A two-step efficient preparation of a renewable dicarboxylic acid monomer 5,5′-[oxybis(methylene)]bis[2-furancarboxylic acid] from D-fructose and its application in polyester synthesis

Article abstract of DOI:10.1039/c6gc03314h

D-Fructose was converted to the dialdehyde 5,5′-[oxybis(methylene)]bis[2-furaldehyde] by heating at 110°C in DMSO with the Dowex 50 W X8 solid acid catalyst in 76% yield without the isolation of the intermediate 5-hydroxymethylfurfural. This dialdehyde was then converted to the dicarboxylic acid monomer, 5,5′-[oxybis(methylene)]bis[2-furancarboxylic acid], using oxygen (1 atm.) and 5% Pt/C catalyst in 1.5 M aqueous NaOH at room temperature in 98% yield. The new dicarboxylic acid monomer can be considered as a renewable resource based alternative to terephthalic acid as demonstrated by the preparation of polyesters with 1,2-ethanediol and 1,4-butanediol in 87-92% yield.

Full text of DOI:10.1039/c6gc03314h

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A two step efficient preparation of a renewable dicarboxylic acid
monomer 5,5'-[oxybis(methylene)]bis[2-furancarboxylic acid] from
D-fructose and application in polyester synthesis
Received 00th January 20xx,
Accepted 00th January 20xx
Ananda S. Amarasekara*, Loc Nguyen, Nnaemeka C. Okorie and Saad Jamal
DOI: 10.1039/x0xx00000x
www.rsc.org/
D-Fructose was converted to the dialdehyde 5, 5'-[oxybis(methylene)]bis[2-furaldehyde] by heating at 110 °C in DMSO with Dowex 50W X8
solid acid catalyst in 76% yield without isolation of the intermediate 5-hydroxymethylfurfural. This dialdehyde was then converted to the
dicarboxylic acid monomer, 5,5'-[oxybis(methylene)]bis[2-furancarboxylic acid] using oxygen (1 atm.) and 5% Pt/C catalyst in 1.5M aqueous
NaOH at room temperature in 98% yield. The new dicarboxylic acid monomer can be considered as a renewable resources based
alternative to terephthalic acid as demonstrated by the preparation of the polyesters with 1,2-ethanediol and 1,4-butanediol in 87-92 %
yield.
22, 23
resins with urea as well as Schiff base polymers with diamines
However, the diacid is probably the most important derivative of
The growing interest in renewable resources based feedstock HMF and in recent years FDCA has been used as a monomer in the
chemicals and polymeric materials has promoted the studies on a preparation of polyesters using range of polymerization
.
1
. Introduction
a
1
number of biomass derived compounds such as triglycerides , lactic techniques including the use of dicarboxylic acid dichloride - diol
2
, 3
4, 5, 6
7
8, 9
24, 25
acid
, levulinic acid
, succinic acid , 1,3-propanediol
, 5- method, trans-esterification, and interfacial poly condensation
, 2,5-furandicarboxylic acid or The most widely studied diol is 1,2-ethanediol
.
1
3, 24, 26
1
0, 11, 12
hydroxymethylfurfural (HMF)
its derivatives
, but
1
3, 14
15, 16
, and vanillin
. Biomass derived furans, polyesters have been prepared using other diols like 1,3-
24 26 26
furfural (FF) and 5-hydroxymethylfurfural constitute an important propanediol , 1,4-butanediol , 1,6-hexanediol , 1,8-octanediol
2
6
,
24
sub-group in these feedstock compounds as most of the abundant
C5, C6 monosaccharides can be dehydrated to these furan benzene
derivatives under relatively mild acidic conditions using inexpensive glycerol
bis(2,5-hydroxymethyl)-furan
,
bis-(1,4-hydroxymethyl)
2
4
24
27
27
,
8
hydroquinone
,
D-isosorbide
, D-isoidide
and
2
as well. In addition, FDCA is listed in a 2004 US
acid catalysts. The large scale commercial preparation of FF is a well Department of Energy National Renewable Energy Laboratory
established process since 1929 due to a relatively easy preparation (NREL) report as one of the twelve building blocks that can be
involving a mineral acid catalyzed aqueous phase process and subsequently converted to a variety of high-value bio-based
1
7
29
distillation . Furthermore, furfural is known as one of the earliest chemicals and polymeric materials
renewable monomers; Durite Plastics Inc. started the manufacture
.
1
8
of phenol−furfural resins and plasꢀc materials in the 1930's . In
contrast, HMF production, is much more problematic due to further
transformation to levulinic acid and formic acid via a rehydration
reaction as well as polymerizations to humins . Albeit the
problems in preparation, isolation and storage of this bifunctional
furan, HMF has received considerable attention as its oxidation
products, 2,5-furandicarboxaldehyde and 2,5-furandicarboxylic acid
HOH C
2
O
OH
a
O
O
O
19
HO
O
O
O
CH OH
H
H
2
1
OH
D-Fructose
b
(
FDCA) are attractive monomers for the synthesis of next
2
0, 21
generation renewable polymeric materials
. The dialdehyde,
O
O
O
OH
2
,5-furandicarboxaldehyde has been used in the preparation of
O
OH
2
_
__________________________________________________
Figure 1. Synthesis of 5,5'-[oxybis(methylene)]bis[2-furancarboxylic
Department of Chemistry, Prairie View A&M University,
Prairie View, Texas 77446, USA
acid] (OBFC, 2) via 5,5'-[oxybis(methylene)]bis[2-furaldehyde]
(
OBFA, 1) from D-fructose. a = Dowex 50W X8 10% (w/w), DMSO,
1
4
10 °C, 24 h, b = 5% Pt/C, O2 , 1 atm., 1.5M aqueous NaOH, 23 °C,
8 h.
E-mail: asamarasekara@pvamu.edu Tel: +1 936 261 3107;
Fax: +1 936 261 3117
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Furthermore, this aromatic diacid has been considered as a concentrated under reduced pressure to give the crude product,
potential replacement and the renewable resources based which was recrystallized from 50% aqueous ethanol to give 5,5'-
equivalent of terephthalic acid, which is a monomer in polyethylene [oxybis(methylene)]bis[2-furaldehyde] as tan crystals, 8.89 g, 76 %
2
9
36
terephthalate (PET) plastics . The market for terephthalic acid yield. M.pt. 112-114 °C, Lit. M. pt. 113-115 °C
.
exceeds 50,000 ktons/year, demonstrating the large potential for IR (ATR) 730, 828, 947, 1029, 1193, 1268, 1351, 1402, 1447, 1518,
-
1
FDCA for the preparation of polyethylene furanoate (PEF) as a 1663, 2845 cm
replacement for PET . In theory the use of FDCA as a substitute for
3
0
1
H NMR (CDCl ) δ 4.63 (4H, s, 2X CH -O), 6.57(2H, d, J = 3.6 Hz, Fu -
3
2
13
terephthalic acid together with biomass based diols allows the 4,4' ), 7.21 (2H, d, J = 3.6 Hz, Fu - 3,3'), 9.62 (2H, 2X CHO), C NMR
preparation of completely renewable polyesters, leading to a (CDCl ) δ 64.8, 112.1, 122.2, 153.0, 157.4, 177.9.
3
30
significant reduction of greenhouse gas emissions . In addition,
potential applications of FDCA include its use in the manufacture of 2.3. Synthesis of 5,5'-[oxybis(methylene)]bis[2-furancarboxylic acid]
31, 32 33, 34, 35
,
polyureas, polyamides and polyester-polyols as well
.
A mixture of 5, 5'-[oxybis(methylene)]bis[2-furaldehyde] (234 mg,
.00 mmol) and platinum 5 wt. % on activated carbon (4.7 mg) in 50
1
In our efforts to produce new biomass derived monomers via mL of 1.5 M aqueous sodium hydroxide was stirred under 1.0
efficient catalytic routes, we have recently found that it is possible atmosphere of oxygen for 48 h using an oxygen filled balloon. Then
to prepare 5,5'-[oxybis(methylene)]bis[2-furancarboxylic acid] the reaction mixture was centrifuged at 1700 g for 10 min., the
(
OBFC, 2) from D-fructose using a two step process as shown in recovered catalyst was washed with water (2x5 mL), and the
figure 1, and this difuranic-diacid can be considered as a higher combined aqueous layer was carefully acidified to pH = 2.0 using
molecular weight analog and an alternative to dicarboxylic acid conc. HCl and the solution was left in a refrigerator overnight to
monomer FDCA. In this publication we report an efficient scalable give 5,5'-[oxybis(methylene)]bis[2-furancarboxylic acid] as pale
catalytic approach for the preparation of this versatile bio-based yellow crystals. 260 mg, 98 % yield. M.pt. 207-209 °C, Lit. M. pt.
3
7
diacid monomer and demonstrate the solution polymerization of 209-210 °C
.
the acid dichloride with diols to produce polyesters.
IR (ATR) 761, 891, 951, 1029, 1059, 1159, 1208, 1283, 1342, 1424,
-1
1
525, 1674, 3128 cm
1
H NMR (DMSO-d
6
2
) δ 3.38 (2H, bs, 2XCOOH), 4.51 (4H, s, 2X-CH O ),
1
3
6
.61 (2H, d, J = 3.6 Hz, C-4,4'), 7.15 (2H, d, J = 3.6 Hz, C-3,3').
C
NMR (DMSO-d ) δ 63.8, 112.2, 118.8, 145.3, 155.5, 159.6
6
2
. Experimental
2.1. Materials and Instrumentation
D-Fructose (>99%), Dowex 50W X8 (hydrogen form, 50-100 mesh),
platinum 5 wt. % on activated carbon (Aldrich product number
2
.4. General procedure for the synthesis of polyester-ethers 3a,b
205931), CuO (> 99%), AgO (> 99%), thionyl chloride, pyridine, A mixture of 5,5'-[oxybis(methylene)]bis[2-furancarboxylic acid] (2)
1
,1,2,2-tetrachloroethane (TCE) and 1,4-butanediol (> 99%) were
(
266 mg, 1.0 mmol), thionyl chloride (0.50 mL, 6.9 mmol) and 25ꢀL
1
purchased from Aldrich Chemical Co. H NMR spectra were
recorded in CDCl , DMSO-d or CF CO D on a Varian Mercury plus
spectrometer operating at 400MHz and chemical shifts are given in
of DMF were prepared in a round bottom flask connected to an air
condenser and heated in an oil bath at 80 °C, for 4 h. Then the
mixture was cooled to room temperature and excess SOCl and
3
6
3
2
2
1
3
ppm downfield from TMS (δ = 0.00). C NMR spectra in CDCl3, DMF were removed at room temperature under high vacuum
DMSO-d or CF CO D were recorded on the same spectrometer connected to a liquid nitrogen cooled trap. The acid chloride
operating at 100MHz; chemical shifts were measured relative to formed was dissolved in 0.2 mL of TCE and cooled to 0 °C. Then a
CDCl3, DMSO-d or CF CO D and converted to δ(TMS) using δ(CDCl
mixture of diol (1.0 mmol), 0.2 mL of TCE and 0.3 mL of pyridine
77.00, δ(DMSO) = 39.51 and δ(CF -) = 116.60 ppm. Attenuated was added and stirred under a nitrogen atmosphere, warming to
total reflection infrared (ATR-IR) spectra were recorded in the 650– room temperature in about an hour. The reaction mixture was
6
3
2
6
3
2
3
)
=
3
−
1
4
000 cm range on a Smiths IdentifyIR spectrometer with a further stirred at room temperature for 6-48 h and a gradual
diamond ATR (Danbury, CT, USA). Thermogravimetric analysis (TGA) increase in viscosity was observed due to polymerization. At the
was carried out in air using TA instruments TGA 2050 system and end of the reaction period 20 mL of methanol was added and
platinum crucibles. The TG curves were recorded in the 50-600 °C allowed to stand at room temperature for 1h to precipitate the
temperature range using a scanning rate of 10 °C/min. Elemental polymer, which was separated by decantation. The polymer
analysis was performed at QTI laboratories, New Jersey, USA.
product was repeatedly washed with methanol (3x5mL) dried under
vacuum to give polyester-ethers 3a,b.
2.2. Preparation of 5,5'-[oxybis(methylene)]bis[2-furaldehyde] (1)
from D(-)-fructose
3a, 254 mg, 87% yield.
Anal. Calc. for C14
12 7
H O : C, 57.54; H, 4.14. Found: C, 57.75; H, 4.18.
A mixture of D-fructose (9.00 g, 50 mmol) and Dowex 50W X8 (0.90 IR (ATR) 761, 817, 966, 1022, 1077, 1158, 1208, 1294, 1521, 1626,
-
1
g) in 20 mL of dimethylsulfoxide was heated in an open boiling tube 1719, 2960 cm
in an oil bath at 110 °C for 24 h. Then the solution was cooled to M = 16,800 g/mol and PDI = 1.30 (12 h reaction product)
n
t-
0
0
room temperature, diluted with 50 mL of butylmethyl ether and TGA: T
H NMR (CF CO D): 5.66-5.68 (8H, bs), 7.54 ( 2H, bs), 8.24 ( 2H, bs)
3 2
with butylmethyl ether (3 x 5mL) and the combined filtrate was ppm. C NMR (CF CO D): 64.1, 64.3, 113.8, 121.7, 144.3, 155.9,
= 280 C, DTGA: 380, 484 C
onset
1
filtered to recover the ion exchange resin. The resin was washed
t-
13
3
2
transferred to a separatory funnel and washed with water (3x 25
mL) to remove DMSO. The butylmethyl ether layer was
1
62.7 ppm.
t-
2
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3
b, 294 mg, 92% yield.
Anal. Calc. for C16
IR (ATR) 760, 816, 966, 1022, 1077, 1158, 1208, 1294, 1522, 1712,
At the end of the reaction period Dowex 50W X8 solid acid catalyst
was filtered and the dialdehyde 1 was isolated by solvent extraction
method. The catalyst recovered by filtration could be reused for
four catalytic cycles without appreciable loss in the catalytic
activity. The yields obtained in reusing the catalyst from entry 4 in
table 1 for three more catalysis cycles is shown in table 2.
16 7
H O : C, 60.00; H, 5.04. Found: C, 60.28; H, 5.15.
-1
2964, 3118 cm
M = 17,600 g/mol and PDI = 1.45 (12 h reaction product),
n
0
0
TGA: Tonset = 272 C, DTGA: 371, 492 C
1
13
H and C NMR spectra of polyester-ether 3 are shown in figure 3.
Table 2. The percentage yields of OBFA (1) produced from D-
fructose in reusing of Dowex 50W X8 catalyst. 9.0 g of D-fructose in
2
0 mL of DMSO, Dowex 50W X8 10% (w/w), 110 °C, 24 h, was used
in all experiments
a, b
O
O
O
2
O
O
Trial
Yield (%)
m
O
O
n
3
a,b
1
2
3
4
76
74
71
73
Figure 2. Solution polymerization of OBFC (2) via diacid dichloride to
give polyesters 3a (m = 2) and 3b (m = 4).
2
, DMF, 80 °C, 4 h; b = 1,2-ethanediol or 1,4-butanediol,
pyridine, 1,1,2,2-tetrachloroethane, 0-23 °C, 12 h.
a = SOCl
3
. Results and discussion
The OBFA was further purified by recrystallization from aqueous
ethanol and then both aldehyde groups were oxidized to produce
3.1. Synthesis and characterization of 5,5'-[oxybis(methylene)]bis[2- the dicarboxylic acid monomer OBFC (2) as shown in figure 1. In the
furancarboxylic acid] (2)
initial screening experiments to develop a catalytic oxidation
method four different metal catalysts were tested for the oxidation
of OBFA to OBFC as shown in Table 3.
The dialdehyde 5,5'-[oxybis(methylene)]bis[2-furaldehyde] (1) can
be prepared in good yields by heating D-fructose in DMSO at 110 °C
for 24 h in an open container and using Dowex- 50W X8 (10% w/w)
catalyst as shown in figure 1. During the initial experiments, shorter
reaction times and lower catalyst loadings produced higher yields of Table 3. The percent yield of OBFC (2) produced in the oxidation of
HMF, however longer reaction times with at least 10% (w/w) solid OBFA (1) using oxygen and different metal catalysts
acid catalyst caused the dimerization of the initially formed HMF to
OBFA as shown in table 1. This technique avoids the isolation of the
unstable HMF and allows in situ conversion to the stable
symmetrical dimer OBFA. In addition, the bis aldehyde is a larger
hydrophobic molecule than HMF; more soluble in organic phase
and the favourable partition coefficient makes it easier to isolate by
solvent extraction than HMF. Further oxidation of OBFA to OBFC is
simpler, as only aldehyde groups are oxidized to carboxylic acid
groups; whereas in HMF one aldehyde group and one alcohol group
needs to be oxidized to COOH functions.
Entry
Catalyst
Percent yield
of OBFC (%)
1
2
3
4
CuO
AgO
0
24
0
5% Pd/C
5% Pt/C
98
1
4
mmol of OBFA, 50 mL of 1.5M aqueous NaOH, O
8 h, 2% (w/w) catalyst used in all experiments
2
, 1 atm., 23 °C,
Table 1. Percentage yields of HMF and OBFA (1) produced by
heating D-fructose in DMSO using Dowex 50W X8 catalyst under
different reaction conditions. 9.0 g of D-fructose in 20 mL of DMSO
was used in all experiments
Four catalysts, CuO, AgO, 5% Pd/C, and 5% Pt/C were tested for the
oxidation of OBFA to OBFC; only AgO and 5% Pt/C showed catalytic
activity and 5% Pt/C resulted nearly complete oxidation reaction
after 48 h. The initial screening using air as the oxygen source
2
resulted very slow reactions, therefore O gas was used in later
Entry
Dowex 50
catalyst
loading
Reaction
conditions
Temperature,
Time
Yield (%)
experiments. The catalyst could be recovered by centrifugation of
the solution at 1700 g for 10 min, and then solution was acidified to
pH = 2.0 by careful addition of concentrated HCl, the precipitate
formed was filtered and recrystallized from aqueous ethanol to give
OBFC as a pale yellow solid. The possibility of reusing the catalyst
was also tested and the 5% Pt/C catalyst recovered in the entry 4 of
table 3 was reused in three more catalysis cycles with negligible loss
in the catalytic activity as shown in table 4.
HMF
OBFA
(%, w/w)
1
2
3
4
5
2
80 °C, 4 h
32
54
20
0
0
5
110 °C, 4 h
110 °C, 12 h
110 °C, 24 h
110 °C, 48 h
6
10
10
10
54
76
72
0
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Table 4. The percentage yields of OBFC produced from OBFA in 3.2. Polyester synthesis using OBFC
reusing of 5% Pt/C catalyst. 1 mmol of OBFA, 50 mL of 1.5M
aqueous NaOH, 1 atm. O
experiments
2
, 23 °C, 48 h, 2% (w/w) catalyst used in all Polyester preparations using difuran diacid monomers are reported
in the literature, for example Gandini and co-workers have used the
acid dichloride and diesters of 5,5'-(1-methylethylidene)bis[2-
4
3, 44, 45, 46
Trial
Yield (%)
furancarboxylic acid] for the preparation of polyesters
. In
these examples, the methylene bridged difuran diacid has been
used in the synthesis of a variety of polyesters with aliphatic and
aromatic diols. In the present work we have prepared similar
polyesters using the new ether bridged difuran diacid 5,5'-
1
2
3
4
98
96
97
95
[
oxybis(methylene)]bis[2-furancarboxylic acid] (2) and two common
aliphatic diols as shown in figure 2. We have chosen the solution
polyesterfication technique similar to the one used by Gandini et al.
in the preparation of the polyesters from 2,5-furandicarboxylic acid.
The 1,2-ethandiol and 1,4-butanediol used in the polyester
synthesis can also be prepared from renewable resources, making
We have prepared the FDCA related dimer 5,5'-
oxybis(methylene)]bis[2-furancarboxylic acid] (OBFC, 2) from D-
fructose in 74 % overall yield from D-fructose via the dialdehyde 5,
'-[oxybis(methylene)]bis[2-furaldehyde] (OBFA, 1) as shown in
[
5
4
7, 48, 49
38
all renewable carbon based polymers
. The poly
figure 1 . This is much higher overall yield from a carbohydrate in
comparison with the typical yield in the production of FDCA from
monosaccharides; obviously higher yield in this new approach is
due to in situ dimerization of unstable HMF to the stable dialdehyde
condensations of the diacid dichloride were tested for different
reaction times 6, 12, and 24 h at room temperature. A small
increase in molecular weights were observed from 6 h to 12 h,
however, further increase in reaction time to 24 h failed to yield
improvements in the molecular weight. Polyester-ethers 3a and b
are insoluble in common organic solvents: dichloromethane,
chloroform, hexane, ethanol and methanol, but slightly soluble in
3
9, 40
OBFA
. The diacid OBFC is known as far back as 1933, as Iseki
and Sugiura reported the isolation of this diacid from the urine after
4
1, 37
feeding the dialdehyde OBFA to animals
. Then later Chundury
and Szmant reported the preparation of OBFC by chemical
oxidation of the OBFA by using stoichiometric quantities of
1
3 2
,1,2,2-tetrachloroethane, DMF and CF CO D.
4
2
oxidants, KMnO as well as AgO in 50 and 90% yields respectively
.
4
1
13
The polyester-ethers were characterized by FT-IR, H and C NMR
spectroscopy. FT-IR spectra of the polymers 3a and 3b showed
-1
strong ester carbonyl absorptions at 1719 and 1712 cm
respectively. These values are comparable to similar C=O
24
1
absorptions reported for polyesters prepared from FDCA . The H
NMR of polyester 3a showed a broad peak at 5.60 - 5.68 ppm,
representing eight protons of four -OCH
absorptions at 7.54 and 8.24 ppm for furan ring protons. The
2
- groups, and two
1
3
C
NMR of 3a showed seven peaks, including ester C=O peak at 162.7
ppm, further confirming the repeating unit of the polyester-ether.
The representative NMR spectra of OBFC - 1,4-butanediol polyester
1
(
3b) are shown in figure 3. H NMR of 3b showed five peaks and the
four 1,4-butane diol derived methylene groups were seen as two
1
1
broad peaks at 2.75 and 5.26 ppm. H- H COSY spectrum further
confirmed the coupling of these pairs of methylene groups. The
peak at 5.51 ppm was assigned to methylene groups in the ether
bridge. The furan protons were observed as two 2H peaks at 7.37
1
1
and 8.04 ppm and H- H COSY spectrum showed a cross peak
1
3
confirming the coupling of these peaks as well. C NMR of the
polyester-ether 3b showed eight peaks. The 1,4-butane diol derived
methylene carbons were observed as two peaks at 25.1 and 64.1
ppm, whereas the methylene ether carbons were observed at 66.8
ppm. The four peaks at 113.7, 121.0, 144.7 and 155.4 ppm were
assigned to furan ring carbons. The ester carbonyl carbon was
observed at 162.7 ppm and this value is comparable to the reported
1
3
3 2
ester C=O absorption at 161.0 ppm for PFF in CF CO D .
Thermogravimetric analysis (TGA) of polyesters 3a and 3b showed
decomposition onset temperatures at 280 and 272 °C. These are
comparable to Tonstet values of similar difuranic polyesters reported
in the literature, prepared by polymerization of 5,5'-(1-
methylethylidene)bis[2-furancarboxylic acid] with 1,2-ethanediol
1
13
Figure 3. H (a) and C (b) NMR spectra of polyester-ether 3b in
CF CO D, * solvent
3
2
4
6
and 1,4-butane diol . The polyester 3a decomposed in two steps
with DTGA peaks at 380, 484 °C; whereas the DTGA curve of 3b
showed two similar peaks 371 and 492 °C.
4
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1
2
9. B. Kuster, Starch-Stärke, 1990, 42, 314-321.
0. A. S. Amarasekara, D. Green and E. McMillan, Catal. Commun.,
4
. Conclusion
2
008, 9, 286-288.
monomer 5,5'-[oxybis(methylene)]bis[2-furancarboxylic acid] can 21. A. F. Sousa, C. Vilela, A. C. Fonseca, M. Matos, C. S. Freire, G.-J.
In conclusion, we have shown that renewable resources based
be prepared in 74 % overall yield from D-fructose via the stable
dialdehyde 5,5'-[oxybis(methylene)]bis[2-furaldehyde] without
M. Gruter, J. F. Coelho and A. J. Silvestre, Polym. Chem., 2015, 6,
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DOI: 10.1039/C6GC03314H
1
Renewable monomer 5,5'-[oxybis(methylene)]bis[2-furancarboxylic acid] from D-fructose
HOH C
2
OH
O
HO
CH OH
2
OH
O
O
O
O
O
OH
OH