Introducing the Tishchenko reaction into sustainable polymer chemistry

Article abstract of DOI:10.1039/c9gc03926k

Taking advantage of the structural characteristics of lignin-derived phenolic compounds, a combination of the Williamson and Tishchenko reactions produced a series of new α,ω-diene functionalized carboxylic ester monomers from both petrochemical and renewable resources, which were applicable in subsequent thiol-ene click and acyclic diene metathesis (ADMET) polymerizations, providing a series of poly(thioether esters) and unsaturated aromatic-aliphatic polyesters with high molecular weights.

Full text of DOI:10.1039/c9gc03926k

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DOI: 10.1039/C9GC03926K
Table of Content
The combination of the Williamson and Tishchenko reactions produced series of new
α,ω-diene functionalized carboxylic ester monomers from both petrochemical and
renewable resources, which were applicable in subsequent thiol-ene click and acyclic
diene metathesis (ADMET) polymerizations, providing series of poly(thioether esters)
and unsaturated aromatic-aliphatic polyesters with high molecular weights.

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DOI: 10.1039/C9GC03926K
Introducing the Tishchenko Reaction into Sustainable Polymer
Chemistry
Tianhua Ren,a Qin Chen,*a Changbo zhao,a Qiang Zheng,b Haibo Xie*a and Michael Northc
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Taking advantage of the structural characteristics of lignin-derived furandicarboxylate) (PEF) with superior gas barrier properties to
phenolic compounds, a combination of the Williamson and traditional polyethylene terephthalate.9, 10 Therefore, major
Tishchenko reactions produced series of new α,ω-diene challenges remain in using sustainable resources for polyester
functionalized carboxylic ester monomers from both petrochemical production; especially the design and synthesis of monomers
and renewable resources, which were applicable in subsequent using environmentally friendly methods and their
thiol-ene click and acyclic diene metathesis (ADMET) polymerization under mild reaction conditions.
polymerizations, providing series of poly(thioether esters) and
Lignin is the main component in lignocellulosic biomass and
unsaturated aromatic-aliphatic polyesters with high molecular is the most abundant renewable aromatic chemical source on
weights.
Earth. The catalytic conversion of lignin can produce a library of
(A) Polycondensation
Polymeric materials play an important role in our daily life and
in industry, and are mostly produced from petroleum-based
monomers. However, there are increasing environmental
concerns relating to both the feedstocks used to produce
polymers and their end-of-life treatment options.1 It is well
recognized that the sustainable development of polymer
science and any extension of the applications of polymers are
heavily reliant upon the design of renewable monomers and the
development of new polymerization strategies.2-4
O
C
O
C
HX
HO
X
R
X
O
R
O
C
O
C
O
C
O
C
R'
HX
R'
+
R
O
O
HO
OH
R
X
X = OH, halogen, alkoxy
(B) Ring-opening polymerization
O
O
Polyesters are an important class of polymers which are
ubiquitous in daily life and have many industrial applications.
Most commercially available polyesters are produced by
polycondensations involving transesterification or by ring-
opening polymerization as shown in Scheme 1A,B. Usually,
harsh conditions or complex procedures such as use of high
temperature, vacuum, multiple polymerization steps and toxic
metal catalysts are required in these synthetic protocols,
particularly in the synthesis of aromatic polyesters.5
The biorefinery concept provides a large library of bio-derived
chemicals, but most of these have to be upgraded into
monomers with appropriate functionalities through
environmentally unfriendly or complex protocols.6-8 For
example, the preparation of 5-hydroxymethyl-fufural (HMF)
from carbohydrates has been widely studied. However, HMF
has to be oxidized to 2,5-furandicarboxylic acid (FDCA) before
being used as a monomer to prepare poly(ethylene-2,5-
initiator
O
n
O
n
(C) This work: Ester-containing monomers via the Tishchenko reaction
O
O
ADMET
O
O
n
n
R
R
n
O
O
O
R
Tishchenko
reaction
O
R
O
HO
R
R
O
n
O
n
a. Department of Polymeric Materials & Engineering, College of Materials &
Metallurgy, Guizhou University, West Campus, Huaxi District, Guiyang 550025, P.
R. China.
Thiol-ene polymerization
R'
O
O
E-mail: qchen6@gzu.edu.cn (Qin Chen), hbxie@gzu.edu.cn (Haibo Xie); Tel:
b. Department of Polymer Science and Engineering, Zhejiang University, Hangzhou
310027, China
O
O
S
S
n
n
R
R
c. Green Chemistry Centre of Excellence, Department of Chemistry, University of
York, Heslington, York, YO10 5DD, UK
Scheme 1 Preparation of polyesters.
Electronic Supplementary Information (ESI) available. See DOI: 10.1039/x0xx00000x
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O
O
O
DOI: 10.1039/C9GC03926K
R2
R2
R2
R2
H
H
O
K2CO3/KI
NaH
Br
n
110 oC
HO
O
n
O
n
O
n
EtOH, 80 oC,
reflux
R1
1
R1
2
R1
R1
3
Yields
96%
95%
92%
94%
95%
91%
91%
90%
Yields
2a: R1 = H, R2 = OCH3, n = 1
2b: R1 = H, R2 = OCH3, n = 4
2c: R1 = H, R2 = OCH3, n = 8
2d: R1 = H, R2= H, n = 1
2e: R1 = OCH3, R2 = OCH3, n = 1
2f: R1 = H, R2 = F, n = 1
3a:94%
3b:89%
3c:85%
3d:86%
3e:89%
3f: 92%
3g:94%
3h:84%
2g: R1 = H, R2 = Br, n = 1
2h: R1 = H, R2 = CH3, n = 1
Scheme 2 Synthesis route to ,-diene monomers.
aromatic compounds, in which vanillin usually dominates.11-13 dialdehyde only produced polyester oligomers.38-43 Herein, by
Therefore, vanillin is regarded as a promising bio-derived utilizing the structural characteristics of lignin-derived phenolic
aromatic building block for polymer synthesis through chemical aldehydes, we introduce a toolbox of combining the Williamson
upgrading by taking advantage of its phenol and aldehyde and Tishchenko reactions for the preparation of monomers
groups. For example, an acetyl dihydroferulic acid was prepared ready for subsequent thiol-ene click and ADMET
by reaction of vanillin with acetic anhydride, which could be polymerizations (Scheme 1C).
polymerized to poly(dihydroferulic acid) with similar thermal
Vanillin contains phenol and aldehyde groups. As expected,
properties to PET.14 More recently, a fully bio-based ketone the direct Tishchenko reaction of vanillin does not occur using
containing aromatic-aliphatic monomer was prepared by the various catalysts including potassium tert-butoxide and the
condensation reaction of vanillin and levulinic acid. Its hydrides of calcium, sodium and potassium due to the weak
subsequent polycondensation resulted in formation of novel, acidic phenol group (Scheme S1).33, 34, 36 However, Williamson
fully bio-based, poly(keto-esters).15 Other aromatic polyesters, allylation
of
vanillin
produced
4-(allyloxy)-3-
such as polyalkylenehydroxybenzoates,16 polyacetal ethers,17 methoxybenzaldehyde 2a in 96% yield (Scheme S1, Fig. S1-2).
polyethylene ferulate18 and divanillin-derived polyesters19,
To our delight, compound 2a underwent a Tishchenko reaction
20
also have been prepared through traditional polymerization under solvent-free conditions with sodium hydride as the
protocols. optimal catalyst (Table S1), producing 4-(allyloxy)-3-
The development of mild, new polymerization protocols is methoxybenzyl 4-(allyloxy)-3-methoxybenzoate 3a in 94% yield
also important for the development of sustainable polymer (Fig. S1-2). Monomer 3a is characterized by the presence of
chemistry. For example, the introduction of multicomponent,21, ester and ,-diene functional groups, which provide the
22
thiol-ene click23-26 and acyclic diene metathesis (ADMET)27 opportunity to prepare polyesters via polymerization of the
protocols into polymer chemistry has significantly promoted ,-dienes under appropriate polymerization protocols such as
the development of polymer chemistry. Several studies have metal free thiol-ene click chemistry and acyclic diene
demonstrated that these polymerization protocols are metathesis (ADMET). These have been widely investigated and
applicable to vanillin-derived monomers, giving series of shown to be efficient and green polymerization protocols for
polymers with high molecular weights and satisfactory thermal monomers containing ,-dienes.44-49
properties.28-31 Hence, there is now the potential to develop a
The metal-free thiol-ene click polymerization of 3a with 1,2-
sustainable polymers industry in which the vast majority of dithioethane 4a (Scheme 3) produced a poly(thioether ester)
polymers are produced using bio-based monomers which are P3a4a with a Mw of 50.0 KDa and a polydispersity index (PDI) of
efficiently synthesized and which undergo facile polymerization. 1.4 in 96% yield. The ADMET polymerization of 3a produced an
The Tishchenko reaction is a 100% atom economical process unsaturated aromatic-aliphatic polyester P3a with a Mw of 43.7
in which aldehydes undergo disproportionation or dimerization KDa and PDI of 1.1 in 97% yield when the second generation
to give the corresponding carboxylic esters. It has been known Hoveyda-Grubbs catalyst (HG-II) was used. The satisfactory
for more than a hundred years and is catalyzed by N- molecular weight and PDI values of these polyesters
heterocyclic carbenes, metal hydrides and alkali metal tert- demonstrated the feasibility of our strategy. To also
butoxides.32-37 Although the Tishchenko reaction has been demonstrate the scope of this methodology and to tune the
widely applied in fine chemicals synthesis, it is seldom applied properties of the prepared polyesters, series of ester monomers
in polyester chemistry, as the direct polymerization of a with ,-dienes containing different methylene spacers were
2 | J. Name., 2012, 00, 1-3
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O
O
View Article Online
R2
R2
R2
O
R
DOI:210.1039/C9GC03926K
n
O
O
O
O
R2
H2O2
O
*
S
DMPA
*
O
n
O
S
S
m
*
O
S
*
n
R1
O
R1
4a
R1
R1
PO3a4a
PO3f4a
R1
O
SH
SH
THF,
UV
PO3d4a
PO3g4a
PO3e4a
PO3h4a
: 91%;
: 87%;
: 89%;
: 91%;
: 93%
: 89%
4b
4c
4d
O +
m
O
3a
P3a4a P3a4b P3a4c P3a4d
P3b4a P3b4b P3b4c P3b4d
P3c4a P3c4b P3c4c P3c4d
P3d4a
P3e4a
P3f4a
P3g4a
P3h4a
4a-d
3b
3c
3d
3e
3f
3g
3h
3a
3b
3c
3d
3e
3f
3g
3h
: R1 = H, R2 = OCH3, n = 1
: R1 = H, R2 = OCH3, n = 4
: R1 = H, R2 = OCH3, n = 8
: R1 = H, R2= H, n = 1
: R1 = OCH3, R2 = OCH3, n = 1
: R1 = H, R2 = F, n = 1
R1
4a
4b
4c
4d
: m=2
: m=3
: m=6
: m=10
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
O
R2
n
: R1 = H, R2 = Br, n = 1
: R1 = H, R2 = CH3, n = 1
3a-h
Scheme 3 Novel aromatic polyesters obtained by thiol-ene polymerization and subsequent oxidation.
Table 1. Thermal properties and molecular weights of poly(thioether esters) P3a-h4a-d and poly(sulfone esters) PO3a,d-h4a.
Poly(thioether ester)s P3a-h4a-d
Poly(sulfone ester)s PO3a,d-h4a
b
c
a
a
b
c
Sample
Mna
(KDa)
36.1
Mwa
(KDa)
50.0
PDI
Yield
(%)
96
93
97
93
93
89
89
93
98
88
92
94
93
91
90
90
93
T5%
Tg
Sample
Mn
Mw
PDI
Yield
(%)
T5%
(%)
Tg
(oC)
(oC)
29.3
18.2
11.0
-0.2
7.6
(KDa) (KDa)
(oC)
P3a4a
P3a4b
P3a4c
P3a4d
P3d4a
P3e4a
P3f4a
P3g4a
P3h4a
P3b4a
P3b4b
P3b4c
P3b4d
P4c4a
P4c4b
P4c4c
P4c4d
1.4
1.3
1.1
283.0
295.6
295.3
316.0
276.0
259.5
288.5
277.4
297.2
304.3
288.7
312.7
323.9
300.3
307.0
306.9
313.1
PO3a4a
39.1
47.4
1.21
90.9
173.06
78.0
38.0
48.9
46.4
50.0
d
d
d
-
-
-
38.6
20.2
43.9
41.9
26.7
35.2
33.5
43.2
32.1
44.5
46.8
23.0
50.8
47.4
33.0
45.7
48.0
48.3
51.9
51.0
1.2
1.1
1.2
1.1
1.2
1.3
1.4
1.1
1.6
1.2
PO3d4a
PO3e4a
PO3f4a
PO3g4a
PO3h4a
36.5
26.4
45.5
36.8
29.6
42.4
29.6
54.1
40.1
39.3
1.2
1.1
1.2
1.1
1.3
89
93
87
91
89
252.8
245.0
212.3
269.1
237.1
53.3
46.6
8.1
e
1.5
-
31.5
19.7
10.5
2.9
75.4
60.2
-8.4
-8.7
-6.2
-14.3
-18.5
-17.5
d
d
d
-
-
-
d
d
d
-
-
-
d
d
d
-
-
-
aDetermined by GPC in DMF (0.01 M LiBr) as the solvent against PS standards. bPolymer degradation temperature obtained at 5% mass loss by TGA. cDetermined by
DSC. dInsoluble in DMF or THF at room temperature. eNo Tg was detected by DSC.
prepared using both lignin-derived phenolic aldehydes change significantly after the oxidation. The post-
(syringaldehyde and para-hydroxybenzaldehyde) and polymerization oxidation of thioether-containing polymers into
petrochemical-based phenolic aldehydes (meta-methyl-para- the corresponding sulfoxide or sulfone derivatives can increase
hydroxybenzaldehyde,
meta-bromo-
para-hydroxy- the polarity of the polymers, thus extending their applications
benzaldehyde and meta-fluoro-para-hydroxybenzaldehyde). into fields including organic light emitting diodes, organic
Esters 3a-h were prepared in good yields (Scheme 2) and solvent nanofillers, proton exchange resins, and gas separation
underwent thiol-ene click polymerization with dithiols 4a-d to membranes.53-57
produce poly(thioether esters) P3a-h4a-d in good yields ranging
The thermal properties of poly(thioether esters) P3a-h4a-d
from 88-97% (Scheme 3). Poly(thioether esters) P3a-h4a-d have and poly(sulfone esters) PO3a,d-h4a were evaluated by TGA
Mw ranging from 23.0 to 50.8 KDa and narrow PDIs of 1.1 to 1.6. and DSC, and the results are summarized in Table 1. The TGA
To demonstrate the possibility of post-polymerization traces of the polymers demonstrated that both the
modifications, poly(thioether ester)s P3a,d-h4a were poly(thioether esters) and poly(sulfone esters) show a one-step
quantitatively oxidized to corresponding poly(sulfone ester)s degradation pattern, indicating that the presence of thioether
PO3a,d-h4a using hydrogen peroxide as a green oxidant under and sulfone groups in the polymer chain did not alter the
mild conditions.50-52 The molecular weight and PDI did not thermal stability of the ester linkage (Figure S5-6). The
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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COMMUNICATION
poly(thioether esters) exhibited a 5% weight loss (T5%) in the and the substituent group could have a great effect on the Tg of
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range of 259-324 oC (Fig. S7). Although post-polymerization the polymers. For example, polymers P3d4a and P3e4a with
DOI: 10.1039/C9GC03926K
o
oxidation of the poly(thioether esters) did not affect the symmetric aromatic rings have similar and lower Tg’s (8 C).
molecular weight and PDI of the polymers, the T5% slightly Other than meta-fluoro substitution, meso-substitution
o
decreased to 173-269 C. All the polymers except for PO3f4a resulted in higher Tg than P3d4a, because the introduction of
possess an obvious glass transition temperature (Tg). P3c4d and large substituent groups (e.g. -OCH3, -CH3, -Br) onto the
P3h4a show an obvious cold crystallization peak and melting aromatic ring decreases the symmetry and increase the free
peak from the second heating run (at 98.7 oC and 113.6 oC; and volume of the polymers. Although the symmetry of the polymer
o
o
1.0 C and 16.1 C respectively) (Figures S5 and S6). PO3a4a also decreased slightly by the introduction of small fluoro
shows exothermic and melting peaks from the second heating substituent, the strong electronegativity of fluorine can
run at 136.2 oC, and 172.2 oC respectively (Figure S14). For the decrease π-π interaction, thus facilitating the mobility of the
other polymers, no crystallinity or melting point was observed, macromolecular chains and resulting in a lower Tg of 1.5 oC.
and their amorphous structures are also confirmed by WXRD
To further demonstrate the versatility of polymer synthesis
(Figures S10-13, and S15). As expected, the increase in number facilitated by the toolbox, monomers 3a-h were submitted to
of methylene spacers in the dithiol and aliphatic ,-diene ADMET polymerization to prepare polyesters catalyzed HG-II
chain increases the flexibility of the aliphatic chain in the (Scheme 4). Gratifyingly, a series of unsaturated polyesters
polymers and lowers the Tg of the poly(thioether esters) (Figure (P3a-h) were obtained in high yields (91-98%) with Mw ranging
S8). Oxidation of the thioethers into sulfones significantly from 26.2 KDa to 52.4 KDa and PDI ranging from 1.1 to 1.5
o
increases the Tg of the polymers from 1.5-31.5 C to 46.6-78.0 (Table 2). Furthermore, a series of saturated polyesters (PH3a-
oC, which is comparable or higher than those of PLA and PET, h) can also be prepared by post-polymerization hydrogenation
indicating their potential applications as thermoplastics. The of P3a-h, and the molecular weight and PDI of the polyesters
enhanced Tg can be ascribed to the synergetic effect of the did not change, indicating the chemical stability of the
1
regular tetrahedral structure of the sulfone moiety and the polyesters during the hydrogenation. H NMR spectra of P3a
increased polarity of the polymers. The regular tetrahedral and PH3a allowed the success of the hydrogenation to be
structure of the sulfone moiety may restrict the C-S bond confirmed by the complete disappearance of the peaks
rotation, thus decreasing the mobility of the macromolecular assigned to the internal double bond at 6.1 ppm, and the
chains and leading to higher Tg, and the enhanced polarity will appearance of new peaks at 2.1 ppm assigned to the newly
result in stronger dipole-dipole interactions, thus leading to formed methylene groups
higher Tg. It was found that the symmetry of the aromatic ring
n
O
R2
O
O
R1
R2
R2
O
R2
R2
O
HG-II cat.
p-benzoquinone
p-toluenesulfonyl hydrazide
triethylamine, pyridine
O
O
*
*
O
*
*
O
n
O
n
CH2Cl2, reflux
n
100 o
C
O
n
R1
R1
R1
R1
PH3a-h
P3a-h
R1
O
R2
n
3a-h
Scheme 4 Preparation of unsaturated polyesters P3a-h via ADMET polymerization and their hydrogenation to polyesters PH3a-h.
Table 2 GPC and thermal properties of polyesters P3a-h and PH3a-h.
ADMET polymers P3a-h
Hydrogenated ADMET polymers PH3a-h
a
a
b
c
a
a
b
c
Sample
Mn
Mw
(KDa)
43.7
49.3
51.9
46.2
26.2
52.4
45.7
43.8
PDI
Yield
%
T5%
Tg
Sample
Mn
Mw
PDI
Yield
%
T5%
Tg
(KDa)
38.6
42.1
44.7
30.3
24.2
44.3
29.9
32.8
(oC)
(oC)
59.1
23.4
0.8
(KDa)
35.3
(KDa)
48.0
(oC)
(oC)
57.8
23.4
7.2
P3a
P3b
P3c
P3d
P3e
P3f
1.13
1.2
1.2
1.5
1.1
1.2
1.5
1.3
97
225.6
268.0
348.6
262.7
242.9
259.1
236.4
267.4
PH3a
PH3b
PH3c
PH3d
PH3e
PH3f
PH3g
PH3h
1.4
1.1
90
270.0
330.1
344.2
288.4
303.5
323.8
293.1
299.7
95
49.2
53.5
88
d
d
d
96
-
-
-
94
98
57.5
47.4
15.3
49.2
23.2
29.4
22.0
46.8
35.4
44.5
24.0
52.7
45.9
1.5
1.1
1.1
1.3
93
20.6
46.3
14.8
44.8
19.5
96
92
96
90
P3g
P3h
91
86
d
d
d
92
-
-
-
88
4 | J. Name., 2012, 00, 1-3
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a
b
c
Determined by GPC in DMF (0.01 M LiBr) as the eluent against PS standards. Polymer degradation temperature obtained at 5 % mass loss by TGA.
d
Determined by DSC. insoluble in DMF or THF at room temperature.
View Article Online
DOI: 10.1039/C9GC03926K
(Figure S16).
the use of other phenolic aldehydes and dithiols as well as
The thermal properties of polymers P3a-h and PH3a-h were different polymerization strategies.
evaluated by TGA and DSC and the results indicate that the
unsaturated polyesters are thermally stable with 5% mass loss
occurring between 225 and 348 oC (Figure S18-21, S24-27). The
introduction of substituents at the meso-position in the
aromatic ring results in decreased thermal stability. Conversely,
an increase in the number of methylene spacer units results in
increased thermal stability (Table 2). Although diffractive peaks
were detected in the cases of P3d-f, and P3h by WXRD analysis,
indicating the crystallinity of these polymers, no melting points
were observed in their DSC curves (Figure S20-23). As expected,
the corresponding T5% of PH3a-h are higher than those of P3a-
h due to the hydrogenation of the unsaturated C=C double bond
to a C-C single bond. All the unsaturated polyesters (P3a-h)
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was supported by the National Science Foundation
of China (21704019, 21644012); Science and Technology
Department of Guizhou Province (Grant No. Natural Science Key
Fund [2016]1402; [2017]5788), (Grant No. Platform & Talents
[2016]5652; [2019]5607); Excellent Scientific Innovative Talent
Program from Education Department of Guizhou Province (Grant
No. KY [2015]479).
o
show a prominent Tg at 0.8 to 59.1 C, and the hydrogenation
usually slightly decreased the Tg of PH3a-h to between 7.2 and
o
57.8 C. This can be explained by the hydrogenation of C=C
References
bonds (sp2) with restricted rotation ability to C-C bonds (sp3)
with a free rotation ability, as the rotation of the methylene
groups can allow the polymer chains to bend or curl up in
various ways, thus leading to a lower Tg. A similar effect of the
substituent groups on the aromatic ring on the Tg of polyesters
(P3a-h and PH3a-h) to that discussed above for poly(thioether
esters) P3a-h4a-d was observed. Similarly, no melting points
were observed in the DSC curves of PH3a,d,f,h, although
diffractive peaks were detected in the WXRD patterns,
indicating the crystallinity of these polymers (Figure S26-29).
E-factors were calculated for novel polyesters P3a4a, P3a4b,
P3a4c, P3a4d, PO3a4a, P3a, P3b, P3c and PH3a to obtain an
overview of the environmental impact of our approach to
polyester synthesis. The E-factors were determined to be 3.3,
3.4, 2.9, 2.8, 3.9, 6.1, 5.7, 5.1 and 10.8 respectively (Tables S2-
19). These values are at the level of industrial processes for the
manufacture of bulk and fine chemicals.58-60 The polyesters
obtained from thiol-ene polymerization showed lower E-factors
than those obtained from ADMET polymerization indicating the
lower environmental impact of the thiol-ene polymerization.
In summary, by taking advantage of the structural
characteristics of lignin derived aromatic aldehydes, a toolbox
of combining the Williamson and Tishchenko reactions has been
demonstrated to be a highly efficient and sustainable strategy
to synthesize ,-diene aromatic carboxylic ester monomers
with high structural diversity. The monomers are suitable for
thiol-ene click and ADMET polymerization to obtain new
libraries of poly(thioether esters) and unsaturated polyesters
with high molecular weights and satisfactory thermal properties
as well as functional diversity, which open interesting
possibilities for future applications. Furthermore, the
functionality of the polyesters provides active sites for post-
polymerization modification to produce a variety of new
polymers with desirable properties and functionality. The
applicability of both lignin-based and petroleum-based para-
hydroxy benzaldehyde derivatives demonstrated the potential
of the strategy for sustainable polymer synthesis by enabling
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