Direct synthesis of polycarbonate diols from atmospheric flow CO2 and

diols without using dehydrating agents

Green Chem., 2021, 23, 5786

Prof. LIN, CHING HSUAN

Mahmoud Younis Mohamed

7112065209
 Outlines

 Introduction

 Results and discussion

 Conclusions

 Experimental
Introduction
 Experimental

 General procedure for the reaction of 1,6 hexanediol  Procedure of the reaction carried out in an autoclave
and CO2 in a CO2 flow semi-batch reactor. reactor

 CeO2, 1,6-hexanediol, and a PTFE-coated magnetic

spinner were put into a stainless-steel autoclave reactor
with an inner volume of 190 mL.
 A catalyst and reagents were put into the flask, and then  The autoclave was purged with 1 MPa CO2 three times,
a PTFE tube for CO2 introduction was inserted into the and then pressurized to 5 MPa CO2 [at room
bottom of the flask. temperature, about 22 g (0.5 mol)].
 the flask part was put into an oil bath for heating. When  The autoclave was then heated at 483 K (the heating-up
the reaction was done, the flask was transferred to an ice- took about 1 hour), and the pressure in the reactor
water bath for cooling down. increased to 7.5 MPa.
 The reaction was carried out for a designated reaction
time, and then cooled in an ice water bath.
 Results and discussion

 Application of a CO2 flow semi-batch reactor in the reaction of 1,6-hexanediol and CO2 over CeO2

 the reaction of 1,6-hexanediol with flow CO2 at atmospheric

pressure over CeO2, in triethylene glycol dimethyl ether
(triglyme) solvent at 473 K by using a CO2 flow semi-batch
reactor

 The reaction of flow CO2 and 1,6-hexanediol proceeded

smoothly to reach 50% yield in 24 h with a high diol balance
(>99%)

○, Conversion; ◊, dimer yield; ◆, polymer yield

 CO2, 1,6-hexanediol was reacted with 0.1 MPa of CO2 in
an autoclave reactor

 the formation amount of the target carbonate was below the

detection limit (yield < 0.01%). Even in the reaction with
high-pressure CO2 (7.5 MPa) in the sealed batch reactor
 the conversion was low and became constant at 0.9% (4–24 h)
with a dimer produced as the main product.
 The water content of the reaction mixture in the autoclave
reactor under 7.5 Mpa was 600–700 ppm

 The water content in the reaction media measured by

coulometric Karl-Fischer titration

 The water content in semi batch reactor was below the

detection limit (<4 ppm), suggesting that the coproduced
water was efficiently removed from the reaction media.
 The water content of the reaction mixture in the autoclave
reactor under 7.5 Mpa was 600–700 ppm
Effect of reaction parameters on the reaction of 1,6-hexanedioland CO2 in a CO2 flow semi-batch reactor

 Effect of catalyst

 the reactions without a catalyst and with various solid oxides .

 No products were detected without using a catalyst (yield <
0.01%).
 CeO2 exhibited excellent catalytic activity towards the
reaction of flow CO2 and 1,6-hexanediol under atmospheric
pressure, giving 17% conversion of the diol and >99%
selectivity to organic carbonate species including the dimer
and the polymer.
 Effect of CeO2 amount

 the conversion increased with the increase of the

CeO2 amount in the range of 0–0.08 g and reached
3.8% in this range.

 With larger amounts of CeO2 from 0.08 to 0.20 g,

the conversion became constant at 3.8% .
 the solvent effect on the reaction was investigated with an amount of
the CeO2 catalyst (0.10 g).

 The solvents with low solubility in water (≤2 g L−1-H2O)

including diglyBu, diphenylmethane, phenylcyclohexane, and
diphenyl ether, provided higher conversion (4.7–5.2%) to the
carbonates than triglyme .However, the solidification of 1,6-
hexanediol occurred in the condenser due to their poor ability
to dissolve 1,6-hexanediol, resulting in a lower diol balance
(90–97%) and a difficulty in the prolonged reaction similar to
the case of the neat conditions.
 the reactions with triglyme or tetraglyme that are miscible
with water provided a higher diol balance (>99%) and
adequate conversion (3.8%).
  The effect of reaction temperature was investigated with an adequate amount of
CeO2 (0.10 g) in the range between 333 and 483 K

 The conversion increased with an increase in the reaction

temperature from 333 K to 483 K, and production of the
polymer was observed when the conversion exceeded 3%
at temperatures above 373 K.
 the results suggest that a higher reaction temperature
facilitates the removal of water from the reaction media,
which shifts the equilibrium to the product side to result
in higher conversion.
 The effect of the CO2 flow rate was investigated in the
presence of an adequate CeO2 amount (0.10 g) .

 The conversion increased almost linearly with the increase of

the CO2 flow rate from 0 to 200 mL min−1 and became
constant at 17% when the flow rate was above 200 mL min−1

 the effect of the 1,6-hexanediol concentration on the reaction at

483 K

 The conversion increased with an increase in the 1,6-

hexanediol concentration at lower concentrations from 0.9 to
2.4 M, and the selectivity to the dimer slightly decreased as it
was polymerized into the polymer. At higher concentrations
from 2.4 to 4.9 M, the conversion and selectivities were almost
the same
 The standard reaction conditions were set at a concentration of
2.4 M..
Time-course of the reaction of 1,6-hexanediol and CO2 over CeO2 in the CO2 flow semi-batch reactor and analyses of
the produced polymer

 The reaction proceeded smoothly to reach 95% conversion at 96 h.

 The selectivity to the dimer was high at a low conversion level and
decreased with a longer reaction time.
 the selectivity to the polymer kept increasing and reached 97% at 96 h
 The average molecular weight (Mn) and dispersity (Mw/Mn)
of the produced products were analysed by size-exclusion
chromatography (SEC) .
 Both the Mn and Mw/Mn of the products kept increasing
during the reaction, and polymer with an Mn of 3500 (in the
case of polycarbonate diols, 24 repeating units) was obtained
at 96 h.
1H-NMR (Fig. 6d) spectroscopy
signals at 3.6 ppm “α” assigned to the protons of the methylene group adjacent to the OH group
and 4.0–4.2 ppm ( “1”), which can be assigned to the protons of the methylene group adjacent to the carbonate group.
A triplet signal at 3.4 ppm is assigned to the protons of the methylene group adjacent to the ether bond

MALDI-TOF mass (Fig. 6c)

A series of strong signals with a mass increase of 144 was observed and they were assigned to poly(hexamethylene carbonate) diol .
The other series of minor signals with a lower mass number of 44 than the strong signals was identified as poly (hexamethylene
carbonate) diol with one ether linkage.
 The proposed reaction mechanism of the polycarbonate diols from CO2 and 1,6-hexanediol over CeO2

I. The dissociative adsorption of 1,6-hexanediol on the CeO2

surface gives the alkoxide adspecies.
II. The insertion of CO2 into the alkoxide adspecies provides
Ce-hydroxyhexyl carbonate adspecies.
III. The nucleophilic attack of the oxygen anion in the
alkoxide adspecies to the carbonate group in the Ce-
hydroxyhexyl carbonate adspecies affords the
corresponding linear carbonate (dimer).
IV. Diffusion and purge of the coproduced water from the
reaction media to the gas phase by the gas flow.
V. Further reaction of the produced dimer with CO2 and 1,6-
hexanediol or the produced copolymer results in a step-
growth polymerization with the production of
poly(hexamethylene carbonate) diol.
 The high durability of CeO2 was confirmed by the
reusability test.

 . The CeO2 was used 4 times, providing similar conversions

and selectivities.
 No distinct difference in the XRD patterns, crystallite size,
and specific surface area was observed between fresh CeO2
catalyst and the spent CeO2 catalyst which has been used 4
times
 Conclusions

 direct transformation of atmospheric pressure flowing CO2 with 1,6-hexanediol into the
corresponding polycarbonate diol without any dehydration agents, achieving high yield and
selectivity to the target polycarbonate
 CeO2 worked as the most effective and reusable heterogeneous catalyst and the CO2 flow
system enabled the removal of water from the reaction media to overcome the reaction
equilibrium.