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ARTICLE

Aluminium-Catalyzed Terpolymerization of Furfuryl Glycidyl Ether

Polymer Chemistry Accepted Manuscript

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with Epichlorohydrin and Ethylene Oxide: Synthesis of

Received 00th January 20xx,
Accepted 00th January 20xx
Thermoreversible Polyepichlorohydrin Elastomers with
DOI: 10.1039/x0xx00000x
Furan/Maleimide Covalent Crosslinks††
www.rsc.org/ Ming Deng,a Fang Guo,*a Daohong Liao,a Zhaomin Hou,a,b and Yang Li*a
By use of an alkylaluminium catalyst system i-Bu3Al/H3PO4/1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), the random
copolymerization and terpolymerization of furfuryl glycidyl ether (FGE) with epichlorohydrin (ECH) and ethylene oxide (EO)
have been achieved for the first time to afford a new family of furan functionalized polyepichlorohydrin elastomers. The
composition of obtained FGE/ECH copolymers, FGE/EO copolymers and FGE/ECH/EO terpolymers coincided with the co-
monomer feed ratio, and furan groups could be quantitatively and randomly incorporated into polyepichlorohydrin
elastomers. Based on the Diels-Alder (DA) reaction of furan functionalized polyepichlorohydrin elastomers and 4,4'-
methylenebis(N-phenylmaleimide), a new series of thermoreversible cross-linked polyepichlorohydrin elastomers was
successfully synthesized. These thermoreversible DA cross-linked polyepichlorohydrin elastomers possessed tunable
mechanical properties by adjusting the content of FGE units in FGE/ECH/EO terpolymers. The mechanical properties of DA
cross-linked polyepichlorohydrin elastomers were significantly better than those of the traditional vulcanized
polyepichlorohydrin elastomers, which could be used as structural material without reinforcing agents. More importantly,
the DA cross-linked polyepichlorohydrin elastomers could be remolded and self-healed without loss of performance.

2
temperature and high decoupling temperature. At present,
Introduction furan groups as crosslinking agents have already been randomly
3,4 5,6 7
incorporated into epoxy resin, polyacrylates, polystyrene,
Polyepichlorohydrin elastomers such as epichlorohydrin (ECH) 8 9,10 11,12
polyketones, polybutadiene, ethylene/propylene rubber,
homopolymers and ECH‒ethylene oxide (EO) copolymers are typical 13 14
ethylene/vinyl acetate rubber, and poly(propylene oxide). The
functional polymeric materials with specific characteristics of
incorporation of furan units as a block into poly(EO) by sequential
interest for a wide range of applications in automotive, aerospace,
1 living anionic ring opening polymerization have also been
printing and copying etc. However, these polyepichlorohydrin 15-18
reported. However, the random copolymerization of FGE with
elastomers with excellent properties cannot be reprocessed and
ECH or terpolymerization of FGE with ECH and EO is still a difficult
repaired after damage because of their irreversible cross-linking
and challenging problem due to the reactivity ratios of monomers
structure prepared by traditional vulcanization technologies. The 14, 19-22
differing by several orders of magnitude.
introduction of reversible dynamic cross-linking structure to
The alkylaluminium-based catalysts such as AlR3/H2O/third
polyepichlorohydrin elastomers is highly desirable to construct a 23,24 25,26
component and AlR3/H3PO4/Lewis base are well known as
new type of reversible covalent crosslinking thermoreversible
efficient catalysts for the polymerization of epoxy monomers
elastomers which possess excellent mechanical properties of cross-
because of ease of preparation, good stability, and versatility for
linked rubber under service conditions, while they would be
various monomer substrates. In this paper, we have examined the
remolded just like plastic materials after their product life.
potential of AlR3/H3PO4/Lewis base for the polymerization of FGE
Diels−Alder (DA) reaction between furan and maleimide is an
and its copolymerization with ECH and EO. By use of i-
excellent candidate for reversible polymer cross-linking because of
Bu3Al/H3PO4/1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), the random
relatively fast kinetics, mild reaction conditions, low coupling
copolymerization of FGE with ECH and EO and terpolymerization of
FGE with ECH and EO have been achieved for the first time to give a
a new family of furan functionalized polyepichlorohydrin elastomers.
State Key Laboratory of Fine Chemicals, Department of Polymer Science and
Engineering, School of Chemical Engineering, Dalian University of Technology, The obtained furan functionalized polyepichlorohydrin elastomers
Dalian 116012, China. E-mail: [email protected]; [email protected]
b
were cross-linked in the presence of bismaleimide to afford a new-
Organometallic Chemistry Laboratory and Center for Sustainable Resource
Science, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
style of thermoreversible polyepichlorohydrin elastomers with
† Electronic Supplementary Information (ESI) available: NMR spectra, FT-IR dynamic thermoreversible cross-linked network, which
spectra, GPC, DSC and TGA curves of representative polymer products. See
DOI: 10.1039/x0xx00000x

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demonstrated excellent mechanical properties, self-healing ability, ampoule bottle by syringe; then the i-Bu3Al/H3PO4/DBU
and thermal recyclability. catalyst solution prepared as described above was injected
into the ampoule bottle during stirring with a magnetic stirrer.
o
After the polymerization was carried out at 25 C for 0.5 h,
Experimental section viscous toluene solution of FGE/ECH/EO (ECO/FGE20)
Materials terpolymer was obtained. The solution was poured into a
larger amount of n-hexane to precipitate the ECO/FGE20
Solvents were purified by the use of a SPS-800 solvent purification
terpolymer, which was washed with methanol and dried under
system (Mbraun) and stored over fresh Na chips. Epichlorohydrin o
vacuum at 40 C to a constant weight. The dried ECO/FGE20
(ECH), 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) were dried over
terpolymer was used for chemical analysis. The ECO/FGE20

Polymer Chemistry Accepted Manuscript

CaH2 overnight, vacuum-transferred, and degassed by three freeze-
terpolymer solution for Diels−Alder (DA) cross-linking reaction
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pump-thaw cycles. Ethylene oxide (EO) was dried over CaH2 under 0
o was scale-up synthesized in a 250 mL stainless autoclave with
C for 2 h, vacuum-transferred into toluene with concentration of
same procedures. Other ECO/FGEm terpolymers and
2.0 mol/L. Furfuryl glycidyl ether (FGE) was synthesized according to
27 terpolymer solutions for DA crosslinking were obtained with
the previous method, and purified by same method with ECH. The
same procedure, where m is defined molar percent content of
pure phosphoric acid was diluted with ethyl ether to 1.25 mol/L
FGE in the FGE/ECH/EO terpolymers, and molar ration of ECH
under purified nitrogen atmosphere. i-Bu3Al, 4,4'-Methylenebis(N-
and EO is 1.
phenylmaleimide) (BMI), Pb3O4, imidazolidine-2-thione (NA22),
bis((dibutylcarbamothioyl)thio)nickel (NBC) and carbon black were Diels-Alder cross-linking reaction of FGE/ECH/EO terpolymers
used without further purification. (ECO/FGEm) and preforming.

A typical procedure for preparation of i-Bu3Al/H3PO4/DBU catalyst Antioxidant NBC (2.0 wt% of polymer) and BMI (0.5 equivalent
(Table 1, run 2). of furan group in terpolymers) were added into the toluene
solutions of ECO/FGEm terpolymers prepared as described
i-Bu3Al/H3PO4/DBU catalyst was prepared in a dried ampoule
above. After homogeneous mixing, the resulting mixtures were
bottle equipped with a magnetic stirrer under purified
poured into a larger amount of n-hexane to precipitate
nitrogen atmosphere. The ethyl ether solution of phosphoric
ECO/FGEm terpolymers mixed with BMI (ECO/FGEm/BMI0.5m),
acid (0.175 mmol, 1.25 mol/L) was added dropwise to i-Bu3Al
o which were washed with methanol and dried under vacuum at
(0.500 mmol, 1.0 mol/L in toluene) at 0 C under vigorous o
40 C to a constant weight. The ECO/FGEm/BMI0.5m
stirring. Then, the solution was warm to room temperature o
terpolymers were compression molded for 30 min at 155 C
and DBU (0.130 mmol) was added by syringe. The solution was
o and 100 bar. Then the resulting ECO/FGEm/BMI0.5m
heated to 60 C for 2 h under stirring and gave colorless o
terpolymers plaques were crosslinked for 8 h at 70 C in oven
transparent i-Bu3Al/H3PO4/DBU catalyst solution. 28
to afford red DA cross-linked materials
A typical procedure for the copolymerization of ECH and EO (Table (DA_ECO/FGEm/BMI0.5m). The cross-linking degree of
1, run 2). DA_ECO/FGEm/BMI0.5m could be tuned by adjusting the
Polymerization was carried out in a dried ampoule bottle content of FGE and BMI.
equipped with a magnetic stirrer under purified nitrogen Vulcanization of cross-linking of ECH/EO copolymers and
atmosphere. Toluene (5 mL), ECH (10 mmol), EO (10 mmol, 2.0 preforming.
mol/L in toluene) were injected into the ampoule bottle by Antioxidant NBC (2.0 wt% of polymer), Pb3O4 (6.0 wt% of
syringe; then the i-Bu3Al/H3PO4/DBU catalyst solution
polymer), cross-linking agent NA22 (0.8 wt% of polymer) were
prepared as described above was injected into the ampoule
added into the toluene solution of ECH/EO copolymer
bottle during stirring with a magnetic stirrer. After the
o prepared as described above. After homogeneous mixing, the
polymerization was carried out at 25 C for 0.5 h, viscous
resulting mixture was poured into a larger amount of n-hexane
toluene solution of ECH/EO (ECO) copolymer was obtained.
to precipitate the ECH/EO copolymer mixed with NA22
The solution was poured into a larger amount of n-hexane to
precipitate ECO copolymer, which was washed with methanol (ECO/NA220.8), which was washed with methanol and dried
o
o
and dried under vacuum at 40 C to a constant weight. The under vacuum at 40 C to a constant weight. The products
o
dried ECO copolymer was used for chemical analysis. The ECO were compression molded and vulcanized for 35 min at 155 C
copolymer solution for vulcanization crosslinking was scale-up and 100 bar to afford vulcanization cross-linked material
synthesized in a 250 mL stainless autoclave with same Vulcanized_ECO/NA220.8. Other Vulcanized_ECO/NA22n
procedures. materials were obtained by using the same method, where n is
A typical procedure for the terpolymerization of ECH, EO and FGE defined weight content of NA22 in the ECH/EO copolymers
(Table 1, run 23). (molar ration of ECH and EO is 1). The cross-linking degree of
Vulcanized_ECO/NA22n could be tuned by adjusting the
Polymerization was carried out in a dried ampoule bottle
content of NA22. Carbon black reinforced material
equipped with a magnetic stirrer under purified nitrogen
(Vulcanized/Carbon) was also obtained in same method but
atmosphere. Toluene (6 mL), ECH (8 mmol), EO (8 mmol, 2.0
with extra 40 wt% carbon black.
mol/L in toluene) and FGE (4 mmol) were injected into the

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Kinetic experiments of ECH/EO, EO/FGE and ECH/FGE weights of the swollen and dried samples were used to
copolymerization. calculate the swelling ratio, gel fraction and apparent cross-
In an NMR sample tube, ECH (260 μmol) and FGE (260 μmol) link density using the Flory−Rehner equaƟon.
was added to 1.0 mL of deuterated toluene. After 2
[XLD]S = [ln(1-φ)+φ+χφ ]/[-2ρECOVTHFφ
1/3
];
homogeneous mixing, 0.1 mL of the catalyst solution
(containing 13 μmol of i-Bu3Al, the mole ratio of i- φ = (m3/ρECO)/[(m3/ρECO)+(m2-m1)/ρTHF];
Bu3Al/H3PO4/DBU is 1/0.6/0.26) was added. The NMR sample
Swelling ratio = (m2/m1-1); Gel fraction = m3/m1;
tube was then quickly placed in a Bruker AC-400 NMR
spectrometer, and data were collected until signals of Where ρTHF is density of THF, ρECO is density of polymer, VTHF

Polymer Chemistry Accepted Manuscript

monomers were disappeared. The NMR spectrometer was is the molar volume of THF, χ is the interaction parameter.
Published on 29 November 2017. Downloaded by Fudan University on 29/11/2017 12:02:14.

o
held at 25 C and collected scans at periodic time intervals. The Theoretic cross-link density was calculated according to the
kinetic data and time-dependent composition of ECH/FGE following formula:
copolymerization were used to calculate reactivity ratio
29 [XLD]S = x/(xMFGE+yMECH+zMEO+0.5xMBMI)
adopted a Nonterminal Model of Chain Copolymerization.
The same procedure was used to obtain the reactivity ratio of Where x, y, and z were molar contents of FGE, ECH, EO units
ECH/EO and EO/FGE copolymerization. in terpolymer calculated by NMR analysis, respectively; MFGE,
MECH, MEO, MBMI were molar weight of FGE, ECH, EO and BMI.
Characterization.
The 13C-NMR spectra of ECH/EO, FGE/ECH, FGE/EO copolymers Results and discussion
and FGE/ECH/EO terpolymers were recorded on a Bruker AC- Copolymerization and terpolymerization of furfuryl glycidyl ether
400 spectrometer in C2D2Cl4 at 25 oC. The molecular weights with epichlorohydrin and ethylene oxide
and molecular weight distributions of ECH/EO, FGE/ECH,
FGE/EO copolymers and FGE/ECH/EO terpolymers were The catalytic system i-Bu3Al/H3PO4/Lewis base is a classical
25,26
determined at 135 oC by a high temperature gel permeation catalyst for the polymerization of ECH and other epoxides.
chromatograph (HT-GPC) on an Agilent PL-GPC220 GPC The composites of this ternary catalyst have a serious impact
apparatus. 1,2,4-Trichlorobenzene was employed as an eluent on polymerization activity, copolymerization behaviour and
25,26
at a flow rate of 1.0 mL/min. The calculation was made by stereo-selectivity. To seek a high efficient catalyst for the
polystyrene standard. The DSC measurements of ECH/EO, random copolymerization of FGE with ECH and EO, the
FGE/ECH, FGE/EO copolymers, FGE/ECH/EO terpolymers and copolymerization of ECH with EO was first investigated by
DA crosslinked materials were performed on a TA DSC Q20 using different compositions i-Bu3Al/H3PO4/DBU catalyst.
instrument under a nitrogen atmosphere. Any thermal history When the H3PO4/i-Bu3Al ratio was 0.35, the copolymerization
difference of the polymers was eliminated by first heating to was completed within 30 min, and the yield of ECH/EO
200 oC (100 oC for DA crosslinked materials) at 10 oC /min, copolymer was as high as 100% (Table 1, run 2). When the
cooling to −70 oC at 10 oC /min, then heating to 200 oC (100 oC H3PO4/i-Bu3Al ratio higher or lower than 0.35, the catalyst
for DA crosslinked materials) at 10 oC /min, and then recording almost lost copolymerization activity (Table 1, runs 1 and 3).
the second scan results. Fourier transform infrared (FT-IR) The molar ratio of DBU/i-Bu 3Al had also serious effect on
spectra were acquired on Nicolet 6700 Flex spectrometer. The copolymerization activity. When the range of DBU/i-Bu3Al
film was prepared by dissolving and mixing ECO/FGE20 mole ratio was between 0.26‒0.5, the copolymerization was
terpolymer with BMI (0.5 equivalent of furan group in completed within 30 min with the yield of ECH/EO copolymers
polymer) in dichloromethane, then volatile solvent in a KBr was as high as 100%, while the molecular weight of ECH/EO
pellets. The film was heated to 70 oC to detect DA reaction and copolymers increased with DBU/i-Bu3Al ratio (Table 1, runs 2, 5
150 oC to detect retro-DA reaction. The tensile properties of and 6). When the DBU/i-Bu3Al mole ratio higher than 0.5 or
the DA and vulcanization cross-linked materials were lower than 0.26, the copolymerization activity dramatically
measured with an Instron 5576A instrument at room decreased (Table 1, runs 4, and 7). When DBU/i-Bu3Al ratio
temperature with a humidity of about 30% at a crosshead was high to 0.75, the catalyst lost its catalytic activity (Table 1,
speed of 10 mm/min. Dumbbell specimens with length of 35 run 8). These results suggested that the formation of high
mm, width of 6 mm and thickness of 1 mm were cut from active site required quantitative reaction between i-Bu3Al,
cross-linked plaque. Data analyses were based on five H3PO4 and DBU. Firstly, the reaction i-Bu3Al with H3PO4 at the
measurements on each sample performed at the same ratio of 1/0.35 might afford dialkylaluminum phosphate [(i-
30-32
conditions. The cross-link density ([XLD]S in moles per gram) of Bu2AlO)3P(O)]n; then, the quantitative DBU coordinated to
crosslinked materials were determined from swelling aluminium of dialkylaluminum phosphate could give high
experiments in THF. Approximately 50 mg (m1) of dried, cross- active site. In our experiment range, when the molar ratio of
linked polymer was weighed into a 30 mL bottle and immersed DBU/i-Bu3Al was lower than 0.26, only part of the active center
in 25 mL of THF until equilibrium swelling (1 day) was reached can be formed which resulted in lower activity; When the
(m2). Subsequently, the swollen sample was dried in a vacuum molar ratio of DBU/i-Bu3Al was higher than 0.26, the excessive
oven at 40 oC until a constant weight was reached (m3). The DBU would further coordinated which could result in partial

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Table 1 Copolymerization and terpolymerization of furfuryl glycidyl ether (FGE) with ethylene oxide (EO) and epichlorohydrin (ECH) by i-
a
Bu3Al/H3PO4/DBU

Polymer Chemistry Accepted Manuscript

c
yield composition (mol%) Mn
d e
Tg Tm
e
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run H3PO4b DBUb ECHb EOb FGEb 4 Mw/Mnd o o

(%) ECH EO FGE (×10 ) ( C) ( C)

1 0.2 0.26 20 20 0 trace

2 0.35 0.26 20 20 0 100 50 50 0 9.3 1.43 -39 ‒
3 0.5 0.26 20 20 0 trace
4 0.35 0.10 20 20 0 43 20 80 0 0.9 1.91 -50 ‒
5 0.35 0.40 20 20 0 100 50 50 0 24.1 1.62 -39 ‒
6 0.35 0.50 20 20 0 100 50 50 0 33.3 1.72 -39
7 0.35 0.60 20 20 0 13 21 79 0 3.6 2.23 -49 ‒
8 0.35 0.75 20 20 0 trace
f g
9 0.35 0.26 0 0 40 100 0 0 100 n.d. n.d. -27 ‒
10 0.35 0.26 36 0 4 100 90 0 10 15.2 1.4 -23 ‒
11 0.35 0.26 32 0 8 100 80 0 20 n.d. n.d. -24 ‒
12 0.35 0.26 20 0 20 100 50 0 50 n.d. n.d. -25 ‒
13 0.35 0.26 0 36 4 100 0 90 10 7.6 1.37 -49 54
14 0.35 0.26 0 32 8 100 0 80 20 n.d. n.d -43 38
15 0.35 0.26 0 20 20 100 0 50 50 n.d. n.d. -34 ‒
16 0.35 0.26 4 4 32 100 10 10 80 n.d. n.d. -31 ‒
17 0.35 0.26 10 10 20 96 25 25 50 n.d. n.d. -36 ‒
18 0.35 0.26 14 14 12 100 35 35 30 n.d. n.d. -37 ‒
19 0.35 0.26 16 16 8 100 40 40 20 12.5 1.51 -39 ‒
20 0.35 0.26 18 18 4 100 45 45 10 12.7 1.56 -39 ‒
21 0.35 0.26 19 19 2 100 47 47 6 10.5 1.48 -39 ‒
22 0.35 0.26 38 38 4 100 47 48 5 25.7 1.44 -39 ‒
23 0.35 0.26 2.8 11.2 26 100 7 28 65 n.d. n.d. -31 ‒
24 0.35 0.26 4.8 19.2 16 100 12 48 40 n.d. n.d. -34 ‒
25 0.35 0.26 12 24 4 100 30 60 10 10.4 1.52 -45 ‒
26 0.35 0.26 24 12 4 100 60 30 10 12.2 1.32 -31 ‒
a o b
Reaction condition: i-Bu3Al, 0.5 mmol; monomer concentration, 2 mol/L in toluene; reaction time, 0.5 h; 25 C; unless otherwise noted.
c 13 d o e
Molar ratio of i-Bu3Al. Determined by C-NMR. Determined by GPC in 1,2,4 trichlorobenzene at 135 C against polystyrene standard.
f g
Determined by DSC. Reaction time, 45 min. Not detected because of the very low solubility in THF, CHCl3, DMF, NMP and 1,2,4
trichlorobenzene.

catalyst deactivation; When the molar ratio of DBU/i-Bu3Al Then the copolymerization of ECH and EO with different feed
was up to 0.75, the seriously excess DBU would destroy all the composition was investigated by using i-Bu3Al/H3PO4/ DBU
active center and resulted in no polymerization ability. The (1/0.35/0.26) to examine the catalyst’s ability to control the
copolymerization activity reached the highest values at i- composition and degree of randomness of ECH/EO copolymers
Bu3Al/H3PO4/DBU=1/0.35/0.26, which suggested that the high (Table. S1, ESI†). The copolymerization of ECH and EO was
active site might be a DBU coordinated with four aluminium completed within 30 min, irrespective of monomers feed ratio.
atoms of dialkylaluminum phosphate. The compositions of ECH/EO copolymers coincided with the
co-monomer feed ratio, suggesting that both monomers were

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Fig. 1 13C-NMR spectra (100 MHz, 1,1,2,2-tetrachloroethane-d2, 25 oC) of FGE/ECH copolymers (A and B), FGE/EO copolymers (C and D),
and a FGE/ECH/EO terpolymer (E).

completely incorporated into ECH/EO copolymers. The i-Bu3Al/H3PO4/DBU (1/0.35/0.26) served as an excellent
monomer reactivity ratios rECH = 0.74 and rEO = 1.41 suggested catalyst for the random copolymerization of ECH and EO.
that the formation of ECH/EO random copolymers is preferred Based on the high activity and random copolymerization
in the present ECH/EO copolymerization (Fig. S9A, ESI†). The behavior of i-Bu3Al/H3PO4/DBU in the polymerization of ECH
microstructures of ECH/EO copolymers were characterized by and EO, we then investigated the incorporation of furfuryl
13
C-NMR analyses (Fig. S1, ESI†), the results also showed that glycidyl ether (FGE) into ECH homopolymers, EO
ECH/EO copolymers had a random monomer sequence homopolymers, and ECH/EO random copolymers. Some
distribution. All of these ECH/EO copolymers with different representative results were summarized in Table 1. At first, the
compositions showed a single glass transition temperature (Tg) homopolymerization of FGE by using i-Bu3Al/H3PO4/DBU
which varied with the ECH/EO ratios. The Tgs of ECH/EO afforded 3.0 g (100% yield) homopoly(FGE) in 45 min (Table 1,
copolymers with ECH content = 20−80 mol% fell in a range of run 9), which suggested that furan groups had no effect on the
−46 °C to −28 °C, which are between homopoly(ECH) (-22 °C) catalyst activity. Similarly with the copolymerization ECH and
and homopoly(EO) (-53 °C), and increased linearly with EO, the two-component copolymerization of FGE and ECH
increasing ECH content, in agreement with the random (Table 1, runs 10‒12) and that of FGE and EO (Table 1, runs
distribution of ECH and EO in the copolymers. These results of 13‒15) have been also achieved to afford the corresponding
ECH and EO copolymerization showed that the catalyst system random copolymers with high activity and controllable
composition (rEO/rFGE = 2.42/0.21, rECH/rFGE = 1.34/0.71, Fig. S9B

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13
and 9C, ESI†). The C-NMR spectra of FGE/ECH copolymers 100
25
with FGE content of 50 mol% and 10 mol% were shown in Fig.
1A and 1B, respectively. The similar intensities of peaks

Crosslinked density (10 mol/g)

FGE‒ECH sequences, FGE−FGE sequences, and ECH−ECH 20 80
13
Experimental

-4
sequences were observed in the C-NMR spectrum of

Gel fraction (%)

FGE/ECH copolymer with a FGE content of 50 mol% (Fig. 1A).
15
The isolated FGE units and ECH−ECH blocks were observed in
13 60
the C-NMR spectrum of FGE/ECH copolymer with a FGE
Theoretical
content of 10 mol% (Fig. 1B). These results clearly suggested 10
random microstructure of FGE/ECH copolymers prepared by i-

Polymer Chemistry Accepted Manuscript

13
Bu3Al/H3PO4/DBU. The C-NMR spectra of FGE/EO copolymers 40
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5
with FGE content of 50 mol% and 10 mol% were also shown in
Fig. 1C and 1D. Similarly, the FGE/EO copolymer with a FGE
content of 50 mol% contained FGE‒EO sequences, FGE−FGE 0 20
0 5 10 15 20
sequences, and EO−EO sequences. The FGE/EO copolymer
FGE content (mol%)
with a FGE content of 10 mol% contained FGE‒EO sequences
and EO−EO sequences. The FGE/EO copolymers prepared by i- Fig. 2 Gel fraction and cross-linking density of DA_ECO/
Bu3Al/H3PO4/DBU were also random microstructure. All of FGEm/BMI0.5m materials with different FGE contents.
these novel FGE/ECH and FGE/EO copolymers with different
increase of the feeding amount of the monomers relative to
compositions showed a single Tgs, in agreement with the
the catalyst led to the significant increase of the molecular
random distribution of two monomers in the copolymers.
weights of the terpolymer products (Table 1, run 22). The 13C-
In the presence of FGE, ECH and EO, the three-component NMR spectrum of a FGE/ECH/EO terpolymer with FGE content
copolymerization also took place rapidly irrespective of = 10 mol%, ECH content = 60 mol%, and EO content = 30 mol%
monomer feed ratio within 30 min, also giving exclusively the was shown in Fig. 1E. It was revealed that these terpolymer
corresponding FGE/ECH/EO terpolymers with 100% yield, high products containing FGE‒EO sequences, FGE‒ECH sequences,
4
molecular weights (Mn = 10.5‒25.7×10 ) and narrow molecular ECH‒EO sequences, ECH‒ECH sequences, and EO−EO
weight distributions (Mw/Mn = 1.3‒1.5). The composition of sequences are random terpolymers (Fig. S5, ESI†). All of these
FGE/ECH/EO terpolymers coincided with the co-monomer feed obtained FGE/ECH/EO terpolymers with FGE content= 5‒80
ratio, suggesting that furan groups were quantitatively mol%, ECH content = 7‒60 mol% and EO content = 7−60 mol%
incorporated into the terpolymers (Table 1, runs 16‒26). An showed a single Tgs at -31 °C to -45 °C (Table 1, runs 16‒26),
which suggested the random distribution of FGE, ECH and EO
Scheme 1 Synthesis of DA cross-linked polyepichlorohydrin units in the terpolymers. These polymerization results showed
elastomers. i-Bu3Al/H3PO4/DBU served as an excellent catalyst for the
random copolymerization and terpolymerization of FGE with
ECH and EO to afford a new family of polyepichlorohydrin
elastomers with a controllable number of pendant furan
groups.
Cross-linking and retrocross-linking of furan functionalized
polyepichlorohydrin elastomers
Based on the successful synthesis of polyepichlorohydrin
elastomers with a controllable number of pendant furan
groups, the DA cross-linking reaction of furan functionalized
polyepichlorohydrin elastomers were investigated by directly
mixing 4,4'-methylenebis(N-phenylmaleimide) (BMI) with
FGE/ECH/EO terpolymers solution after the end of
polymerization, as shown in Scheme 1. FGE/ECH/EO
terpolymers mixed with BMI (ECO/FGEm/BMI0.5m) precipitated
from polymerization solution were heated to 70 °C for 8 hours,
a red32 DA cross-linked polyepichlorohydrin elastomer
(DA_ECO/FGEm/BMI0.5m) was successfully obtained. The cross-
linking structure of DA_ECO/FGEm/BMI0.5m almost decoupled
when DA_ECO/FGEm/BMI0.5m was heated to 150 °C for 2 h (Fig.
S11, ESI†).
The gel fraction and cross-linking density of
DA_ECO/FGEm/BMI0.5m materials were shown in Fig. 2. When

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the FGE content in FGE/ECH/EO terpolymers increased from 1 15 3%FGE FGE content
mol% to 20 mol%, the gel fraction of DA cross-linked material 2.1MPa Young's modulus
was above 92%, and the cross-linking density increased from 10%FGE 5%FGE
-4 -4 12 vulcanized/carbon
1.3×10 mol/g to 15.3×10 mol/g. The cross-linking density of 25MPa 3.2MPa
polyepichlorohydrin elastomers could be easily tuned by 2.0MPa
controlling the content of FGE in FGE/ECH/EO terpolymers. In

Stress (MPa)
addition, the cross-link density determined by swelling 9 1%FGE
experiments was on the same order of magnitude as theoretic 2%FGE 0.6MPa
value calculated by NMR analysis. These results in combination 1.2MPa
with the distribution of FGE units in FGE/ECH/EO terpolymers 6

Polymer Chemistry Accepted Manuscript

suggested that there was a random and uniform distribution of
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the intermolecular crosslinks throughout polyepichlorohydrin

elastomers. 3

Thermal and mechanical properties of DA cross-linked 0%FGE

polyepichlorohydrin elastomers 0.1MPa
0
0 200 400 600 800 1000 1200
With the successful synthesis of DA cross-linked
Strain (%)
polyepichlorohydrin elastomers with different cross-linking Fig. 4 Stress-strain curves and Young’s modulus of
density, their thermal and mechanical properties were also DA_ECO/FGEm/BMI0.5m materials with different FGE contents.
determined by DSC, TGA and tensile tests. The decomposition
temperatures of DA_ECO/FGEm/BMI0.5m materials defined by 0 1 2 3 4
the onset point of 5% degradation were all over 280 °C, which
15
demonstrated that these DA cross-linked polyepichlorohydrin DA cross-linked
elastomers possessed good thermostability (Fig. S23, ESI†). Tensile stress (MPa) Vulcanized
DSC curves of DA_ECO/FGEm/BMI0.5m materials were shown in
10
Fig. 3. When the FGE content in FGE/ECH/EO terpolymers was
lower than 10 mol%, DA_ECO/FGEm/BMI0.5m materials
possessed a low Tgs, which suggested these materials shown 5
good low temperature resistance. When the FGE content in
FGE/ECH/EO terpolymers was higher than 20%, the Tg of (A)
DA_ECO/FGEm/BMI0.5m materials disappeared because of high 0
cross-linking degree.
Young's Module (MPa)

4
The tensile stress−strain curves of DA_ECO/FGEm/BMI0.5m
materials were shown in Fig. 4. First, the non-cross-linked
FGE/ECH/EO terpolymers (Table. S4 Runs 2, ESI†) and the
ECH/EO copolymers were similar in the tensile strength (about 2
1.0 MPa), the elongation at break (about 600%), and the
Young´s Modulus (about 0.1 MPa), which suggested these non-
(B)
0

1200
-39oC
Elongation (%)

0% FGE
-39oC
800
2% FGE
-39oC
Heat flow

5% FGE 400
o
-35 C (C)
10% FGE 0
0 1 2 3 4
20% FGE Crosslinking density (10-4mol/g)
Fig. 5 Tensile strength (A), Young’s modulus (B), and elongation at
Endo
50% FGE break (C) of DA_ECO/FGEm/BMI0.5m materials (blue) and vulcanized
ECO/NA22n materials (red) with a series of cross-linking density.
-50 -25 0 25 50 75 100
Temperature (oC)
cross-linked polymers were soft and weak rubbers. In sharp
Fig. 3 DSC curves of DA_ECO/FGEm/BMI0.5m materials with different
FGE contents. contrast, the cross-linked DA_ECO/FGE1/BMI0.5 material

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containing 1 mol% FGE possessed the tensile strength 7.3 MPa, 20

the elongation at break 1221%, and the Young´s Modulus 0.6
MPa, and DA_ECO/FGE1/BMI0.5 materials has become a strong
and tough material. Increasing FGE content to 3 mol% could 16 Original 2nd
increase the tensile strength of DA cross-linked Recycle
polyepichlorohydrin elastomer up to 15.0 MPa, while the 1st

Stress (MPa)
elongation at break still reached to 504%. As we all know, 12
traditional vulcanized ECH/EO copolymers with carbon black as
reinforcing agent (Vulcanized/carbon) has the tensile strength
8 3rd
12.9 MPa, the elongation at break 620%, and the Young´s

Polymer Chemistry Accepted Manuscript

Modulus 2.0 MPa. The mechanical properties of
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DA_ECO/FGE3/BMI1.5 material has exceeded traditional

4
vulcanized rubbers with carbon black as reinforcing agents, so
DA_ECO/FGE3/BMI1.5 material without reinforcing agents can
be used as structural material. Further increasing FGE content 0
from 3 mol% to 10 mol%, the Young´s Modulus of DA cross- 0 100 200 300 400 500
linked polyepichlorohydrin elastomers was increased from 2.1 Strain(%)
MPa to 25.0 MPa (Table. S4, run 9, ESI†), while the elongation Fig. 6 Stress-strain curves of thermal recyclability of
at break was decreased from 504% to 58% with the tensile DA_ECO/FGE3/BMI1.5 material.
strength shifting around 12.0 MPa. Based on the above tensile
testing, the DA cross-linked polyepichlorohydrin elastomers
showed tunable mechanical properties by changing FGE A B
content in great freedom. 98 μm
The relationships of mechanical properties versus 46 μm
crosslinking density for DA cross-linked polyepichlorohydrin 106 μm
elastomers (DA_ECO/FGEm/BMI0.5m) and traditional vulcanized
ECH/EO copolymer materials (ECO/NA22n) were also shown in C D
-4
Fig. 5. When cross-linking density was 1.2×10 mol/g, the 68 μm
tensile strength of traditional vulcanized ECH/EO copolymer
reached the highest value 7.3 MPa, then reduced extremely
with the increase of cross-linking density. Compared with two Cracked film Self-healed film
methods of cross-linking, DA cross-linked polyepichlorohydrin
elastomers possessed the tensile strength significantly higher E F
than those of the traditional vulcanized materials (Fig. 5A), not
130 μm
only that, DA cross-linked polyepichlorohydrin elastomers had
the similar excellent the elongation at break and the Young´s
Modulus as the traditional vulcanized materials (Fig. 5B and
133 μm
5C). The uniform FGE distribution in FGE/ECH/EO terpolymers
145 μm
and uniform intermolecular DA cross-linking should be
important factors of excellent mechanical properties.
Thermal recyclability and self-healing ability of DA cross-linked
Cracked film Self-healed film
polyepichlorohydrin elastomers
The DA cross-linked polyepichlorohydrin elastomers not only Fig. 7 Microscopic images for self-healing process of DA cross-linked
possessed excellent mechanical properties than traditional polyepichlorohydrin elastomers at high temperature and room
vulcanized rubber, but also possessed thermal recyclability temperature. DA_ECO/FGE3/BMI1.5 material with a scratch at room
because of reversible DA cross-linking structure. As shown in temperature (A and C), and self-healed film at 150 °C for 3h (B and
Fig. 6, the pieces of broken representative D); DA_ECO/FGE20/BMI1.5 material with a scratch at room
DA_ECO/FGE3/BMI1.5 material were reprocessed under a temperature (E), and self-healed film at room temperature for 3
pressure of 100 bar for 2 h at 155 °C, and a solid film was re- day (F).
formed again. Then the remolded film was cut into pieces, and
recycling process was repeated two times. The mechanical
2.0~2.1 MPa). The DA cross-linked polyepichlorohydrin
properties of the remolded film exhibited almost the same
elastomers not only can be used as structural material without
mechanical properties even through three generations of
reinforcing filler, but also could be repossessed like plastics
recycling (the range is for tensile strength 13.1~15.0 MPa,
materials.
elongation fluctuates 455.8%~520.7%, Young’ modulus

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Except repossess like plastics materials, the self-healing that the well-defined DA cross-linked polyepichlorohydrin
property of DA cross-linked polyepichlorohydrin elastomers elastomers with excellent recycling properties and self-healing
based on retrocross-linking process was also examined. The ability can be used as structural material without reinforcing
representative DA_ECO/FGE3/BMI1.5 material was created filler, which provide more energy-efficient, more
cracks with different widths by a scalpel, then the cracked film environmentally friendly new method for the synthesis of
was heating at 150 °C for 3 h. Microscopic images indicated cross-linked polyepichlorohydrin elastomers.
the cracks about 100 μm width greatly decreased to 46 μm
width (Fig. 7A and 7B), while smaller cracks such as 68 μm
width disappeared completely (Fig. 7C and 7D). This result Conflicts of interest
showed that DA cross-linked polyepichlorohydrin elastomers There are no conflicts to declare.

Polymer Chemistry Accepted Manuscript

can be well repaired itself with an ease retrocross-linking
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process at high temperature. The self-healing process is

finished at room temperature would be more attractive than Acknowledgements
that of at high temperature because it is friendly to heat-
This work was financially supported by National Natural
sensitive complex devices. The representative
Science Foundation of China (No. 21674016, 21429201,
DA_ECO/FGE20/BMI1.5 material that has rich unreacted furan
21034001, U1508204).
groups was chosen to achieve self-heal based on the further
cross-linking of uncross-linked furan groups at room
33
temperature. The cracks in the DA_ECO/FGE20/BMI1.5 Notes and references
material was filled with chloroform solution of BMI, then the
1 R. Klingender, In Handbook of Specialty Elastomers, 1st ed.;
film was placed at room temperature for 3 days to finish DA
CRC Press: 2008. p245-288.
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Polymer Chemistry Accepted Manuscript

28 A red color for the crosslinked FGE-containing material
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mainly came from DA cross-linked structure. The ECO/FGEm,

BMI and ECO/FGEm/BMI0.5m were colorless, yellow and
yellow respectively and there were no color changes when
o
FGE, BMI was heat separately to 70 C under N2 atmosphere.
o
Only when the mixture of FGE and BMI was heated to 70 C,
a time dependent color changes from yellow to red can be
observed during heating procedure and a red DA product
was obtained after heating procedure.
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