G an Ag eemen numbe : 101058371
P ojec ac onym: ESTELLA
P ojec i le: Design o bio-based he mose
polyme wi h ecycling capabili y by
dynamic bonds o bio-composi e
manu ac u ing
DELIVERABLE 2.2
De elopmen o he mose epoxy esins wi h
CAN
Con ac ual Da e o Deli e y: 30/09/2024
Ac ual Da e o Deli e y: 30/09/2024
Lead con ac o o his deli e able: NIC
Au ho (s):
Gio gio To ani, Filipa A. Vicen e, Damian
Ghazal Ta akoli Gheinani, Willem Vogelzang
Pa icipan s(s):
WP
con ibu ing o he deli e able:
WP2
Na u e: Con iden ial
Ve sion V. 4
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Execu i e Summa y
In he ESTELLA P ojec , Task 2.2 is desc ibed as ollows:
Sub ask 2.2.1 De elopmen o associa i e bio-based epoxy om lignin wi h CAN
[NIC]
Bio-based epoxy esin will be ob ained using a lignin-based pla o m. NIC will
de elop a bio-based epoxy esin using a glycidyla ion p ocess wi h low Mw lignin
ac ions ha will be u he upg aded using a CAN. NIC will ollow he eac ions
and e alua e he dynamic bonds in he sys em wi h s a e-o he a analy ics (in-
si u FTIR p obe, SS-NMR, TGA, dynamic mechanical analysis (DMA), HPLC-CAD
and GC-MS) enabling he ine uning o he eac ion condi ions. The ob ained
ma e ial will be es ed in e ms o mechanical, heological, mo phological, and
physicochemical p ope ies. CAN o ma ion will be pe o med by ca ying ou
he epoxy esin om he lignin-based pla o m cu ing i sel h ough a dynamic
anses e i ica ion eac ion, hus leading o he c ea ion o highly ecyclable bio-
based c oss-linked he mose s uc u e. A e he e alua ion o mechanical
p ope ies and ecyclabili y, wo epoxy esins will be chosen o e alua e o
scalabili y in he T2.4.
Conside ing his sub ask, all expe imen s we e pe o med a he Na ional Ins i u e
o Chemis y (NIC) labo a o ies in Ljubljana, Slo enia, in he pe iod M3-M28.
Conside ing he de elopmen o associa i e bio-based epoxy om lignin wi h
CANs, wo dis inc pa hways we e explo ed: i) eac ion be ween lignin
monome s ( anillin and sy ingaldehyde) and a ious diamines o c ea e imine
bonds (Schi bases), ii) unc ionaliza ion o highe molecula weigh (MW)
ac ions o lignin de i ed om so wood K a lignin o c ea e es e and e he
bonds. In he i s pa hway, he ob ained Schi bases we e u he eac ed wi h
epichlo ohyd in o p oduce lignin monome epoxides, which we e subsequen ly
mixed wi h a c osslinke o ob ain he inal epoxy esin. The di icul y wi h his
app oach was ha he pu i ica ion o hese compounds equi ed ex ensi e use
o liquid ch oma og aphy and high consump ion o o ganic sol en s, hinde ing
i s u he applica ion and scale-up. Consequen ly, his me hod was no u he
pu sued o la ge-scale s udies.
In he second pa hway, he lignin was solubilized and unc ionalized using
succinic anhyd ide in he p esence o THF and 1-me hyl-imidazole as a ca alys .
The unc ionalized lignin was hen mixed wi h a ious g eene epoxides
(polyp opylene diglycidyl e he , 1,4-bu anediol diglycidyl e he , neopen yl
diglycidyl e he , and polye hylene diglycidyl e he ) han bisphenol A de i a i es
and cu ed o o m he inal epoxy esin. Tensile s eng h wi h each epoxide was
measu ed in o de o selec he mos p omising epoxy esin. The epoxy esin
p epa ed using 1,4-bu anediol diglycidyl e he me he ini ial equi emen s,
including a ensile s eng h g ea e han 40 MPa and a Young's Modulus o e 1
GPa. The e o e, his me hod using 1,4-bu anediol diglycidyl e he was chosen o
scaling up, and p epa a ion o epoxy esin samples o deli e o he pa ne s.
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Sub ask 2.2.2. De elopmen o associa i e ossil epoxy esins wi h CAN [ICSO]
Epoxy by (ICSO) will be based on c osslinked wi h ca boxylic acids and/o
anhyd ides in ing opening condensa ion eac ion. Epoxidized plan oils will be
used as eac i e diluen s o modi y p ope ies o esin. Also, he addi ion o
epoxidized plan oils will inc ease enewable con en . Resea ch wo ks will ocus
on he p oduc composi ion, especially selec ion o p ope ca alys allowing o
in
e ms o p oduc mechanical p ope ies and ecyclabili y. Designed epoxy will
be cha ac e ized by DSC, TGA, FT-IR, HPLC and high empe a u e gel
ch oma og aphy. Basic mechanical pa ame e s and heological p ope ies will
be de e mined. A e e alua ion o mechanical p ope ies and ecyclabili y, 2
epoxy esins (one wi h Tg<60ºC and Tg>60ºC) will be chosen o e alua e o
scalabili y in T2.4.
Rela i ely o his sub ask, all expe imen s we e pe o med a he Ins y u Ciezkiej
Syn ezy O ganicznej Blachownia (ICSO) labo a o ies in - ,
in he pe iod M3-M28.
This sub ask summa izes wo ks on he de elopmen o associa i e ossil epoxy
esins wi h CAN. Se ies o als o epoxy esins c osslinked wi h ca boxylic acids
and/o anhyd ides in ing opening condensa ion eac ion we e ca ied ou .
Epoxidized soybean oil, so bi ol and p opylene glycol we e used o modi y
p ope ies and inc ease o enewable con en o epoxy i ime s. Resea ch wo ks
we e ocus on:
- choosing he igh amoun and combina ion o ha dene s o ge he bes
mechanical and he mal p ope ies o he cu ed ma e ials,
- choosing he p ope ca alys and i s amoun o speed up he cu ing
eac ion,
- op imisa ion o empe a u e and ime in he cu ing s age
- main ain he igh balance o ha dness and lexibili y o he p oduc s
The bes esul s we e ob ained wi h succinic anhyd ide and succinic acid as a
ha dene s, and epoxidized soybean oil as a eac i e diluen . Ob ained p oduc s,
con aining Co alen Adap able Ne wo ks (CAN) we e cha ac e ized by he
highes glass ansi ion empe a u e (76.1 °C) and a ensile s eng h o 49,8 MPa.
Sub ask 2.2.3 De elopmen o dissocia i e ecyclable esins [WR]
Bio-based monome s o esins con aining Diels-Alde ac i e unc ional g oups
will be designed and syn hesized. In o al, a minimum o h ee di e en Diels-Alde
pai s will be compa ed (o which a leas u an-maleimide, he o he wo
candida es can be chosen om, o example: cyclopen adiene-
cyclopen adiene, u an-i aconimide, cyclopen adiene-benzoquinone). The
esins will be de eloped on a lab scale (10-50 g esin). The emainde o he esin
s uc u e will be kep as cons an as possible o allow compa ison o he di e en
Diels-Alde pai s. The e ec o he chosen Diels-Alde pai on he esins p ope ies
(DSC, TGA and mechanical) and ecyclabili y by a he mal s imulus will be
s udied. The mos p omising esin will be con e ed in o a one-
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Conside ing his sub ask, all expe imen s we e pe o med a Wageningen Food
and Biobased Resea ch labo a o ies in Wageningen, The Ne he lands, in he
pe iod M3-M28.
The aim o he sub ask 2.2.3 was o de elop DA-con aining dissocia i e
ecyclable esins wi h >60% biobased monome s and building blocks. Two
di e en DA-con aining hyb id sys ems ha e been s udied in his wo k: i) hyb id
epoxy/ DA sys em; and ii) hyb id aza-Michael/ DA sys em. The la e app oach
has he po en ial o he ull back- o-monome eco e y o he s a ing ma e ials
a highe empe a u es. Di e en biobased esin componen s ha e been
designed and syn hesized in his sub ask. The ollowing esea ch ques ions ha e
been in es iga ed:
- Can BADGE which is a ossil-based and oxic commonly used epoxy
de i a i e be eplaced wi h biobased epoxy de i a i es?
- Does he posi ion o DA bonds ha e an e ec on he ma e ial p ope ies
and ecycling beha iou ?
- Does he concen a ion o DA bonds ha e an e ec on he ma e ial
p ope ies and ecycling beha iou ?
- Does he c osslinking densi y ha e an e ec on he ma e ial p ope ies
and ecycling beha iou ?
Among all he DA-con aining he mose s ha ha e been p epa ed in his wo k,
he bes esul s in aspec o he mal and mechanical s abili y ha e been
ob ained using he ollowing o mula ions: i) BADGE-FA-BMI-689; and ii)
50%BADGE-50%DFGE-BMI-1,3-BAC. These ma e ials we e used o u he
e e sibili y and ecyclabili y s udies in o he asks/ wo k-packages.
This D2.2 deli e able has ully me i s objec i es. No de ia ions ha e been ound
in he deli e able o in he p ojec p og ess in con en , ime o impac s, as se ou
in he G an Ag eemen .
