cong et al., 2019). It is worth noting that
polyurethane precursors with isocyanate as active functional groups are
also used for asphalt modification (Li et al., 2021a).
2.2. Other additives
Additives mainly include compatibilizers, chain extenders and
crosslinkers, which are often added to upgrade the asphalt performances.
The structures of some additives were shown in Fig. 5. Compatibilizers
can promote the compatibility of polyurethane and asphalt, such maleic
anhydride (MAH), pentaerythritol, naphthalene oil, etc. Chain extenders
and crosslinkers, such as 4,4-diamino-3,3-dichlorodiphenylmethane
(MOCA) and 1,4-butanediol, promote polyurethane prepolymer to
generate polymer chains and heighten the mechanical properties of PU
modified asphalt.

Fig. 6. PU content and classification. (a) Numerical statistics of PU material content. (b) PU modified asphalt types (Awazhar et al., 2020; Ban, 2017; Bazmara et al.,
2018; Cuadri et al., 2014a, b; Faridah et al., 2019; Gallu et al., 2020; Guo et al., 2018; He et al., 2020; Mana et al., 2020; Shu, 2016; Sun et al., 2018; Wei et al., 2019a,
b; Xia, 2016; Xia et al., 2016b; Yu et al., 2018a; Zeng et al., 2017; Zhang, 2020).

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Fig. 7. The schematic diagram of preparation process.

2.3. Material ratio To determine the appropriate PU contents, the contents of PU in

PU modifier was mainly prepared by the reaction of MDI and poly-
ether, so PU content was mainly considered in the follow-up study. PU
content was one of the main indicators affecting the performance of
asphalt, but consistent views on it are not reached. Awazhar et al. (2020)
determined 3 wt% as the optimal PU content by central composite design.
Fang et al. (2019) believed that polyurethane would be adverse to the
storage stability and viscosity of asphalt, and recommended 6 wt% as the
best content. Lyu et al. (2021) believed that the PU content for asphalt
modification was generally at 2 wt% to 12 wt%. Zeng et al. (2017) re-
ported that PU content had obvious effects on the high-temperature per-
formance and elastic recovery performance of asphalt, suggesting that the
PU content should be controlled at 15 wt% to 25 wt%. He et al. (2020)
reported that the high-temperature performance, low-temperature per-
formance and viscosity of asphalt could be raised with the addition of
polyurethane, and 25 wt% was optimum content.
asphalt were summarized, as shown in Fig. 6.
As shown in Fig. 6(a), the content data of PU modified asphalt were
highly dispersed and mainly distributed in 5 wt%–30 wt%. The average
value was evidently higher than the median, indicating that the center of
gravity of data was lower. The high-content polyurethane should be
selected based on consideration of performances, while the low-content
should be selected based on consideration of economy. In addition, the
PU would markedly increase the viscosity of modified asphalt. Therefore,
it was recommended that PU content should be selected between 5 wt%
and 15 wt%. PU modified asphalt was divided into three categories for
conveniently studying performance of PU modified asphalt: low-content
PU modified asphalt, medium-content PU modified asphalt and high-
content PU modified asphalt, as shown in Fig. 6(b). Where, low-
content PU modified asphalt represented PU content in asphalt was
less than 5 wt%, medium-content PU modified asphalt represented PU
content in asphalt was between 5 wt% and 15 wt%, high-content PU

Fig. 8. Preparation process parameters. (a) Numerical statistics of shear time. (b) Numerical statistics of shear temperature. (c) Numerical statistics of shear rate (Ban,
2017; Bazmara et al., 2018; Fang et al., 2019; Gallu et al., 2020; He et al., 2020; Jia et al., 2021; Lyu et al., 2021; Shu, 2016; Sun et al., 2019; Wei et al., 2019b; Xia
et al., 2016a; Zeng et al., 2017; Zhang, 2020; Zhang et al., 2021c).

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Fig. 9. Basic properties of asphalt. (a) Numerical statistics of the penetration. (b) Numerical statistics of the softening points. (c) Numerical statistics of the ductility.
(d) Numerical statistics of the viscosity (Cuadri et al., 2014a, b; Fang et al., 2019; He et al., 2020; Jin et al., 2021; Wei et al., 2019a, b; Xia, 2016; Xia et al., 2016b;
Zhang et al., 2021c).

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modified asphalt represented PU content in asphalt was more than 15 wt
% (The following meanings were the same.)
3. Preparation of PU modified asphalt
The preparations of polymer modified asphalt mainly included me-
chanical stirring method, solvent method, colloid mill method and shear
method. The preparation processes of PU modified asphalt in different
studies were different. The shear method and mechanical stirring method
were mainly used to, especially shear method. Likely as the shear ma-
chine made the modifier finer and more evenly dispersed in the asphalt.
The preparation process schematic diagram of PU modified asphalt was
shown in Fig. 7.
3.1. Material adding order
There were five ways to add polyurethane:
(1) Add isocyanates. For example, Fang et al. (2016) added quanti-
tative isocyanate into the base asphalt to prepare isocyanate
modified asphalt samples.
(2) Add polyurethane prepolymer directly. For example, Zhang et al.
(2020b) added all additives to the asphalt and sheared at 2000
r/min and 140  C  10  C for 30 min. Then some PU prepolymers
were added to asphalt, stirring at 90  C and 3000 r/min for 5 min.
Finally, mixture were placed in oven at 120  C for 2 h.
(3) Add polyols first, then isocyanates. For example, Peng et al.
(2020) prepared lignin based PU modified asphalt. Firstly, the
base asphalt was placed in the oven at 150  C for 0.5 h. Then the
polyether and chain extender were slowly added into asphalt at
170  C to shear 4000 r/min. After shearing for 30 min, toluene
diisocyanate and catalyst were added to asphalt to shear for 1 h
until the raw materials fully reacted.
(4) Add polyols and isocyanates at the same time. For example, Kok
et al. (2021) prepared new palm oil based PU modified asphalt.
Asphalt and additives were mixed in high shear mixer at 180  C
and 2000 r/min for 1 h. When the asphalt temperature reached
180  C, MDI and polyols were added into the asphalt and mixed.
(5) Physically mixing PU with asphalt. For example, Bazmara et al.
(2018) and Zhang et al. (2021c) added PU and asphalt into a high
shear to mix at 4000 r/min and 175  C  5  C temperature for 1 h.
The second method was widely adopt because the NCO– group of
isocyanates was easy to react with the active components of asphalt. The
addition of polyurethane prepolymer reduced the uncertainty of the test.
At the same time, polyurethane prepolymer was active.
3.2. Preparation process parameters
The parameters such as the shear temperature, shear rate and shear
time should be considered in the preparation of PU modified asphalt in-
door laboratory. He et al. (2020) reported that the shear time and shear
temperature had distinct effects on the performance of modified asphalt,
and the optimal preparation process was to shear at 170  C and 6000 r/min
for 60 min. Jin et al. (2021) analyzed the influence of reaction temperature,
shear time and shear revolution, and determined the appropriate prepa-
ration parameters of PU modified asphalt. Zeng et al. (2017) reported that
the shear temperature had significant influence on the performance of
modified asphalt and the optimal preparation parameters were 120  C,
1500–3000 r/min for 10–40 min. Fang et al. (2019) determined the best
shear temperature, shear rate and shear time were 4000 r/min, 150  C and
40 min, respectively. Li et al. (2021a, b) reported that polyurethane was
uniformly dispersed in asphalt with stirring at 120  C for 15 min.
The shear temperature, shear rate and shear time of PU modified
asphalt prepared by the first method were summarized, as shown in
Fig. 8.
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As shown in Fig. 8, the shear times were basically lower than 60 min,
of which nearly 50% were concentrated on 30–60 min. The Q1, Q2 and
Q3 of the shear temperature were 120  C, 130  C and 140  C, respec-
tively. Where, Q1 represented smaller quartile, Q2 represented median,
Q3 represented larger quartile, and interquartile range (Iqr) value rep-
resented the difference value between Q3 and Q1. The Iqr value was 40

C, indicating that the shear temperature concentrated on 120  C–165  C
and the center of data distribution was higher. The Q1, Q2 and Q3 of
shear rate were 1500 r/min, 3000 r/min and 4000 r/min, respectively.
The shear rates were mainly concentrated on 1500–4000 r/min.
Although the preparation process had some differences, the prep-
aration of PU modified asphalt indoor laboratory was mainly to add
polyurethane prepolymer. Usually, the asphalt was heated to 120

C–160  C, then the polyurethane prepolymer and other additives
were mixed and PU modified asphalt was prepared through shearing
at 1500–4000 r/min for 30–60 min. Finally, PU modified asphalt was
obtained. There were some differences in the process of preparation of
PU modified asphalt between laboratory and factory production, so
the subsequent research should be combined with the actual condi-
tions of the factory to achieve PU modified asphalt the large scale
production.
4. Properties of polyurethane modified asphalt
4.1. Single polyurethane modified asphalt
(1) Basic properties
The evaluation of the conventional properties of PU modified asphalt
mainly included penetration, softening point, ductility and viscosity, as
shown in Fig. 9.
As shown in Fig. 9(a), PU content had an effect on the penetration of
asphalt. The penetration medians of base asphalt, low-content PU
modified asphalt, medium-content PU modified asphalt and high-content
PU modified asphalt were 71.0, 61.6, 55.4 and 63.0, respectively.
Compared with base asphalt, the penetrations of PU modified asphalt
were reduced and the maximum decrease degree was more than 60%. It
indicated that polyurethane could improve the stiffness, consistency and
deformation resistance of asphalt. In addition, the types of polyurethane
also affected the penetration of asphalt, for example, polyether poly-
urethane increased the penetration of asphalt (Jin et al., 2021). The
penetration quartile ranges of PU modified asphalt with three contents
were 12.0%–43.9%, 13.7%–47.7% and 1.65%–24.9%, respectively. With
the increase of PU content, the penetration of asphalt decreased firstly
and then increased. The trend of penetration decrease degree was
opposite. Therefore, it was recommended adopting the medium-content
PU modified asphalt.
As shown in Fig. 9(b), the medians of the softening point of base
asphalt, low-content PU modified asphalt, medium-content PU modified
asphalt and high-content PU modified asphalt were 48.0  C, 56.0  C, 52.5

C and 78.5  C, respectively. Researchers had an agreement on problem
that polyurethane could increase the softening point of asphalt. The
softening point improvement degree medians of the three contents
modified asphalt were 11.9%, 14.1% and 56.4%, respectively. The
improvement degree of the softening point and the softening point
increased with the addition of PU, indicating that polyurethane had a
positive effect on the high-temperature performance of asphalt. The
higher the content was, the better the performance was.
It was not reached consistent opinion about the effect of polyurethane
on asphalt ductility. At 5  C, the ductility of asphalt increased with the
addition of PU. The maximum was more than 100 cm, showing that the
low-temperature performance of PU modified asphalt was significant (Yu
et al., 2018a; Zhang et al., 2021c). However, polyurethane reduced the
ductility of asphalt and even brittle fracture likely as it was affected by
type of polyurethane materials (Sun et al., 2018; Zhang, 2020). At 10  C,
polyurethane had a negative impact on the ductility of asphalt (Fang and
C. Wang et al. Journal of Road Engineering 3 (2023) 16–34

Fig. 10. The DSR results of asphalt. (a) Rutting resistance factor of PU modified asphalt at different temperatures. (b) Rutting resistance factor of modified asphalt
with different content at 70  C (Ban, 2017; Fang et al., 2019; Liu, 2018; Wei et al., 2019).

Fig. 11. The BBR results of asphalt. (a) Creep stiffness of asphalt at different temperatures. (b) Creep rate of asphalt at different temperatures. (c) Creep stiffness and
creep rate of with different PU content at 12  C (Ban, 2017; Fang et al., 2019; Jia et al., 2021; Liu, 2018; Wei et al., 2019a; Zhang et al., 2020b).

Tu, 2019; Wei et al., 2019a). Therefore, the test temperature would affect requirement of the Chinese Technical Specifications for Construction of
the ductility of PU modified asphalt. From the analysis of statistical data, Highway Asphalt Pavements (JTG F40-2004, the following abbreviation
polyurethane heighten the ductility of asphalt. Most of the ductility of PU Specification). Therefore, the ductility of PU modified asphalt needed
modified asphalt were less than 20 cm, which did not meet the further to be studied.

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Table 1
Polyurethane composite modified asphalt types and performances.
Reference Composite Optimal dosage Basic property Rheological property Mechanical property
modified asphalt by weight of
type base asphalt

Zhang et al. PU/epoxy resin 13.9%/55.5% Rs, 0.023 – Tensile strength, about
(2021b) 1.75 MPa; elongation at
break, about 240%
Bu and PU/epoxy resin 30%/54% Softening point difference, 1.2  C – Tensile strength, 1.75
Cheng MPa; elongation at
(2016) break, 378%
He et al. PU/epoxy resin – Softening point difference, 0.9  C G*/sin(δ) at 90  C  1.0 kPa; S at 6  C, 173 Tensile strength, 3.16
(2021) MPa; m at 6  C, 0.294; 60  C, R at 0.1 kPa, MPa; elongation at
63.7%; R at 3.2 kPa, 61.0%; break, 392%;
Jnr at 0.1 kPa, 0.043 kPa1; Jnr at 3.2 kPa, adhesive strength at 20
0.047 kPa1; Jnr-diff, 9.3% 
C, about 1.35 MPa
Zhang et al. PU/unsaturated 5.2%/34.8% Softening point difference, about 1.7  C G*/sin(δ) at 76  C  1.0 kPa; S at 22  C, 323 Tensile strength, 1.62
(2020a) polyester resin MPa; m at 22  C, 0.303 MPa; elongation at
break, 305.2%
Zhang et al. PU/SBS 5.6%/4.0% Penetration, 54.3 (0.1 mm); softening S at 18  C, 180 MPa; m at 18  C, 0.320; 64  C, –
(2020d) point, about 88.5  C; ductility, 25.2 cm; Jnr at 0.1 kPa, 0.601 kPa1; Jnr at 3.2 kPa,
softening point difference, 2.3  C 0.953 kPa1; Jnr-diff, 58.4%
Wen et al. PU/SBS 5.5%/3.5% Penetration, 36 (0.1 mm); softening point, G*/sin(δ) at 100  C  1.0 kPa; 64  C, R at 0.1 –
(2022) about 73  C; ductility, 31.1 cm; softening kPa, about 90%; R at 3.2 kPa, about 80%; Jnr at
point difference, 1.2  C; index, 1.2 0.1 kPa, about 0.125 kPa1; Jnr at 3.2 kPa, about
0.125 kPa1
Tian et al. PU/SBS 5.6%/4.0% Softening point difference, 0.7  C; Rs, 64  C, R at 0.1 kPa, about 45%; R at 3.2 kPa, –
(2020) 0.07 about 42%; Jnr at 0.1 kPa, about 0.68 kPa1; Jnr
at 3.2 kPa, about 0.8 kPa1; Jnr-diff, 60%
Yan et al. PU/waste rubber 12%/15% – G*/sin(δ) at 76  C  1.0 kPa; S at 18  C  300 –
(2019) powder (WRP) MPa; m at 18  C  0.3
Jin et al. PU/rock asphalt 5%/5% Penetration, about 74 (0.1 mm); softening G*/sin(δ) at 76  C, 1.20 kPa; S at 22  C, 299 –
(2020) point, about 55  C; ductility, about 7.1 MPa; m at 22  C, 0.301; 64  C, Jnr at 0.1 kPa,
cm; penetration index, about 1.02 1.1  104 kPa1; Jnr at 3.2 kPa, 2.18  104
kPa1; Jnr-diff, 60%
Jia et al. PU/montmori- 9%/2% Penetration, about 49 (0.1 mm); softening G*/sin(δ) at 76  C  1.0 kPa; S at 18  C  300 –
(2019) llonite point, about 55.5  C; ductility at 5  C, MPa; m at 18  C  0.3
about 61 cm; softening point difference,
about 1.1  C
Zhou et al. PU/siloxane 27.4%/9.6% – – –
(2019)
1
Ji and He PU/nano 4%/1% Penetration, about 82 (0.1 mm); softening 64  C, Jnr at 0.1 kPa, about 0.0025 kPa ; Jnr at –
(2022) titanium point, about 48.5  C; ductility at 5  C, 3.2 kPa, about 0.0029 kPa1; Jnr-diff, 16%
about 22 cm

Note: Rs is the segregation rate, R is the percent recovery, Jnr is the non-recoverable compliance, Jnr-diff is the stress sensitivity (Tian et al., 2020; Zhang et al., 2021b).

Viscosity reflected the fluidity of asphalt, which was evaluated by
135  C rotational viscosity index in this paper. The addition of poly-
urethane increased the viscosity of asphalt. With the addition of PU, the
viscosity of asphalt increased. The viscosity of PU modified asphalt were
less than 3.0 Pa⋅s except the literature (Fang and Tu, 2019), which met
the Specification requirement. The method of adding diluents had been
used to overcome the problem of excessive viscosity (Guo et al., 2018;
Liu, 2018).
In summary, the penetration was reduced, and the ductility, the
softening point and viscosity of asphalt were intensified after adding
polyurethane. The performance was affected by the content and the type
of polyurethane and test temperature. However, the low-temperature
performance of PU modified asphalt needed further to enhance.
(2) Rheological properties
The rheological property evaluation of polyurethane modified asphalt
included high-temperature performance, intermediate-temperature per-
formance and low-temperature performance. SHRP plan proposed to use
dynamic shear rheological test (DSR) to evaluate the high-temperature
performance of asphalt, requiring rutting resistance factor G*/sin(δ) 
1.0 kPa. The low-temperature performance was evaluated by bending
rheological beam test (BBR), which required creep stiffness (S)  300
MPa and creep rate (m)  0.3. The rheological test results of PU modified
asphalt were shown in Figs. 10 and 11.
Fig. 10 showed that polyurethane could strengthen the high-
temperature deformation resistance of asphalt. The rheological proper-
ties of PU modified asphalt were affected by PU content and type.
Polyurethane could upgrade the deformation recovery ability of base
asphalt at high temperature. The larger the content was, the more
obvious the effect was. Under the same test conditions, polyester poly-
urethane modified asphalt had better high-temperature performance
than polyether polyurethane (Zhang et al., 2021a). The increase of
temperature increased complex modulus G* and decreased the phase
angle δ, promoting the transition of asphalt from high elastic state to
viscous flow state (Zhang et al., 2021c). Based on the statistical data
analysis, the quartile ranges of rutting resistance factor of PU modified
asphalt at 64  C, 70  C and 76  C were 3.7–17.1 kPa, 1.7–7.9 kPa and
0.9–2.4 kPa, respectively. These were higher than 1.0 kPa and met the
requirements of PG-76, showing that PU modified asphalt had eximious
high-temperature performance. At 70  C, rutting resistance factor me-
dians of PU modified asphalt were 1.3, 1.5, 4.5 and 3.6 kPa, respectively.
After adding polyurethane, the G*/sin(δ) of PU modified asphalt
increased, improving the high-temperature performance of asphalt.
At present, there were few studies on the fatigue property of PU
modified asphalt. Bazmara et al. (2018) reported that fatigue resistance
of PU modified asphalt was raised with the increase of PU content.
Fig. 11 showed that the low-temperature performance of PU modified
asphalt met the Specification for Superpave at 12  C, it did not met the
Specification for Superpave at 18  C. The low-temperature rheological

24
C. Wang et al.
Fig. 12. Tensile test results of PU/epoxy resin composite modified asphalt (Bu
and Cheng, 2016).
property of PU modified asphalt basically met the requirements of PG-22.
At 12  C, the creep stiffness of PU modified asphalt decreased and the
creep rate increased with the addition of PU. It indicated that PU
heightened the low-temperature performance of asphalt.
In summary, polyurethane could improve the high- and low-
temperature performance of asphalt, especially high-temperature per-
formance. Based on the statistical principle analysis, the PG grade of PU
modified asphalt investigated basically met the requirements of PG 76-
22. The comprehensive performance of modified asphalt was signifi-
cant as the addition of 5%–15% PU, which was consistent with the
conclusion of material ratio in section 1.4 above. The evaluation of
rheological properties of PU modified asphalt mainly focused on high-
temperature rheological property and low-temperature rheological
property, and the research on medium-temperature fatigue performance
and elastic recovery ability were a little. The multiple stress creep re-
covery test (MSCR) and linear amplitude scanning (LAS) test were di-
rections for further studies on evaluating PU modified asphalt
performance.
Fig. 13. Rheological test results of PU/WRP composite modified asphalt. (a) The BBR results of different asphalt samples. (b) The DSR results of different asphalt
samples (Yan et al., 2019).
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Journal of Road Engineering 3 (2023) 16–34
4.2. Composite polyurethane modified asphalt
Previous studies showed that single polymer could strengthen asphalt
performance while it had some shortages. Therefore, composite modified
asphalt were gradually used to overcome the above problem. PU was
used for composite modified asphalt with epoxy resin, SBS, rock asphalt,
montmorillonite and other materials, as shown in Table 1.
Epoxy resin modified asphalt was commonly used pavement materials
in bridge deck pavement because epoxy resin (EP) can endow asphalt with
excellent mechanical properties. However, epoxy asphalt binder has poor
flexibility which limited its application to some extent. PU was selected to
improve the flexibility of epoxy resin modified asphalt, as presented in
Table 1 (Bu and Cheng, 2016; He et al., 2021; Zhang et al., 2021b). The
flexibility of PU/epoxy resin composite modified asphalt increased with
the increase of PU, as shown in Fig. 12. Zhang et al. (2021b) pointed that
PU/epoxy resin composite modified asphalt has satisfactory storage sta-
bility, high-temperature properties and mechanical strength, and the
C–O–C group in PU improved the flexibility of the binder. Bu and Cheng
(2016) showed that serious segregation occurred when the content of
polyurethane exceeds 30%. He et al. (2021) used polyurethane/epoxy
resin modified asphalt as bridge deck waterproof adhesive layer material,
which had obvious mechanical property and high-temperature perfor-
mance. However, the creep stiffness and creep rate at 6  C did not meet
the requirements of the Specification, indicating that the low-temperature
crack resistance was not enough. In addition, Zhang et al. (2020a) showed
that PU also could raise the tensile properties and low-temperature
properties of unsaturated polyester resin modified asphalt, but slightly
reduce the high-temperature properties. As shown in Table 1, PU/SBS
composite modified asphalt had great high- and low-temperature perfor-
mance and storage stability. It is worth noting that PU/SBS composite
significantly reduced the temperature sensitivity of asphalt. Yan et al.
(2019) studied the performance of PU/WRP composite modified asphalt.
The results showed that the performance of high-temperature, low--
temperature, aging resistance of composite modified asphalt were raised,
as shown in Fig. 13.
On the other hand, other composite modifiers have also been employed
to improve the performance of the PU-modified asphalt. Jin et al. (2020)
considered that PU improved the low-temperature rheological property of
asphalt and added rock asphalt to modify for high-temperature performance
of asphalt, and they had great compatibility with asphalt. The recommended
C. Wang et al. Journal of Road Engineering 3 (2023) 16–34

Fig. 14. FTIR spectra of PU modified asphalt before and after modification. (a) Transmittance. (b) Absorbance. (c) FIRT spectra of different PU content modified
asphalt. (d) Modification process (Cong et al., 2019; Cuadri et al., 2014a; Sun et al., 2018; Xia et al., 2016).

26
C. Wang et al.
Fig. 15. Four groups content changes of asphalt. (a) Asphalt SARAs fractions as a function of curing time (1 month, 2 months and 6 months). (b) Asphalt SARAs
fractions as a function of content (Cuadri et al., 2014b; Li et al., 2021a).
dosage of PU and rock asphalt all was 5%. Ji and He (2022) also introduced
nano titanium dioxide to ameliorate the high-temperature deformation
resistance of asphalt. Jia et al. (2019) showed that the montmorillonite was
beneficial to the storage stability and flame retardant performance of com-
posite modified asphalt, but was unfavorable to the low-temperature per-
formance. The optimal dosage was recommended to use 9% PU and 2%
montmorillonite. Zhou et al. (2019) studied the self-healing mechanism and
hydrophobic properties of siloxane and polyurethane modified asphalt. The
results showed that siloxane could improve the hydrophobic performance of
PU modified asphalt, and deduced van der Waals force and hydrogen bond
interaction might be the driving force for self-healing of composite modified
asphalt.
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Journal of Road Engineering 3 (2023) 16–34
In summary, polyurethane could enhance the high- and low-
temperature performance of composite modified asphalt. However,
different PU types, content and use conditions had significant effects
on the performance of asphalt, so it was a challenge to carry out
subsequent performance research. The performance of composite
modified asphalt mostly stayed in the macroscopic appearance, and
lacked the relationship between the microscopic characteristics and
chemical components of asphalt. Considering composite modified
asphalt involved various materials, the compatibility stability was the
key to the performance of modified asphalt. Therefore, the modifica-
tion mechanism and compatibility stability of polyurethane modified
asphalt needed further exploration.
C. Wang et al.
Fig. 16. The microstructure of PU modified asphalt. (a) FM of PU modified asphalt. (b) Schematic representation of the swelling of the PU in bitumen. (c) SEM of PU
modified asphalt. (d) AFM of base asphalt. (e) AFM of PU modified asphalt (Fang et al., 2019; Gallu et al., 2020; Jin et al., 2021; Xia et al., 2016a; Zhang et al., 2021c).
5. Modification mechanism
The modification mechanism of PU on base asphalt was analyzed
from the aspects of functional group change, asphalt composition change,
micro-structure and thermal.
5.1. Functional groups changes
The functional groups of modified asphalt was identified by the FTIR.
Sun et al. (2018) found that a new characteristic peak of NHCOO–
appeared through the spectrum, indicating that polyurethane reacted
with the active components in asphalt, as shown in Fig. 14(a). Bazmara
et al. (2018) also obtained consistent conclusion. The absorbance of
asphalt before and after PU modification had some changes (Cuadri et al.,
2014a), as shown in Fig. 14(b). The NCO group in polyurethane pre-
polymer reacted with the active components in asphalt to form urethane
group. Zhang et al. (2021c) confirmed this phenomenon. The urethane
group increased with increase of PU content (Xia et al., 2016a), as shown
in Fig. 14(c). As shown in Fig. 14(d), the modification process could be
explained as that the isocyanate group in PU reacts with the hydroxyl
(main), carboxyl and other active groups on the asphaltene to form
strong chemical bonds, and the number of chemical bonds increases with
the increase of PU content. Physical hydrogen bonds were formed at the
same interface, which made polyurethane and asphalt became a whole
and improved the performance of asphalt.
5.2. The change of asphalt compositions
Colloid theory divided asphalt into four components: saturated
component, aromatic component, resin and asphaltene. Component
content had a noticeable influence on asphalt performance and de-
termines the colloidal structure of asphalt. Cuadri et al. (2014b) reported
that PU changed the four components content of asphalt and the struc-
ture of asphalt. Li et al. (2021a, b) also reached the same conclusion. As
shown in Fig. 15, an increase in the asphaltene fraction was seen after
adding PU. In addition, asphalt SARAs fractions were increased as a
28
Journal of Road Engineering 3 (2023) 16–34
function of curing time and content of polyurethane. However, the effect
of polyurethane on asphalt SARAs fractions was less studied.
5.3. Microstructure
The fluorescence microscope (FM), scanning electron microscope
(SEM) and atomic force microscope (AFM) were used to analyze the
changes of microstructure of asphalt before and after modification. The
FM diagram of PU modified asphalt showed that polyurethane particles
were uniformly distributed in asphalt, and the modified asphalt had
excellent compatibility and stability (Xia et al., 2016a), as shown in
Fig. 16(a). When the content of polyurethane was low, it was dispersed in
the continuous asphalt phase, and the phase transition occurred with the
PU content increase. The soft segment of polyurethane absorbed some
light components (oil) of asphalt to swell (Gallu et al., 2020; Jin et al.,
2021). The polyurethane and asphalt formed a continuous network
structure, and the high-temperature performance of asphalt was
improved, as shown in Fig. 16(b). In addition, SEM images also showed
that polyurethane formed a network structure in asphalt, which limited
the fluidity of asphalt colloid and enhanced the ability to resist external
forces. The low-temperature performance and viscoelasticity of asphalt
were strengthened, and PU modified asphalt had outstanding compati-
bility (Jin et al., 2021; Lu et al., 2021), as shown in Fig. 16(c). The AFM
morphology of asphalt before and after polyurethane modification were
shown in Fig. 16(d) and (e). It was found that polyurethane promoted
asphalt to transform from dispersed phase and continuous phase into
single phase structure, improving the compatibility, elasticity, mechan-
ical properties and anti-aging of modified asphalt (Fang and Tu, 2019;
Zhang et al., 2021c). Therefore, the addition of polyurethane promoted
the asphalt phase transformation and absorbed swelling to form network
structure, improving the performance of asphalt.
5.4. Thermal stability analysis
The thermal analysis of asphalt was often carried out by thermal
gravimetric method (TG), DSC, DMA, as shown in Fig. 17(a)–(c).
C. Wang et al. Journal of Road Engineering 3 (2023) 16–34

Fig. 17. Thermal analysis of PU modified asphalt. (a) TG curve. (b) DSC curve. (c) DMA curve (Sun et al., 2018; Yu et al., 2018a; Zhang et al., 2021a).

29
C. Wang et al.
Fig. 18. Asphalt aggregate ratio and aggregate gradation of PU modified asphalt mixture. (a) Numerical statistics of asphalt aggregate ratio. (b) The types of aggregate
gradation (Cuadri et al., 2014a; Faridah et al., 2019; He et al., 2020; Liu, 2018; Lyu et al, 2020; Peng et al., 2020; Shu, 2016; Sun et al., 2018; Wei et al., 2019a; Zhang
et al., 2021c).
Fig. 17(a) showed that the degradation of TPU absorbed heat and
delayed the decomposition of asphalt. The thermal stability of asphalt
was heightened with the increase of TPU content (Yu et al., 2018a). The
polyester polyurethane modified asphalt showed better
high-temperature performance than polyether polyurethane, and the
MDI content was an important factor affecting the high-temperature
stability of asphalt (Jin et al., 2021). The polyether polyurethane modi-
fied asphalt had lower glass transition temperature and the
bettelow-temperature performance, as shown in Fig. 17(b). As shown in
Fig. 17(c) that the changes of storage modulus and loss modulus of PU
modified asphalt with temperature were relatively flat compared with
that of asphalt. It indicated that polyurethane improved the thermal
stability of asphalt. According to above research, it could be concluded
that polyurethane upgraded the thermal stability of asphalt, and the type
of polyurethane had a conspicuous impact on asphalt performances.
In summary, the modification mechanism of polyurethane on asphalt
could be summarized as chemical bond, physical crosslinking and phase
structure transformation. In the process of modified asphalt, poly-
urethane reacted with the active groups of asphalt to form strong
chemical bonds and physical crosslinking. Polyurethane absorbed the
light components in asphalt to swell, which promoted the structural
transformation of asphalt colloid. A continuous and stable three-
dimensional network structure was formed, which hindered the move-
ment of asphalt components and improved the performances of asphalt.
However, most of the existing mechanism analysis focused on the anal-
ysis of functional groups, micro-structure and thermal analysis, the
change of chemical composition was less involved. The follow-up study
should further clarify the modification mechanism of polyurethane on
asphalt from the component content change and colloidal structure. A
unified and effective relationship between the chemical composition,
microscopic characteristics and macroscopic performance indexes of
asphalt should be also established.
6. Performances of polyurethane modified asphalt mixture
6.1. Polyurethane single modified asphalt mixture
(1) Asphalt aggregate ratio and aggregate gradation of modified
asphalt mixture
Asphalt aggregate ratios and aggregate gradations of PU modified
asphalt mixture were investigated, as shown in Fig. 18.
Fig. 18 showed that the quartile range of asphalt aggregate ratio was
5.1%–5.8% and the data distribution was uniform. The typical gradations
of AC-13, SMA-13 and OGFC-13 were adopted. The AC, SMA and OGFC
respectively represented dense-graded asphalt concrete mixture, stone
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Journal of Road Engineering 3 (2023) 16–34
mastic asphalt and open-graded friction courses. The number 13 repre-
sents that the nominal maximum particle size of the mixture was 13 mm.
Among the known gradation types, nearly 80% of the researchers used
the gradation of AC-13, and the passing rate of each sieve hole met the
Specification.
(2) The road performances of PU modified asphalt mixture
The performances of PU modified asphalt mixture mainly include
high-temperature stability, low-temperature crack resistance and water
stability. The road performance test data of polyurethane modified
asphalt mixture were shown in Fig. 19.
As shown in Fig. 19(a), the dynamic stability (DS) of PU modified
asphalt mixture was higher than 2800 times⋅mm1 and met the
requirement of specification. Most of the data exceed 8000 times⋅mm1,
which were better than SBS modified asphalt mixture investigated.
Compared with base asphalt mixture, the dynamic stability of PU
modified asphalt mixture were increased by about 3–6 times. It indicated
that PU modified asphalt mixture had great high-temperature perfor-
mance, which was consistent with the conclusion of PU modified asphalt.
As shown in Fig. 19(b), the maximum bending strain (MBS) data of
PU modified asphalt mixture were more than 2800 με, which met the
Specification requirement for winter cold region (annual extreme tem-
perature was between 21.5  C and 37.0  C). After adding polyurethane,
the maximum bending strain of asphalt mixture increased by 40%–
90%.The data were mainly concentrated on 3000–4500 με, indicating
that PU modified asphalt mixture had superior low-temperature
performance.
As shown in Fig. 19(c), more than 40% of the residual stability ratio
(RSR) test data of PU modified asphalt mixture were lower than the
Specification requirement of 85% and slightly lower than SBS modified
asphalt mixture investigated. Compared with the base asphalt mixture,
the residual stability of some PU modified asphalt mixture increased
negatively, and the maximum increase degree was less than 15%. It
indicated that the water stability of PU modified asphalt mixture was
ordinarily. As shown in Fig. 19(d), the tensile strength ratio (TSR) was
basically consistent with the influence law of residual stability. Thus, the
water stability of PU modified asphalt mixture needed further to study.
The pavement suffered from repeated cycles of load and temperature
in the actual service process, causing fatigue damage. Shu (2016) re-
ported that polyurethane could extend the fatigue life of asphalt mixture
according to the results of four-point bending fatigue life test. The fatigue
resistance of asphalt mixture increased with increase of PU content.
Under the condition of 1150 με, the fatigue life of the polyurethane
modified asphalt mixture reached 53,330 times, which was better than
that of SBS modified asphalt mixture. Qi (2018) studied the fatigue life of
C. Wang et al. Journal of Road Engineering 3 (2023) 16–34

Fig. 19. The road performance of mixture. (a) Numerical statistics of dynamic stability. (b) Numerical statistics of maximum bending strain. (c) Numerical statistics of
residual stability ratio. (d) Numerical statistics of Tensile strength ratio (Liu, 2018; Lyu et al., 2020; Shu, 2016; Sun et al., 2018; Wei et al., 2019a, b; Zhang
et al., 2021c).

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C. Wang et al. Journal of Road Engineering 3 (2023) 16–34

Table 2
Road performance of polyurethane composite modified asphalt mixture.
Investigator Type of asphalt mixture Dynamic stability (time⋅mm1) Maximum bending strain (με) Tensile strength ratio (%) Residual stability ratio (%)

Zhang et al. (2021b) Epoxy resin 27,640 2460.0 93.90 91.80

PU 5250 5230.0 86.70 81.20
Epoxy resin/PU 23,880 3230.0 92.10 91.60
Zhang et al. (2020d) SBS 5381 3807.3 83.68 –
PU 2165 2124.7 81.73 –
SBS/PU 5890 3287.1 86.23 –
Bu and Cheng (2016) Epoxy resin 18,437 5882.0 87.80 96.70
Epoxy resin/PU 18,257 8603.0 85.50 95.20
Zhang et al. (2020b) Unsaturated resin – 4550.0 91.70 89.27
Unsaturated resin/PU – 4800.0 90.60 89.50
Zhao (2018) Epoxy resin 27,636 7250.0 91.82 95.87
Epoxy resin/PU 25,414 9210.0 92.63 96.17
Zhang et al. (2020c) Epoxy resin 27,636 2693.0 91.80 94.90
PU 5250 5234.0 82.20 87.10
Epoxy resin/PU 23,876 3229.0 91.40 92.30

mixture of polyether polyurethane modified asphalt, polyether poly-
urethane modified asphalt, epoxy asphalt and SBS modified asphalt by
three-point bending fatigue test. When the stress ratio was 0.5, the fa-
tigue life of four asphalt mixture were 4587 times, 3157 times, 5421
times and 2538 times, respectively. In contrast, polyether polyurethane
modified asphalt mixture had better fatigue resistance. However, there
were few studies on the fatigue resistance of PU modified asphalt
mixture, which needed further study.
In summary, polyurethane could improve the high-temperature sta-
bility and low-temperature crack resistance of modified asphalt mixture,
but weaken water stability. Few studies have been carried out on the
fatigue resistance of PU modified asphalt mixture. Future research should
focus on the water stability and fatigue resistance of PU modified asphalt
mixture. In addition, the durability of PU modified asphalt mixture under
different working conditions should be explored to adapt to the complex
and changeable natural environment.
6.2. Composite polyurethane modified asphalt mixture
There were few studies on polyurethane composite modified asphalt
mixture. The road performance index data were summarized as Table 2.
The purpose of composite modification is to make the performance
of asphalt more balanced or outstanding. PU/SBS composite modified
asphalt mixture had better high-temperature performance, low-
temperature performance and water stability than PU modified
asphalt mixture. Polyurethane improved the low-temperature crack
resistance of epoxy modified asphalt mixture and slightly reduced water
stability, while had indistinct influence on the high-temperature sta-
bility. Polyurethane could upgrade the low-temperature performance of
unsaturated resin modified asphalt mixture, but reduced the high-
temperature performance and water stability. Yu et al. (2018b) re-
ported that polyurethane and graphene oxide changed the failure
properties of base asphalt, heightened low-temperature crack resistance
and prolong the fatigue life of asphalt pavement. Compared with the
pavement performance of polyurethane single modified asphalt mixture,
the performances of composite modified asphalt mixture were raised on
the whole, especially the water stability. The research on polyurethane
composite modified asphalt mixture mainly focused on the road per-
formance such as high-temperature performance, low-temperature per-
formance and water stability performance. It failed to establish an
effective connection between the performance of modified asphalt and
the performance of mixture, and lacked the research on the fatigue
performance and the performance comparison of different composite
modified asphalt mixture. It was worth noting that the similarities and
differences between the site construction technology of composite
modified asphalt mixture and conventional modified asphalt mixture
were not clear. Therefore, the research on composite modified asphalt
mixture needed more exploration. In addition, Zhao (2018) paved 3 cm
thick PU-EP modified asphalt concrete and pavement has no disease
development after 8 months of construction.
7. Conclusions
PU is gradually applied to pavement engineering because of its
excellent high-temperature performance, toughness, wear resistance,
aging resistance, oil resistance. In this paper, the research status of PU
modified asphalt and its mixture was systematically reviewed. Firstly, the
PU materials and the preparation of PU modified asphalt were intro-
duced. Secondly, the performance of PU modified asphalt and its mixture
was evaluated. Finally, the modification mechanism of PU in asphalt was
analyzed. The primary conclusions could be drawn as follows.
(1) Polyurethane was recommended synthesizing by MDI and poly-
ether. The preparation process of modified asphalt was suggested
that base asphalt was heated to 120  C–165  C and added 5%–
15% polyurethane, then mixture were sheared and developed at
1500–4000 r/min for 30–60 min.
(2) Based on the basic performance and rheological properties anal-
ysis, the effect of high-temperature performance and low-
temperature performance of polyurethane on asphalt were sig-
nificant. The PG grade of PU modified asphalt was PG 76-22, and
PU content was suggested at 5%–15%. Polyurethane could
improve the compatibility stability, high-temperature perfor-
mance and low-temperature performance of composite modified
asphalt.
(3) Polyurethane reacted with the active groups of asphalt to form
strong chemical bonds and physical crosslinking. Polyurethane
absorbed the light components in asphalt to swell, which pro-
moted the structural transformation of asphalt colloid. A contin-
uous and stable three-dimensional network structure was formed,
which hindered the movement of asphalt components and
improved the performance of asphalt.
(4) The asphalt aggregate ratios of PU single modified asphalt mixture
was 5.1%–5.8%, and the gradation of AC-13 was mostly used. The
mixture had much superior high-temperature performance and
low-temperature performance, and the water stability was gen-
eral. Based on the numerical results, the dynamic stability of the
PU single modified asphalt mixture was about 3–6 times larger
base asphalt mixture. The maximum flexural strain is about 40%–
90% larger than base asphalt mixture. The residual stability and
the freeze-thaw splitting strength were reduced after adding PU.
On the whole, the road performances of polyurethane composite
modified asphalt mixture were better than that of polyurethane
single modified asphalt mixture, especially the water stability.

32
C. Wang et al.
The future prospect and suggestions of polyurethane modified asphalt
and their mixture are as follows.
(1) The influence of polyurethane types on asphalt performance and
the modification mechanism should be deeply studied. Mean-
while, the water stability and fatigue performance of PU modified
mixture are always great concern, and further attempts can be
studied.
(2) The performance evolution of PU asphalt and its mixture under
different working conditions is not yet clear, and there are some
differences between indoor test and field test. Long-term field
performance of PU asphalt and its mixture should be monitored.
(3) In view of the characteristics of polyurethane dual component,
rapid curing and high viscosity, the construction technology is
different from that of conventional modified asphalt. The con-
struction technology and quality control method suitable for
polyurethane modified asphalt can be investigated.
(4) Methods and techniques for recycling and reusing PU modified
asphalt mixture that reach the end of service life in pavements
should also be seriously considered, and the corresponding spec-
ifications should be completed.
(5) The environment and economy are also the key issues to be
considered when PU modified asphalt were applied for pavement.
The comprehensive environmental and economic assessments of
PU modified asphalt mixture should be considered.
Declaration of competing interest
The authors do not have any conflict of interest with other entities or
researchers.
Acknowledgments
The authors would like to acknowledge was financially supported by
Innovation Capability Support Program of Shaanxi (2022TD-07).
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Tian, Z., Zhang, Z., Zhang, K., et al., 2020. Preparation and properties of high viscosity Dr. Chaohui Wang is a professor of road engineering at School of
and elasticity asphalt by styrene-butadiene-styrene/polyurethane prepolymer Highway, Chang'an University. He is selected as the World's Top
composite modification. Journal of Applied Polymer Science 137 (38), e49123. 2% Scientists 2022, the Young Scientific and Technological
Wang, C., Chen, Q., Guo, T., et al., 2020. Environmental effects and enhancement Pacesetter of Shaanxi Province, the Young and Middle-Aged
mechanism of graphene/tourmaline composites. Journal of Cleaner Production 262, Scientific and Technological Leading Talent of the Ministry of
121313. Transport, and the Young Scientific and Technological Talent of
Wang, C., Li, Y., Wen, P., et al., 2023. A comprehensive review on mechanical properties the Ministry of Transport. He is the leader of Key Scientific and
of green controlled low strength materials. Construction and Building Materials 363, Technological Innovation Teams in Shaanxi Province. He has
129611. hosted more than 50 national, provincial, ministerial and other
Wang, C., Wang, M., Chen, Q., et al., 2022. Basic performance and asphalt smoke scientific research projects. He has won the first and second
absorption effect of environment-friendly asphalt to improve pavement construction prizes of more than 10 provincial and ministerial scientific
environment. Journal of Cleaner Production 333, 130142. research awards. He has published 6 monographs and partici-
Wang, M., Wang, C., Huang, S., et al., 2021. Study on asphalt volatile organic compounds pated in 6 industry and local standards. He has also published
emission reduction: a state-of-the-art review. Journal of Cleaner Production 318, more than 110 SCI/EI academic papers, and authorized more
128596. than 80 national invention patents.
Wei, K., Ma, B., Duan, S., 2019a. Preparation and properties of bitumen-modified
polyurethane solid-solid phase change materials. Journal of Materials in Civil
Engineering 31 (8), 04019139.
Shuai Huang is a master candidate at School of Highway,
Wei, K., Wang, X., Ma, B., et al., 2019b. Study on rheological properties and phase-change
Chang'an University. His research interests include asphalt
temperature control of asphalt modified by polyurethane solid-solid phase change
pavement maintenance materials and asphalt VOCs emission
material. Solar Energy 194, 893–902.
reduction technology.
Wen, Y., Xu, L., Xie, M., et al., 2022. High temperature performance of PU-SBS composite
modified asphalt. Journal of Civil & Environmental Engineering 44 (6), 162–169.
Xia, L., 2016. Research on the Performance of Polyurethane Modified Asphalt. China
University of Petroleum, Qingdao.
Xia, L., Cao, D., Zhang, H., et al., 2016a. Study on the classical and rheological properties
of castor oil-polyurethane pre-polymer (C-PU) modified asphalt. Construction and
Building Materials 112, 949–955.
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polyurethane modified asphalt. Journal of Highway and Transportation Research and
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Xu, S., Xu, M., Zhang, Y., et al., 2020. An indoor laboratory simulation and evaluation on
the aging resistance of polyether polyurethane concrete for bridge deck pavement.
Frontiers in Materials 7, 237.
Yan, T., Ran, X., Chen, Z., 2019. Preparation and properties of polyurethane/waste rubber Dr. Qian Chen is a lecturer of road engineering at School of
powder composite modified asphalt. Highway 64 (6), 214–219. Highway, Chang'an University. He is selected into the Young
Yu, R., Zhu, X., Zhang, M., et al., 2018a. Investigation on the short-term aging-resistance Key Talents Program of Chang'an Scholars. He is the key
of thermoplastic polyurethane-modified asphalt binders. Polymers 10 (11), 1189. member of Key Scientific and Technological Innovation Teams
Yu, R., Zhu, X., Zhang, M., et al., 2018b. Performance and mechanism of graphene oxide/ in Shaanxi Province. He has won the first and second prizes of
polyurethane modified asphalt mixture. Science Technology and Engineering 18 three provincial and ministerial scientific research awards. He
(33), 209–214. has published more than 20 SCI/EI academic papers.
Zeng, L., Wei, J., Hou, J., et al., 2017. Development and evaluation of polyurethane
modified asphalt. Journal of Changsha University of Technology (Natural Science
Edition) 14 (4), 24–29.
Zhang, H., 2020. Study on Road Performance of Polyurethane Modified Asphalt and its
Mixture (master thesis). Harbin Institute of Technology, Harbin.
Zhang, Z., Huang, T., Zhu, Y., et al., 2021a. The influence of PU soft segment structure
type on the performance of PU modified asphalt. Journal of Chang'an University
(Natural Science Edition) 41 (6), 1–9.
Zhang, H., Su, C., Bu, X., et al., 2020a. Laboratory investigation on the properties of
polyurethane/unsaturated polyester resin modified bituminous mixture. Dr. Xiaoping Ji is a professor of road engineering at School of
Construction and Building Materials 260, 119865. Highway, Chang'an University. He is selected as the Young
Zhang, Z., Sun, J., Huang, Z., et al., 2021b. A laboratory study of epoxy/polyurethane Scientific and Technological Talent of the Ministry of Transport.
modified asphalt binders and mixtures suitable for flexible bridge deck pavement. He is the key member of Key Scientific and Technological
Construction and Building Materials 274, 122084. Innovation Teams in Shaanxi Province. He has presided over
Zhang, Z., Sun, J., Jia, M., et al., 2020b. Study on a thermosetting polyurethane modified more than 20 important scientific research projects, and won 8
asphalt suitable for bridge deck pavements: formula and properties. Construction and provincial and ministerial scientific research awards. He has
Building Materials 241, 118122. published more than 40 SCI/EI academic papers, and autho-
Zhang, Z., Sun, J., Jia, M., et al., 2021c. Effects of polyurethane thermoplastic rized more than 20 national invention patents.
polyurethane elastomer on properties of asphalt binder and asphalt mixture. Journal
of Materials in Civil Engineering 33 (3), 04020477.
Zhang, Z., Sun, J., Wang, F., et al., 2020c. Epoxy resin/polyurethane composite modified
asphalt and its mixture performance research. Functional Materials 51 (12),
12198–12203.
Zhang, Z., Zhang, Y., Huang, S., 2020d. Study on road performance of SBS-PU composite
modified asphalt and its mixture. Journal of Chongqing Jianzhu University 39 (5),
76–84. Kaixi Duan is a master candidate at School of Highway, Chan-
Zhao, D., 2018. Preparation and Properties of Polyurethane-Epoxy Modified Asphalt g'an University. His research interests include polymer modified
(master thesis). Chang’an University, Xi’an. asphalt materials and pavement service state detection.
Zhou, X., Sun, B., Wu, S., et al., 2019. Evaluation on self-healing mechanism and
hydrophobic performance of asphalt modified by siloxane and polyurethane. Journal
of Wuhan University of Technology 34 (3), 630–637.

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