Polymer 192 (2020) 122299

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Polymer
journal homepage: http://www.elsevier.com/locate/polymer

Photo-induced topological self-reorganization and self-growth of polymer

based on dynamic reversible aromatic pinacol units
Yuan Li a, Ze Ping Zhang a, *, Wei Jie Mo a, Min Zhi Rong a, **, Ming Qiu Zhang a, ***, Dong Liu b
a
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, GD HPPC Lab, School of Chemistry, Sun Yat-sen University, Guangzhou,
510275, PR China
b
Key Laboratory of Neutron Physics and Institute of Nuclear Physics and Chemistry (INPC), China Academy of Engineering Physics (CAEP), Mianyang, 621999, PR
China

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

Keywords: Crosslinked polyurethane containing aromatic pinacol units as novel reversible C–C bonds provider is synthe­
Aromatic pinacol sized. For the first time, photo-induced topological self-reorganization through the reversible C–C bonds leads to
Topological self-reorganization the transformation of micro-phase separation structure, realizing improvement of the tensile strength and failure
Rehealable
strain from 23 MPa to 34 MPa and from 1205% to 1695%, respectively. In contrast, mechanical properties of the
reference sample without pinacol moieties decrease sharply after the same UV irradiation. Internal structural
variations are analyzed in detail by equilibrium swelling experiment, dynamic mechanical analysis (DMA),
differential scanning calorimetry (DSC), small angle neutron scattering (SANS) and positron annihilation lifetime
spectroscopy (PALS). Moreover, the carbon radicals generated from homolysis of the aromatic pinacol are found
to be able to further initiate polymerization of vinyl monomers, which helps to achieve crack healing, surface
self-growth and formation of semi-interpenetrating polymer networks. This kind of macromolecular initiator-
embedded polymer could re-initiate polymerization when the surface arrays are wiped away to expose the
fresh underlying aromatic pinacol units. It is believed that the outcomes may enrich and expand the applications
of dynamic covalent polymers.

1. Introduction polymerization of vinyl monomers to obtain distinct polymer architec­

Crosslinked polymers with reversible covalent bonds can undergo
exchange reaction in the presence of external stimuli (such as heat, pH,
light and catalyst), leading to reorganization of the topological network
structures [1]. Accordingly, not only intrinsic self-healing, but also a
series of processing technologies such as reprocessing, plastic defor­
mation, surface welding, injection and extrusion molding can be ach­
ieved [2–7]. This kind of dynamic covalent polymers combines the
excellent mechanical properties, solvent resistance and reprocessability,
showing broad application prospects and becoming one of the research
hotspots in recent years [2,3].
As one of the types, dynamic covalent polymer networks containing
macromolecular initiator units can generate free radical fragments upon
application of a specific stimulus (e.g., light or heat), which not only can
realize reorganization of network structures, but also initiate
tures and morphologies [8–13]. In 2010, Matyjaszewski et al. [10,11]
demonstrated that reshuffling of iniferter units such as trithiocarbonate
(TTC) and thiuram disulfide (TDS) in dynamic covalent polymers could
implement intrinsic self-healing under irradiation of ultraviolet and
visible light, respectively. Subsequently, Zhou and Johnson [12] syn­
thesized a TTC groups-containing poly(N-isopropylacrylamide) gel,
which allowed for photo-growth of macromolecular chain after swelling
in vinyl monomers. Recently, Kloxin et al. [13] proposed a strategy to
initiate free radical polymerization of divinyl monomers by carbon
radicals produced from photosensitive dithiocarbamate (DTC) moieties
within dynamic networks. As a result, photo-induced self-healing and
strengthening of the polymer can be simultaneously achieved.
In the meantime, Wang et al. [14] reported that mechanical strength
of poly(butylene fumarate) cross-linked by Diels-Alder (DA) bonds could
be adjusted within a wide range (19–123 MPa) through the dynamic

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: 357386053@qq.com (Z.P. Zhang), cesrmz@mail.sysu.edu.cn (M.Z. Rong), ceszmq@mail.sysu.edu.cn (M.Q. Zhang).

https://doi.org/10.1016/j.polymer.2020.122299
Received 3 January 2020; Received in revised form 6 February 2020; Accepted 15 February 2020
Available online 17 February 2020
0032-3861/© 2020 Elsevier Ltd. All rights reserved.
Y. Li et al.
competition between DA reversible reaction and crystallization. Subse­
quently, Otsuka and co-workers investigated network reorganization of
dynamic covalent polymers with exchangeable diarylbibenzofuranone
from the perspective of both macroscopic and microscopic changes
[15–18]. We have incorporated aromatic pinacol monomers containing
dynamic covalent C–C bonds into crosslinked polyurethane [19]. Dy­
namic exchange reaction among macromolecules successfully cooper­
ated with solid-state drawing that used to be only applicable to
thermoplastics, realizing strengthening of the thermosetting polymer,
whose tensile strength and elongation-to-break were tunable from 27.3
MPa to as high as 115.2 MPa and from 324% to 1501%, respectively.
Afterwards, similar solid-state drawing method was used by Guo et al.
[20] to improve the strength of styrene-butadiene rubber/graphene
composites carrying dynamic imine bonds. It is worth noting that,
however, the above-mentioned systems [14–22] mostly adopt thermal
excitation. Light stimulation with the advantages of simplicity, rapidity,
cheapness and regional controllability has seldom been utilized for
property modulation of dynamic covalent polymers so far.
Interestingly, apart from heating, the aromatic pinacol units can also
undergo homolysis equilibration in the presence of UV light [23]
(Fig. 1a). It is believed that the above-mentioned functionalities like
topological reorganization and polymerization initiation would be
realized for the macromolecules including aromatic pinacol moieties
with the stimulation of UV illumination. By taking advantage of the
hydrogen transfer polymerization mechanism of the generated carbon
radicals [24], interpenetrating polymer networks (IPNs) with property
superposition and complement among components would thus be ob­
tained, which differ from the block polymers derived from living poly­
merization [12,13].
According to the consideration, crosslinked polyurethane containing
aromatic pinacols are designed and synthesized in the current work
(Fig. 1b). Its intrinsic microphase separation structures are regulated by
topological rearrangement under UV irradiation (Fig. 1ci), significantly
enhancing the mechanical strength of the materials. Furthermore, the
carbon radicals generated from aromatic pinacol are used to initiate
polymerization of vinyl monomers, which can achieve crack healing,
surface self-growth and formation of semi-IPNs (Fig. 1cii). Meanwhile,
structure-property relationships of the resultant materials are studied in
detail, which may provide insights into the expanded applications of
dynamic covalent polymers.
2. Experimental
2.1. Materials and reagents
Hexamethylene diisocyanate (HDI, 99%), polytetramethylene ether
glycol (PTMEG, Mn ¼ 2000 g mol 1), potassium carbonate (99%), iso­
propyl alcohol (IPA, 99.5%), triethanolamine (TEOA, 98%), 1,4-butane­
diol (BDO, 99%), dibutyltindilaurate (DBTDL, 95%), glycidyl
methacrylate (GMA, 97%), trifluoroethyl methacrylate (TFEMA, 98%),
acetic acid (99.5%) and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl
(4-OH-TEMPO, 98%) were supplied by Aldrich, Shanghai, China. 4-
Hydroxybenzophenone (HBP, 98%) and 2-bromoethanol (95%) were
purchased from TCI, Shanghai, China. PTMEG were dehydrated at 100
�
C in vacuum for over 24 h prior to use. N0 N-dimethylformamide (DMF,
99.9%) was dried over activated molecular sieves (4 Å) before usage. All
the other chemicals and solvents were used as received.
2.2. Synthesis of 4-(2-hydroxyethoxy) benzophenone (HEBP)
HEBP was synthesized following the route described in Ref. [19]
(Scheme S1a). HBP (7.929 g, 40 mmol) was completely dissolved in 20
ml DMF and heated up to 90 � C. Then, 2-bromoethanol (7.497 g, 60
mmol) was slowly dropped into the solution from a dropping funnel,
followed by adding of anhydrous potassium carbonate (11.057 g, 80
mmol) as the catalyst and stirring in argon for 24 h. Afterwards, the
2
Polymer 192 (2020) 122299
yellow mixture was cooled down and filtered for removal of the solid
catalyst. The filtrate was precipitated into deionized water, followed by
vacuum suction filtration and freeze-drying to obtain white crystals with
a yield of 50%. FTIR (KBr, Fig. S1): ν ¼ 3291, 3051, 2949, 2877, 1640,
1603–1443, 1417, 1378, 1254, 1094, 1052, 847, 693 cm 1; 1H NMR
(400 MHz, DMSO‑d6, δ, Fig. S2a): 3.754 (q, J ¼ 5.2 Hz, 2H; CH2), 4.098
(t, J ¼ 4.8 Hz, 2H; CH2), 4.946 (t, J ¼ 5.6 Hz, 1H; OH), 7.394–7.763 (m,
9H; Ar–H); 13C NMR (400 MHz, DMSO‑d6, δ, Fig. S2b): 59.639, 70.093,
114.713, 129.014, 129.696, 132.509, 132.654, 137.957, 162.956,
194.942.
2.3. Synthesis of 1,2-bis(4-(2-hydroxyethoxy)phenyl)-1,2-diphenyl­
ethane-1,2-diol (DHETPED)
DHETPED was synthesized according to our previous report [19]
(Scheme S1b). HEBP (4.854 g, 20 mmol) was completely dissolved in 20
ml DMF in a 50 ml quartz tube, and then isopropanol (IPA, 30 ml) and
two drops of acetic acid were added to the mixture. After homogeneous
mixing, the solution was exposed to ultraviolet light (350 nm, 4 mW
cm 2) for 4 days and poured into deionized water to obtain the crude
product, which was further purified by column chromatography (silica
gel) eluting with 1:1 petroleum ether-ethyl acetate (v/v), achieving the
yield of 31.9%. FTIR (KBr, Fig. S1): ν ¼ 3571, 3556, 3513, 3051, 2926,
2870, 1605–1443, 1418, 1374, 1248, 1074, 1035, 825, 707 cm 1; 1H
NMR (400 MHz, DMSO‑d6, δ, Fig. S3a): 4.806 (t, J ¼ 5.6 Hz, 2H; OH),
5.745 (s, 2H; OH), 3.659 (q, J ¼ 5.2 Hz, 4H; CH2), 3.865 (t, J ¼ 5.2 Hz,
4H; CH2), 6.605–7.282 (m, 18H; Ar–H); 13C NMR (400 MHz, DMSO‑d6,
δ, Fig. S3b): 59.867, 69.626, 82.936, 112.304, 125.998, 126.467,
129.542, 130.901, 138.913, 147.349, 157.040.
2.4. Synthesis of the polyurethanes
Preparation of the pinacol-containing polyurethane HDI/PTMEG/
DHETPED/TEOA (P1, Fig. 1b) was conducted through solution poly­
merization in a four-neck flask. PTMEG (10.000 g, 5 mmol) was
completely melted at 60 � C and mixed with 100 ml DMF containing one
drop of DBTDL. Next, HDI (1.766 g, 10.5 mmol, nNCO/nOH ¼ 1.05) was
slowly dropped into the mixed solution from a dropping funnel, fol­
lowed by stirring using a mechanical stirrer in argon for 6 h. Afterwards,
the prepolymer solution was cooled down to 45 � C and further reacted
with DHETPED (1.216 g, 2.5 mmol) and TEOA (0.239 g, 1.7 mmol) for
additional 18 h. At last, the mixture was poured into a silicone mold, and
then vacuum dried to obtain the product. FTIR (ATR, Fig. S4): ν ¼ 3344,
2939, 2852, 1721, 1664, 1625, 1577, 1534, 1443, 1255, 1099 cm 1.
The control material that excludes pinacol moieties, HDI/PTMEG/
BDO/TEOA (P2, Scheme S1c), was made following similar procedures
by using BDO instead of DHETPED. The chemical structure of the
product was proved by FTIR spectrum (Fig. S4).
2.5. Preparation of the polyurethanes with rearranged network structure
and semi-interpenetrating polymers
The film of P1 was swelled in dimethylbenzene (DMB) for 2 h, fol­
lowed by sealing in quartz tube at argon atmosphere and exposing to UV
light (365 nm, 6.5 mW cm 2) for 20 min on each side. Keep turning over
the film for every 2 min. Subsequently, the sample was vacuum dried to
obtain the rearranged topological network structure (P1-DMB-UV).
When P1 was replaced by P2, the control material (P2-DMB-UV) was
prepared by the same process. In order to ensure that the UV light can
reach inside the samples to trigger the reversible reactions of pinacol
units, the thickness of the samples was kept less than 1 mm (which is
similar to the values reported by the earlier works (0.8–1.2 mm) [10,13,
32]).
When the solvent was replaced by acrylate monomers (i.e. GMA or
TFEMA), a series of semi-interpenetrating polymers were obtained. The
samples are coded as Semi-IPN P1/A B/C, where A represents the
Y. Li et al. Polymer 192 (2020) 122299

Fig. 1. (a) Dissociation/association of the pinacol unit. (b) Synthesis of the pinacol units-containing polyurethane, P1. (c) Schematic diagrams of the topological
network reorganization (ci) and formation of semi-IPNs (cii).

3
Y. Li et al. Polymer 192 (2020) 122299

polyacrylate component and B/C indicates the mass ratio of P1/A

controlled by swelling time.
2.6. Characterization
Proton nuclear magnetic resonance (1H NMR) and Carbon-13 (C13)
nuclear magnetic resonance (13C NMR) spectra were measured by
AVANCE III 400 MHz spectrometer (400 MHz) with DMSO‑d6 as solvent.
Molecular weights were determined at ambient temperature using Wa­
ters Breeze gel permeation chromatography (GPC) system with DMF as
eluent and polystyrene standards for calibration. Dynamic mechanical
analysis (DMA) was conducted on METRA-VIBDMA25 using tension
mode under 1 Hz at a heating rate of 3 � C min 1 in nitrogen. Stress
relaxation behavior was recorded by DMA using tension mode, which
operated at 10% strain applied at t ¼ 0 min. Fourier transform infrared
(FTIR) spectra were recorded by Nicolet NEXUS 670 spectrometer.
Differential scanning calorimetry (DSC) measurements were per­
formed on a PerkinElmer Instrument DSC8500 equipped with Omni­
Cure®2000 ultraviolet accessory. UV initiated polymerization of the
vinyl monomers by circular P1 specimen (diameter ¼ 4 mm) was per­
formed at 30 � C and 5% open mode of aperture. Crystallinity (X) was
calculated from:
f v ¼ C � Vf � I 3 (5)
where I3 is the intensity (%) of the o-Ps, and C is an empirical constant
(0.018 nm 3) [29].
Small angle neutron scattering (SANS) beamline of China Academy
of Engineering Physics (CAEP) was used to study nanostructure of the
crosslinked networks. We employed two instrument configurations with
different sample-to-detector distances (SDDs) of 10.25 and 4.25 m. The
wavelength of the incident neutron beam was 8 Å for the first instrument
configuration and 5.3 Å for the latter. The disk-shaped samples with
thickness of 1 mm were soaked in deuterated solvent and sealed in
quartz cells. Before testing, all samples were kept at room temperature
for certain time to reach the equilibrium swelling state. Testing data
were collected at room temperature in each of the two configurations
and merged in a single one-dimensional SANS profile. The scattering
data were fitted to Teubner-Strey (TS) model according to Equations
(6)–(8), which describes a random two-phase structure with locally
lamellar order:
IðqÞ ¼
1
þb (6)
a2 þ c1 q2 þ c2 q4
2� �1=2 3
a2
1=2

6 c2 c1 7
ΔHf ξ¼6 þ 7 (7)
X¼ (1) 4 2 4c2 5
f ΔH *f

where ΔHf* denotes the melting enthalpy of 100% crystallized poly­
tetrahydrofuran glycol (236.1 J g 1) estimated according to literature
[25], ΔHf the melting enthalpy of the polymer, f the weight percentage
of polytetrahydrofuran glycol in the polyurethane.
Molecular weight between crosslinks of the polyurethane, Mc, was
measured by equilibrium swelling experiment. Mc was determined from
swelling ratio in dioxane according to Flory-Rehner equation [26]:
� �
V1 ρ V 1=3
2 0:5V2
Mc ¼ (2)
lnð1 V2 Þ þ V2 þ χ V 22
where ρ is the density of polymer, V2 the volume fraction of polymer in
the swollen mass, V1 (85.2128 cm3 mol 1) the molar volume of the
solvent (dioxane), and χ the Flory-Huggins polymer-solvent dimen­
sionless interaction term (obtained by Gauss fitting curve of swelling
degree and solvent parameters).
Electron spin resonance (ESR) spectroscopy study was conducted on
a Bruker A300-10-12 spectrometer equipped with LSB610 Hg lamp
(90–100 mW cm 2, 350–450 nm) operating at 8.85 Hz. The modulation
frequency and amplitude were 100 kHz and 0.1 mT, respectively. Test
conditions: 0.243 g DHETPED (0.1 mol L 1) and 0.009 g 4-OH-TEMPO
(0.01 mol L 1) were completely dissolved in 5 ml DMF and tested in a
sealed quantitative capillary tube.
Free volume reflects the compatibility of multicomponent system
[27]. Here in this work, the fractional free volume and pore radius of the
materials were investigated by means of positron annihilation lifetime
spectroscopy (PALS, ORTEC 0107A) with the radiation source of Na22.
The quantitative relation between orth-positronium (o-Ps) lifetimes (τ3)
and cavity radius of free volume (R) is described as follows [28]:
� � �� 1
1 R 1 2π R
τ3 ¼ 1 þ sin (3)
2 R0 2π R0
2� �1=2 3 1=2
a2
6 c2 c1 7
D ¼ 2π6
4
7 (8)
2 4c2 5
where I(q) is the scattering intensity, q is the scattering vector, b is the
background and a2, c1 and c2 are composition-dependent coefficients,
related to two characteristic lengths, D and ξ, which appear in the spatial
correlation function of the system. D represents the quasi-periodic
repeat distance of hard domains, and ξ is the correlation length [30].
Qualitative evaluation of remendability was carried out by visual
inspection of crack healing. P1 film was scratched with a knife. Then,
GMA was dropped onto the damaged area, followed by polymerization
under UV light (6.5 mW cm 2, 365 nm) for 20 min. Photos recording the
changes of the crack were taken by a camera attached to a KEYENCE
VHX1000C 3D optical microscope.
To quantitative evaluate healing ability of the materials, tensile test
was conducted on dumbbell-shaped specimens (50 � 4 � 0.2 mm3, grip
to grip separation: 20 mm) by a SANSCMT6103 universal tester ac­
cording to ISO527-2 at a crosshead speed of 50 mm min 1. The healing
process was conducted as follows. The specimen was cut to the half of
the thickness, followed by dropping GMA monomer onto the damaged
zone and polymerizing under UV light. Efficiency of healing (η) is
defined as:
σhealed σcut
η¼ (9)
σvirgin σcut
where σvirgin, σcut and σ healed are the tensile strengths of virgin, damaged
and healed specimens, respectively.
3. Results and discussion

where R0 ¼ R þ Rδ, and Rδ is a semiempirical constant, 1.656 � 10 1 nm. 3.1. Photoinduced dynamic reversibility of the pinacol units
Assuming that the free volume hole is spherical, its volume (Vf) can be
calculated from: To reveal whether the pinacol units in P1 exist in a state of equi­
librium of cleavage and recombination under UV radiation, electron
4 spin resonance (ESR) spectroscopy measurements were conducted. Due
Vf ¼ π R 3 (4)
3 to the fast coupling rate of carbon radicals derived from fission of the
The fractional free volume (fv) is given by: reversible C–C bonds, they are difficult to be detected directly.

4
Y. Li et al.
Therefore, a certain amount of nitroxide radicals (i.e. 4-OH-TEMPO) is
added to capture the carbon radicals. It is found that homolysis of
DHETPED can be triggered by UV light, resulting in the dramatical
decrease of intensity of 4-OH-TEMPO within 200 s (Fig. 2a~2c).
Moreover, the reversible C–C bonds can also be stimulated to lead to
visible discoloration of the mixed solution by taking advantage of the
trace ultraviolet light in sunlight (Fig. S5).
The dynamic reversible characteristics of P1, which originate from
the aromatic pinacol moieties, are also reflected by stress relaxation test.
As shown in Fig. 2d, stress relaxation is obviously promoted for the
swelled sample in solvent under the radiation of xenon lamp. For
excluding the influence of solvent, the specimen of P1 under swelling
state without UV stimulus was also detected. Interestingly, an unusual
stress intensification phenomenon appears, which may be attributed to
the increased hydrogen bonding density accompanied by Poisson’s
contraction [31]. It means that the topological network of P1 is allowed
to be rearranged to a less stretched state in solvent owing to bond fis­
sion/recombination of the aromatic pinacol units. Similar results were
found in other polymers carrying dynamic reversible covalent bonds
[32,33].
3.2. Tuning mechanical properties by photo-induced topological
reorganization
In order to improve the mobility of molecular chains, the dynamic
covalent polymer P1 was first fully swelled in DMB solvent and irradi­
ated with ultraviolet light, followed by removing the solvent to obtain
the P1-DMB-UV. Since carbon-centered radicals are generally sensitive
to oxygen [15], the swollen P1 was sealed in quartz tube in argon at­
mosphere to ensure the activity of the carbon radicals generated from
the cleavage of pinacol units. Nevertheless, in the follow-up studies we
found that there is no difference between the results obtained in argon
Fig. 2. Characterization of dynamic reversibility. (a) Typical ESR spectra of DHETPED/4-OH-TEMPO measured under UV irradiation for various exposure times. (b)
Normalized ESR absorption of DHETPED/4-OH-TEMPO obtained from the data of (a). (c) UV irradiation time dependences of relative ESR signal intensities
calculated from integral areas of the normalized absorption curves of (b). (d) Stress relaxation of P1 measured under various conditions.
5
Polymer 192 (2020) 122299
and those in air. The finding coincides with our earlier conclusion of the
oxygen tolerance of the carbon-centered radicals from the pinacol units
under thermal stimulation [19]. In this context, the related results ob­
tained in air are shown hereinafter unless otherwise specified.
Polyurethanes used to be considered to be extremely susceptible to
UV irradiation, which would result in unfavorable changes in their
structure and chemistry, and largely affect their physical and mechan­
ical properties [34,35]. Contrary to ordinary conception, the tensile
strength and failure strain of the dynamic covalent polymer P1-DMB-UV
(Fig. 3a, Table 2) are significantly improved from 23 MPa to 34 MPa and
from 1205% to 1695% after exposure to UV light, while those of the
reference sample P2-DMB-UV decrease sharply (e.g., the failure strain is
reduced from 1336% to 429%).
To reveal the microscopic variation of topological network structure
(i.e. domain structure and free volume characteristics) before and after
UV radiation, PLAS and SANS (Fig. 3b) measurements were conducted,
and the results are summarized in Table 1. Clearly, after UV irradiation,
the correlation length (ξ, 6.5 nm) of P1-DMB-UV is basically the same as
that of P1 (6.4 nm), but the characteristic length (D) decreases from 22.3
to 19.8 nm. It indicates that the hard domain size (i.e. ξ) of P1-DMB-UV
remains nearly unchanged (~1.3%), while the distance between the
adjacent hard domains (i.e. D) decreases by 11.2%. The phenomena
should be attributed to the exchange reaction of the pinacol units in the
hard blocks triggered by UV light, which results in the closer distance
and more favorable microphase separation (Figs. S7a and 7b). More­
over, larger o-Ps lifetime (τ3, 2.56 ns), free volume size (0.152 nm3) and
fraction of free volume (fy, 8.2%) are observed after exposure to UV
light. The significant increase in free volume from 0.121 to 0.152 nm3 is
interpreted as the enhancement of microphase separation [38].
It is seen that the ξ value of the irradiated reference sample P2-DMB-
UV (5.7 nm) decreases as compared to the virgin material P2 (7.4 nm),
which is consistent with the results of Almasy et al. [39]. Since UV
Y. Li et al. Polymer 192 (2020) 122299

Fig. 3. (a) Typical stress-strain curves of P1, P1-DMB and P1-DMB-UV. (b) SANS data of the polyurethane networks. The solid lines are the fitting results by TS
model. (c) Tan δ and (d) DSC heating curves of the polyurethane networks with different treatment conditions.

Table 1 Table 2
The characteristic parameters of the polyurethane networks obtained from PALS Properties of the polyurethane networks estimated from Figs. 3a, 3c, 3d and S6.
spectra and SANS test. Propertiesa P1 P1-DMB- P2 P2-DMB-
Samples Parametersa UV UV

τ3 I3 R Vf fv ξ D Tensile strength (MPa) 23.0 � 2.1 34.0 � 3.1 35.4 � 4.7 5.9 � 1.3
(ns) (%) (nm) (nm3) (%) (nm) (nm) Elongation at break 1205 � 1 1695 � 92 1336 � 148 429 � 113
(%)
P1 2.25 49.8 0.307 0.121 8.1 6.4 22.3 Tgb (oC) 40.9 48.4 55.0 47.2
P1-DMB- 2.56 62.1 0.331 0.152 8.2 6.5 19.8 Tmc (oC) 11.5 13.0 13.0 14.6
UV ΔHfc (J g 1) 28.9 26.8 74.9 17.8
P2 1.98 50.9 0.283 0.095 5.2 7.4 19.8 X (%) 16.2 15.0 38.9 9.2
P2-DMB- 1.77 51.0 0.262 0.076 4.2 5.7 21.7 Mcd (g mol 1) 1936 2087 2388 2279
UV
a
a Glass transition temperature (Tg), melting temperature (Tm), melting
o-Ps lifetime (τ3), o-Ps intensity (I3), free volume radius (R), free volume (Vf),
enthalpy (ΔHf), 5 wt% weight loss temperature (T5%), molecular weight between
fractional free volume (fv), correlation length (ξ), characteristic length (D).
crosslinks (Mc), crystallinity (X).
b
Measured by DMA.
irradiation can cause partial cross-linking between macromolecular c
Measured by DSC.
chains [40], the contractile force of the soft domains with larger mass d
Measured by equilibrium swelling experiment in dioxane.
fraction increases more obviously, which would pull a part of the hard
segments into the soft domains. Therefore, the average size of the hard crystallization behavior of PTMEG soft segments within the dynamic
domain decreases (Figs. S7c and S7d). Meantime, the D value of covalent polymer samples. The Tg value of P1-DMB-UV decreases from
P2-DMB-UV increases from 19.8 nm of P2 to 21.7 nm, which well agrees 40.9 � C to 48.4 � C (Fig. 3c, Table 2), which implies an enhancement
with the previous PALS studies of common polyurethanes under UV of microphase separation between the soft and hard domains has taken
irradiation [41,42]. In addition, P2-DMB-UV shows smaller values of τ3, place [37]. On the contrary, the crystallinity of PTMEG soft segments of
free volume size and fraction, which should also result from the UV P2-DMB-UV greatly decreases from 38.9% of P2 to 9.2%, accompanied
light-induced increase of crosslinking density [41,42]. by the increase of Tg value from 55.0 � C to 47.2 � C (Fig. 3c, Table 2).
For understanding the effect of UV irradiation on the chain mobility, It is evident that the trend of phase mixing is enhanced [36]. Meanwhile,
crystallinity and crosslinking density of dynamic covalent polymers, the slightly increase of crosslinking density of P2-DMB-UV due to UV
DMA (Fig. 3c), DSC (Fig. 3d) and swelling test (Fig. S6 and Table S1) illumination can also be seen from the fact that the swelling degrees in
were further carried out. The collected data are summarized in Table 2. various solvents and molecular weight between the cross-links (Mc)
The P1 and P1-DMB-UV show almost identical DSC curves and crys­ insignificantly decrease (Fig. S6).
tallinity, suggesting that UV exposure had no apparent impact on the In this context, it can be concluded that the increase of microphase

6
Y. Li et al.
separation through photo-induced topological reorganization is
responsible for improvement of mechanical strength of P1-DMB-UV. On
the contrary, the deterioration of the mechanical properties of P2-DMB-
UV upon UV irradiation is related to the phase mixing between hard
segments and soft segments [43].
3.3. Photo-polymerization assisted crack healing
Carbon-centered radicals derived from aromatic pinacol units have
long been used for initiation of polymerization of vinyl monomers. The
mechanism lies in the hydrogen transfer of primary carbon-centered
radicals to form monomer radicals that initiate the polymerization
[24]. As shown in Fig. 4a, the DSC measurements evidence that the
photo-induced polymerization of GMA and TFEMA on the surface of P1
film can proceed as expected, showing obvious exothermic peak within
5 min. While the DSC curves of P1, GMA and TFEMA exhibit no obvious
change with increasing the UV irradiation time. Interestingly, this
photo-initiated polymerization behavior can be utilized for healing of P1
films. Disappearance of artificial crack can be observed after dropping
GMA monomers onto the damaged area and subsequently polymerizing
in the presence of UV light (Fig. 4c and 4d). Furthermore, quantitative
characterization of the healing efficiency was carried out by tensile tests
(Fig. 4b). The original specimen was cut to the half of the thickness, and
then healed by the above-mentioned process. It is found that the tensile
strength can recover to 71.6% that of the original value, and the average
healing efficiency is about 50% as calculated by Eq. (9).
In the meantime, we also conducted control healing experiments in
terms of (i) UV light driven intrinsic healing of P1 and (ii) filling with P1
gel in association with UV light. The healing efficiencies are rather low
(<10%) as few interactions can be established across the interfaces.
Fig. 4. (a) UV curing curves of GMA and TFEMA initiated by P1 film. (b) Typical stress-strain curves of original (P1), cut (P1-cut) and healed (P1-healed) spec­
imens. (c, d) Photos showing photo-polymerization assisted healing of P1 film: (c) before dropping GMA monomers, (d) after healing. The conditions of UV illu­
mination for (b) and (d): 6.5 mW cm 2, 365 nm, 20 min.
7
Polymer 192 (2020) 122299
3.4. Photo-induced self-growth of semi-interpenetrating polymer networks
and surface arrays
Dynamic covalent polymer networks containing macro-iniferter
units can generate radical fragments upon application of a particular
stimulus (e.g., light or heat), and then initiate further polymerization to
achieve distinct polymer architectures and morphologies [44]. It pro­
vides a facile route for tailoring surface properties through the
self-growth of functional polymers from the initiator-embedded sub­
strate. Meanwhile, the substrate can re-initiate polymerization when the
grafted polymer layer is mechanically wiped away to expose the flesh
surface. As shown in Fig. 5, renewable surface arrays (Fig. 5b) can be
obtained by using stainless steel mesh (1500 mesh, Fig. 5a) as photo­
mask and GMA as polymeric monomer, which is expected to be applied
in surface sensors.
Moreover, semi-interpenetrating polymer networks composed of
vinyl monomer-grafted P1 and homopolymer of vinyl monomers (see
Fig. S8 for the photo-initiation polymerization mechanism) can be ob­
tained in the presence of GMA or TFEMA as the polymerization mono­
mers. This strategy is actually a secondary photo-polymerization within
the dynamic covalent networks triggered by UV light. According to this
behavior, P1 is swelled in GMA or TFEMA for various times (Fig. 6a) to
Fig. 5. SEM photographs of (a) stainless-steel mesh and (b) poly(glycidyl
methacrylate) (PGMA) micro-arrays.
Y. Li et al. Polymer 192 (2020) 122299

Fig. 6. (a) Room temperature swelling

curves of P1 in GMA and TFEMA. (b) Tan δ
of semi-interpenetrating polymers measured
between 100 � C and 150 � C. (c)-(h) SEM
images and (i)-(k) EDS mapping of the frac­
ture surfaces of (c) Semi-IPN P1/PGMA 1/
0.76, (d) Semi-IPN P1/PGMA 1/1.07, (e)
Semi-IPN P1/PGMA 1/1.39, (f, i) Semi-IPN
P1/PTFEMA 1/0.36, (g, j) Semi-IPN P1/
PTFEMA 1/0.48, and (h, k) Semi-IPN P1/
PTFEMA 1/0.65. Conditions for the mate­
rials preparation: P1 was swelled in GMA or
TFEMA for (c, f, i) 10 min, or (d, g, j) 30 min,
or (e, h, k) 24 h, and then exposed to UV
light (6.5 mW cm 2, 365 nm) for 20 min.
The arrows indicate the thickness direction
of the specimens.

control the contents of the second component in the resultant semi-
interpenetrating networks, followed by polymerization under irradia­
tion of UV light.
The stretching vibration of C–O at about 1160 cm 1 is obviously
observed on the FTIR spectrum, which demonstrates the successful
incorporation of polyacrylate components (Fig. S9) [45]. Properties of
those semi-interpenetrating polymer networks estimated from DSC
(Fig. S10), DMA (Figs. 6b and S11) and TGA (Figs. S12 and S13) are
shown in Table 3. All the resultant polymers exhibit two Tg, corre­
sponding to the polyurethane soft segments and vinyl homopolymers,
respectively (Fig. 6b). The Tg values of the soft segments in Semi-IPN
P1/PGMA ( 17.1 � C ~ 20.6 � C) shift to much higher regime in

Table 3
Properties of the semi-interpenetrating polymer networks determined from Fig. 6 and Figs. S10–S13.
Propertiesa P1 Semi-IPN P1/PGMA Semi-IPN P1/PGMA Semi-IPN P1/PGMA Semi-IPN P1/PTFEMA Semi-IPN P1/PTFEMA Semi-IPN P1/PTFEMA
1/0.76 1/1.07 1/1.39 1/0.36 1/0.48 1/0.65

Tgb (oC) 40.9 20.6, 97.9 16.5, 96.9 17.1, 96.5 55.0, 93.1 53.8, 93.1 53.8, 96.0
Tmc (oC) 11.5 8.3 8.0 7.3 16.1 15.6 12.9
ΔHfc (J g 1) 28.9 10.2 7.1 4.1 14.8 13.1 11.5
T5%d (oC) 318.6 300.8 299.8 298.3 284.7 289.5 282.6
1st weight lossd 14.1 29.8 34.4 42.1 91.5 93.4 93.1
(%)
2nd weight lossd 82.2 64.2 58.1 51.1 – – –
(%)
a
Glass transition temperature (Tg), melting temperature (Tm), melting enthalpy (ΔHf), 5 wt% weight loss temperature (T5%).
b
Measured by DMA.
c
Measured by DSC.
d
Measured by TGA.

8
Y. Li et al.
comparison with pure P1 ( 40.9 � C, Table 2), which coincides with the
observation made by Desai et al. [46]. It is suggested that grafting of
GMA onto P1 chains as well as partial spontaneous mixing may be
responsible for this phenomenon. However, the Tg values of Semi-IPN
P1/poly(trifluoroethyl methacrylate) (PTFEMA) shift to lower side (i.
e., 55 � C ~ 53.8 � C, Fig. 6b), which means an inferior interpene­
tration in comparison to Semi-IPN P1/PGMA [47]. The relatively lower
compatibility between the fluorinated polyacrylate PTFEMA and P1
should take the responsibility. Nevertheless, compared with the con­
ventional sequential interpenetrating networks of polyurethane-vinyl
polymers [48,49], the interpenetrating structures obtained in this
paper have no obvious phase separation or material aggregation ac­
cording to the SEM images (Fig. 6c~6h). The results imply that the
compatibility of as-obtained interpenetrating structure may be
enhanced by the chain entanglement between the two components,
ascribing to the effective bridging and compatibilization effect of the
in-situ vinyl-grafted P1 products. It is noteworthy that the EDS mapping
of the resultant samples obtained before the swelling equilibrium of
vinyl monomers (i.e. 10 min) shows gradient changes of PTFEMA along
the thickness of the composite after polymerization (Fig. 6i) [45]. In
general, such gradient structures often possess properties different from
homogeneous structures or layered composite structures, and have po­
tential applications in optical devices, thermal stress mitigation, etc.
[49,50] As the swelling reaches equilibrium (i.e. 2 h), the PTFEMA
component is evenly dispersed in PU matrix, which can be observed by
EDS mapping of the fluorine element (Fig. 6k).
The aim of the elaboration of interpenetrating networks is to obtain
materials with potential synergy of the component properties [51]. As
shown in Fig. S11, the incorporation of acrylate polymers, especially
PGMA component, can significantly improve the elastic modulus of the
matrix polyurethane, and the result is in accordance with that reported
by Wang et al. [45]. For PTFEMA, it can significantly increase the sur­
face contact angle from 63.2� of the pristine P1 to 90.4� (Fig. S14),
which is in good agreement with the reported values of PTFEMA poly­
mer brushes [52]. It implies a significant shift from hydrophilicity to
hydrophobicity with the incorporation of the low surface energy fluo­
ropolymer. Nevertheless, both PGMA and PTFEMA lead to slight
decrease of thermal stability of the resultant materials (Figs. S12 and
S13 and Table 3). In the case of Semi-IPN P1/PGMA 1/1.39, for
example, the 5 wt% weight loss temperature (T5%) decreases from 318.6
�
C of the pristine P1 to 298.3 � C. As the PGMA content increases, peak
area of the first decomposition peak increases accompanied by
decreasing of the second decomposition peak (Fig. S12b). Usually, the
thermal stability of strong polar groups is relatively poor [53,54], so that
the polyurethane with a large proportion of low polar polyols has higher
stability than the acrylate polymers with high ester bonds content.
Moreover, the T5% values of Semi-IPN P1/PTFEMA are also reduced by
about 29 � C–36 � C.
4. Conclusions
Aromatic pinacol, as a traditional radical initiator, is now utilized as
a novel photo-reversible unit for preparing dynamic covalent polymers,
which can be cleft and rebonded under UV irradiation. Accordingly, the
UV light-triggered dynamic reversible crosslinked polyurethane can
adjust its micro-phase separation structure through reshuffling of the
topological networks, realizing improvement of both tensile strength
and failure strain. Meanwhile, the initiator-embedded polymer matrix
itself is allowed to initiate polymerization of vinyl monomers by utiliz­
ing the carbon radicals derived from fission of the reversible C–C bonds
under UV irradiation. It results in not only photo-polymerization assis­
ted crack healing, but also different polymer architectures including
semi-interpenetrating polymer networks and surface arrays. Further
investigation in this aspect is required to yield various functional poly­
mer structures and morphologies, such as sensing and hydrophobic ar­
rays, through precise design of the second network polymers. The
9
Polymer 192 (2020) 122299
outcomes of this study may enrich the application scope of polymer
engineering based on reversible covalent chemistry.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Yuan Li: Data curation, Investigation. Ze Ping Zhang: Conceptual­
ization, Writing - original draft, Writing - review & editing, Visualiza­
tion, Funding acquisition. Wei Jie Mo: Data curation, Investigation.
Min Zhi Rong: Writing - review & editing, Funding acquisition. Ming
Qiu Zhang: Methodology, Writing - review & editing, Supervision,
Funding acquisition. Dong Liu: Resources.
Acknowledgements
The authors thank the support of the Natural Science Foundation of
China (grants: 51603235, 51773229, 51873235 and 51973237), the
Scientific and Technological Program of Guangdong Province (Grant:
2017A010103008), Natural Science Foundation of Guangdong Province
(Grant: 2018B030311017) and the Fundamental Research Funds for the
Central Universities (Grant: 181gpy41).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymer.2020.122299.
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