Synthesis of bio-based functional polymers using

Acyclic Diene Metathesis (ADMET) polymerization

1
2
 O

O
Castor oil Eugenol M2
O
Clove oil
O MeO O
M3

O Ru cat. CH2Cl2
M1 G2 - CH2=CH2

Ru cat. CH2Cl2 O
- CH2=CH2
O
P2 n Ru cat.
O MeO
PCy3 Ar N N Ar Ar N N Ar
O
Cl Cl Cl
O
n O Ru CHPh Ru CHPh Ru CH
n
P1 P3
Cl Cl Cl
PCy3 PCy3 O
i
Pr
G1 G2
HG2
Cy = cyclohexyl, Ar = 2,4,6-Me 3C6H2

3
RSC Adv. 2019, 9, 10245-10252.
Why carbohydrates are
regarded as promising
renewable feedstock?

- Availability with low price.

- Hydrophilicity
- Hydrolytic degradability
- Non-toxicity
- Display extensive structural
and stereochemical diversity

Conversion Pathway from

Cellulose to Isosorbide
4
Plant oil
Sugar moiety

5
J. AM. CHEM. SOC. 2009, 131, 1664–1665
2010, 31, 368–373 6
7
 The attempt to synthesize regular polymer architectures by the
addition of BQ to suppress the isomerization reaction, was rather
unsuccessful at high temperature 100-120 ºC. 8
Isosorbide, the structural analogue glucarodilactone
(GDL)

9
ACS Macro Lett. 2015, 4, 284−288
 Representative stress vs strain curves for the
homopolymers and the two copolymers.
The copolymers were amorphous and rubbery, with a
high degree of elasticity quite different from the
semicrystalline and brittle homopolymers.
May be due to physical cross-linking via
dipole interactions between the GDL units or partial
lactone opening creating ionic (−COOH) and H-
bonding (−OH) net points of IU

Thermocyclical shape memory testing

Photo series showing the macroscopic shape-
memory effect in P(GDLU-co-IU).

The spiral was removed from a 0 ºC ice water bath, and

placed on a Teflon sheet on a hot plate set to 35 ºC

Copolymers were rubbery materials

displaying shape memory effects

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Hydrolytic degradation products resulting from decomposition of P(GDLU-co-IU)

All of the polymers were stable in acidic and

neutral aqueous conditions, the two analogs
containing GDLU hydrolytically degraded in
the presence of base 11
Polym. Chem. 2017, 8, 3746–3754.

12
 ADMET
polymerization
Ru cat.

EVE

13
Confirmation of End-functionalization using H NMR
1
2012, 1, 423−427

Confirmation of End-functionalization
via subsequent polymerization and
attachment of PEG via click reaction

14
 15
Thermal and mechanical evalution of homopolymers and copolymers
 A Rouse-like relaxation resulting
from the equilibrium relaxation of
trapped chains between the
temporary transient network
points that known to arise from
either hydrogen-bonds or ionic
interactions

Linear viscoelasticity of P(GDLU52-co-IU48) compositions (small-amplitude oscillatory shear)

Copolymers containing BHMFU

Showed enhanced mechanical strength,

elastic and rheological behavior

Importance of GDL for

mechanical strength

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 17
ACS Omega 2020, 5, 18301−18312
 Antoine Buchard
Polym. Chem., 2020, 11, 2681–2691
ADMET polymerization of xylose-derived monomer 1

a
Polymerization conditions: 1 (1 equiv., 0.25 g), G-II (0.04–0.005 equiv.), dynamic vacuum, 20 hours, magnetic stirring.
b
Calculated by SEC relative to polystyrene standards in THF eluent, ĐM = Mw/Mn. cTheorical Mn, calculated according to
Carothers equation as MWrepeat unit × (1 + r)/(1 +r − 2 × r × conv.), where r = (N1)/(N1 + 2NG-II). dReplicate of entry 2.
e
Conducted in presence of methyl 10-undecenoate (0.08 equiv.). fTheorical Mn calculated according to Carothers equation
(see note c) where r = (N1)/(N1 + 2(NG-II + Nmethyl 10-undecenoate)). g Conducted in presence of methyl10-undecenoate (0.16 equiv.).
h
19
 ADMET polymerization of mannose-derived monomer 2

a
Polymerization conditions: Mannose monomer 2 (1 equiv., 0.25 g), G-II (0.001–0.04 equiv.), bulk, 90 ºC, 20
hours, 0.1 mbar, magnetic stirring. Conversion (NMR): 100%. bCalculated by SEC relative to polystyrene
standards in THF eluent, ĐM = Mw/Mn. cTheorical Mn, calculated according to Carothers equation as MW repeatunit
× (1 + r)/(1 + r −2 × r × conv.), where r = (N2)/(N2 + 2NG-II) and conv. = 1. dConducted with mechanical
overhead stirrer on 1.0 g of 2.
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 Amphiphilic behavior for casted
film of poly(1)-depr2h

Contact angels’ values obtained

for water were found in the range
of 70–85º ,
while dodecane did not form
droplets but rapidly wetted

Strategy for the post-polymerization deprotection and functionalization of poly(1) by

21
reaction with chlorodiphenylphosphine.
Thermal properties of polymers poly(1) and poly(2) as determined from
TGA and DSC

a
Temperature at which 5% mass loss is observed. bTemperature at which maximum mass loss is observed for the considered
decomposition step. c Relative mass loss for the considered decomposition step. dResidual mass at 600 ºC. eGlass transition
temperature determined for the second heating cycle. fMelting temperature determined for the second heating cycle. gNot
detected. hAn additional decomposition step was observed with Tinf 196 ºC (17.7% mass loss).

Thermal analyses of selected poly(1) and poly(2) samples: (a) thermogravimetric analysis (TGA); (b) differential scanning
calorimetry (DSC) (2nd heating cycle) 22
Conclusions
• Acyclic diene metathesis (ADMET) polymerization of α,ω-diene monomers
derived from castor oil and sugar (xylose and mannose) using 2nd generation
Grubbs catalyst has been conducted.

• High molecular weight bio-based polyesters [Mn= 71.4, Mw/Mn= 2.2] have been
obtained using the following conditions bulk, 0.5 mol% of catalyst, 90 ºC,
dynamic vacuum (0.1 mbar) with mechanical stirring.

• High thermal stability of the resultant polymers up to 350 ºC was shown using
TGA.

• The production of transparent thin films with amphiphilic behavior using partial
ketal moieties deprotected polymers.

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The investigation of
the influence on the
chiral/achiral and
polar/nonpolar
nature of the amino
acids on the Prof. Wolfgang H. Binder
crystallization
behavior 24
RSC Adv., 2017, 7, 47507–47519
Yield %= 64-76 Yield %= 63-86

25
Obtained molecular weights calculated by NMR and GPC, PDI's, yields and trans : cis ratio
of the internal double bonds for ADMET polymerization of the monomers 2a–2e to
polymers 3a–3e by using different types of catalyst

Bulk polymerization at 65 ºC, catalyst amount 1 mol%, the reaction temperature was increased stepwise from 85 ºC
up to 165 ºC in the last hour. 26
 Obtained molecular weights calculated by NMR, DP and yields of the unsaturated ADMET
polymers 3a–3e obtained with Grubbs 1st catalyst and saturated polymers 4a–4e

6 h, depr. 24h
TsNHNH2: p-toluenesulfonhydrazide

Calculation of Mn not possible due to overlapping of the methyl end groups and
a

methyl groups in the repeating unit.

1
H-NMR spectra of monomer 2c (top), ADMET-polymer 3c (middle) and
hydrogenated polymer 4c (bottom) 27
Hydrogenation and deprotection
28
(a) MALDI-ToF-MS of ADMET polymer 3b (b) zoom in to [E-M2-EK]+ to show isomerization of the olefin
(c) measured and simulated pattern for [E-M2-EK]+.
Two series can be assigned and the distance between signals of the same series amounts to 512 g
mol-1 (repetitive unit). The distance between signals of different series is 14 g mol -1

Olefin isomerization is leading to polymers having a slightly

different chain length of the alkyl chain 29
MALDI-ToF-MS of ADMET polymer 4e (b) zoom in to [E-M-EK]+ to show isomerization
of the olefin (c) measured and simulated pattern for [E-M-EK] +.

Distance between the main series is 434 g mol-1 (repetitive unit), three different
series with a distance of 14 gmol-1 can be observed, this indicating the higher
isomerization
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(a) DSC thermograms of monomer 2a (dotted lines) and the hydrogenated polymer 4a (straight
lines) (b) DSC thermograms of monomer 2b (dotted lines) and the hydrogenated polymer 4b
(straight lines).

2c–2e and polymers 4c–4e (with an aliphatic

backbone) no crystalline behavior was
observed
Only amino acids with a functional group
able to form defined crystal structures with an
additional intermolecular interaction
31
Conclusions
• Acyclic diene metathesis (ADMET) polymerization of α,ω-diene monomers
derived from castor oil and aminoacids (chiral and achiral) using ruthenium-
carbene catalysts (Grubbs 1st and 2nd and Hoveyda-Grubbs 1st) has been conducted.

• Bio-based polyamides [Mn(NMR)= 22,000, Mw/Mn= 1.9] have been obtained using
bulk conditions, 1 mol% of catalyst, 65 ºC (increased ). Followed by complete
hydrogenation of the internal double bonds with p-toluenesulfonhydrazide
(TsNHNH2).

• Grubbs 1st generation was found to be the best catalyst in handling and in
synthesizing low isomerized, high molecular weight polymers in good yields.

• The monomers and the hydrogenated polymers of polar amino acids (glutamic and
aspartic acid) show crystalline morphologies.

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