Design of Waterborne Isocyanate -free Poly (Hydroxy Urethane)s- Poly (Butyl Methacrilate) Hybrids via Miniemulsion and Properties of the Cast Films.

THÈSE PRÉSENTÉE POUR OBTENIR LE GRADE DE
DOCTEUR DE
L’UNIVERSITÉ DE BORDEAUX
ÉCOLE DOCTORALE DES SCIENCES CHIMIQUES
Spéciali é : Polymè es
ET
DOCTEUR DE
L’UNIVERSITÉ DU PAYS BASQUE
ÉCOLE DE MASTER ET DOCTORAT
Spéciali é : Chimie appliquée e polymè es
Pa Bo is BIZET
Design o Wa e bo ne Isocyana e- ee Poly(Hyd oxy U e hane)s –
Poly(Bu yl Me hac yla e) Hyb ids ia Miniemulsion and P ope ies o he
Cas Films
Concep ion d’hyb ides PolyHyd oxy U é hanes sans Isocyana e – Poly(Mé hac yla e de Bu yle)
en mini-émulsion e p op ié és des ilms ésul an s
Sous la co-di ec ion de : P Hen i CRAMAIL (Uni e si é de Bo deaux)
P José Ma ia ASUA (Uni e si é du Pays Basque)
Co-encad an : D E ienne GRAU (Uni e si é de Bo deaux)
Sou enance p é ue le : 27 Fé ie 2020
Memb es du ju y :
D . Elodie Bou gea -Lami
Di ec eu de Reche che, Uni e si é Claude Be na d Lyon
Rappo eu
D . Ch is ophe De embleu
Che cheu con i mé, Uni e si é de Liège
Rappo eu
D . Lise Maisonneu e
Doc eu , Michelin
Examina eu
P . Ma ia Paulis
P o esseu , Uni e si é du Pays Basque
Examina eu
P . Sébas ien Lecommandoux
P o esseu , Uni e si é de Bo deaux
Examina eu
(cc)2020 BORIS ERIC ALAIN BIZET (cc by-nc-nd 4.0)
GENERAL TABLE OF CONTENT
Chap e 1: S a e o he A & Objec i es …………………………………….. 5
Pa A: Hyb id – Non Isocyana e Polyu e hanes (H-NIPUs).. 7
1. In oduc ion ………………………………………………………………………………………………………….. 9
2. NIPUs in a nu shell ………………………………………………………………………………………………. 10
2.1. NIPUs – wha a e hey? ………………………………………………………………………………………. 10
2.1.1. Di e en pa hways o make NIPUs …………………………………………………………… 10
2.1.2. T ansu e haniza ion and Aminolysis o cyclic-ca bona es compounds ............ 11
2.2. Challenges o o e come ……………………………………………………………………………………… 12
2.2.1. T ansu e haniza ion p ocess ……………………………………………………………………. 12
2.2.2. Aminolysis o cyclic-ca bona es – Towa ds PHUs ……………………………………… 14
2.3. Valo iza ion o NIPUs …………………………………………………………………………………………. 18
3. Hyb id-NIPUs: no el ma e ials o a b oad ange o p ope ies ………………………........... 18
3.1. NIPU-Epoxy ……………………………………………………………………………………………………….. 19
3.1.1. Epoxy-NIPUs h ough he eac ion o pa ially ca bona ed epoxy compounds 20
3.1.2. Epoxy-NIPUs h ough he eac ion o homo elechelic p epolyme s wi h cu ing
agen s ……………………………………………………………………………………………………………………………… 21
3.1.3. Epoxy-NIPUs h ough he inco po a ion o hyd oxyu e hane modi ie s …….. 25
3.1.4. Epoxy-NIPUs om bio-based esou ces ……………………………………………………. 26
3.2. NIPU-Ac ylics …………………………………………………………………………………………………….. 27
3.2.1. Unsa u a ed cyclic ca bona es and hei ac ylic polyme iza ion ………………… 29
3.2.2. (Hyd oxy)u e hane me hac yla es – (H)UMAs ………………………………………….. 32
3.2.3. Unsa u a ed NIPU-p epolyme s: Poly(hyd oxy)u e hane me hac yla es –
P(H)UMAs ……………………………………………………………………………………………………………………….. 37
3.2.4. Radical eac i e (H)UMAs – Summa y o he syn he ic s a egies ………………. 42
3.3. O he Hyb id-NIPUs …………………………………………………………………………………………… 46
3.3.1. Si-con aining H-NIPUs ……………………………………………………………………………… 46
3.3.2. Biopolyme -con aining NIPUs ………………………………………………………………….. 54
4. Concluding ema ks …………………………………………………………………………………………….. 58
5. Re e ences …………………………………………………………………………………………………………... 59
6. Sho ened o ms ………………………………………………………………………………………………….. 70
2
Pa B: Hyb id – Non Isocyana e Polyu e hanes (H-NIPUs) 73
1. In oduc ion ………………………………………………………………………………………………………… 75
2. Wa e -soluble NIPUs …………………………………………………………………………………………… 76
2.1. NIPU syn hesis using wa e as eac ion medium ………………………………………………….. 76
2.2. Modi ica ion o NIPUs syn hesized on o ganic sol en s ………………………………………... 78
3. Hyd ogels ……………………………………………………………………………………………………………. 81
4. Wa e -bo ne Dispe sions ……………………………………………………………………………………... 82
4.1. Ace one-like p ocess …………………………………………………………………………………………... 82
4.1.1. NIPUs dispe sion by ace one-like anses e i ica ion p ocesses ………………… 83
4.1.2. NIPUs dispe sion by ace one-like aminolysis p ocesses …………………………….. 87
4.2. NIPU dispe sions h ough in e acial polyme iza ion ………………………………………....... 89
4.3. NIPU dispe sions by mini-emulsion polyme iza ion …………………………………………….. 89
4.4. PHU dispe sions by nano-p ecipi a ion ……………………………………………………………... . 90
5. Wa e -bo ne Hyb id-NIPUs (H-NIPUs) ………………………………………………………………..... 91
5.1. NIPU-Ac ylics – HUMAs ………………………………………………………………………...................... 91
5.2. NIPU-Epoxy ……………………………………………………………………………………………………….. 92
6. Conclusions …………………………………………………………………………………………………………. 94
7. Re e ences …………………………………………………………………………………………………………... 95
8. Sho ened o ms ………………………………………………………………………………………………... 100
Pa C: Objec i es & Ou line ....................................................... 101
Chap e 2: Bulk Syn hesis o Bio-Based Poly(Hyd oxy U e hane)s
– PHUs…………………………………………………………………………………..... 105
1. In oduc ion …………………………………………………………………………………………………….... 107
2. Expe imen al ……………………………………………………………………………………………….…….. 109
2.1. Ma e ials and me hods ……………………………………………………………………………….…….. 109
2.2. S anda d P ocedu e o polyme iza ion …………………………………………………….………. 111
2.3. Bis-cyclic ca bona e syn hesis ………………………………………………………………….……….. 111
3. Resul s and Discussion ………………………………………………………………………………………. 112
3.1. Ac i a ed bio-sou ced bis-cyclic ca bona es (bisCCs) …………………………………………. 112
3.2. Copolyme iza ion o bisCC-C4 and bisCC-C10 wi h mix u es o diamines ……………. 115
3.3. The mal cha ac e iza ion …………………………………………………………………………………. 120
3.4. Viscoelas ic beha io …………………………………………………………………………………….….. 121
3.5. Theo e ical s udy o he polyme iza ion beha io s o bisCC-C4 and bisCC-C10 ….….. 122
4. Conclusion ………………………………………………………………………………………………………… 124
5. Re e ences ………………………………………………………………………………………………………… 125
3
6. Sho ened o ms ……………………………………………………………………………………………...… 129
7. Suppo ing In o ma ion ……………………………………………………………………………………… 130
7.1. NMR analyses ………………………………………………………………………………………………...… 130
7.2. IR analyses ……………………………………………………………………………………………….……… 140
7.3. DSC analyses (Tempe a u e amp: 10°C.min-1) …………………………………………….……. 141
7.4. TGA analyses …………………………………………………………………………………………….……… 143
7.5. SEC aces …………………………………………………………………………………………….……..…… 145
7.6. DFT S udy – S uc u es o he in e media es ………………………………………….……....……145
Chap e 3: Miniemulsion o Non-Isocyana e Polyu e hane-Ac ylics
Hyb ids and P ope ies o he Cas Films The eo …………...…….. 147
1. In oduc ion …………………………………………………………………………………………….……...… 149
2. Expe imen al …………………………………………………………………………………………….……..... 150
2.1. Ma e ials …………………………………………………………………………………………….……........… 150
2.2. Expe imen al design …………………………………………………………………………….…….......... 150
2.3. Miniemulsi ica ion and miniemulsion polyme iza ion …………………………….……......... 151
2.4. Film cas ing …………………………………………………………………………………………….……...... 152
2.5. Cha ac e iza ion ……………………………………………………………………………………….…….... 153
3. Resul s and Discussion ……………………………………………………………………………….…….... 155
4. Conclusions …………………………………………………………………………………………….……........ 165
5. Re e ences …………………………………………………………………………………………….…….......... 166
6. Sho ened o ms …………………………………………………………………………………….……......... 169
7. Suppo ing In o ma ion …………………………………………………………………………….……...... 170
7.1. Side Reac ions …………………………………………………………………………………………….……. 170
7.2. Solubili y …………………………………………………………………………………………….……........... 175
7.3. Miniemulsion polyme iza ion using he mal ini ia o s ………………………….……........... 179
7.3.1. Fo mula ions wi h he mal ini ia o s …………………………………………….……...... 179
7.3.2. Resul s and discussion …………………………………………………………………………… 182
7.4. Fo mula ions wi h edox ini ia o s …………………………………………………………………… 184
7.5. SEC-MALLS T aces …………………………………………………………………………………………… 187
7.6. DSC T aces ………………………………………………………………………………………………………. 188
7.7. Minimum Film Fo ming Tempe a u e (MMFT) …………………………………………………. 189

4
Chap e 4: Bulk Syn hesis o Bio-Based Poly(Hyd ocyU e hane)s –
PHUs……………………………………………………………………………………… 9
1. In oduc ion ……………………………………………………………………………………………….… 193
2. Expe imen al ………………………………………………………………………………………………... 194
2.1. Ma e ials and me hods …………………………………………………………………………………. 194
2.2. Syn hesis o wa e bo ne g a ed PHU-(me h)ac ylic hyb ids ……………………………. 194
2.3. Cha ac e iza ion ………………………………………………………………………………………..… 199
2.4. Film cas ing ……………………………………………………………………………………………….... 201
3. Resul s and discussion ………………………………………………………………………………….... 201
3.1. Syn hesis o he unc ionalized PHUs ……………………………………………………………... 201
3.1.1. Me hac yla e- e mina ed PHUs …………………………………………………………… 201
3.1.2. Me hac yla e g oups dis ibu ed along he PHU chains (mul i unc ionalized) 206
3.2. Syn hesis o he hyb id la exes ………………………………………………………………….…… 209
3.3. Film p ope ies ……………………………………………………………………………………………. 213
4. Conclusions …………………………………………………………………………………………………... 218
5. Re e ences …………………………………………………………………………………………………..... 220
6. Sho ened o ms ……………………………………………………………………………………………. 223
7. Suppo ing In o ma ion …………………………………………………………………………….…… 224
7.1. monoCC-GMA – Ca bona ed Glycidyl Me hac yla e ……………………………………….…. 224
7.2. Telechelically- unc ionalized PHUs ……………………………………………………………...… 224
7.2.1. Fo mula ions ………………………………………………………………………………..…… 224
7.2.2. NMR Spec a ………………………………………………………………………………...…… 228
7.3. Mul i- unc ionalized PHUs …………………………………………………………………….....…… 232
7.4. Fo mula ions used o he miniemulsions ……………………………………………….....…… 233
Chap e : Gene al Conclusions …………………………………………….. 235
Conclusions Géné ales ..……………………………………….. 
Resumen y Conclusiones ..………………………………….... 247
CHAPTER 1
STATE OF THE ART
& OBJECTIVES
PART A
HYBRID – NON ISOCYANATE POLYURETHANES
(H-NIPUS)
A PATHWAY TOWARDS A BROAD RANGE OF NOVEL
MATERIALS
Keywo ds: Non Isocyana e Polyu e hanes - NIPUs
Poly(Hyd oxy)u e hanes - PHUs
Polyme -Polyme Hyb ids
NIPU-Epoxy
NIPU-Ac ylics
NIPU-Siloxane
Chap e 1 – Pa A
14
o en equi ed. This usually yields ime and ene gy consuming p ocesses ha is he bo leneck
o upscaling.
Scheme 2: Backbi ing ollowed by u ea o ma ion in he ansu e haniza ion eac ion o bis-
hyd oxyalkylca bama es – adap ed om Maisonneu e e al.14
2.2.2. Aminolysis o cyclic-ca bona es – Towa ds PHUs
2.2.2.1. Monome syn hesis
In a simila way o ansu e haniza ion, he o ma ion o PHUs elies on he a ailabili y o
e y speci ic monome s, namely cyclic ca bona e compounds. So a , esea ch ac i i ies ha e
been mos ly ocused on he syn hesis o bis-cyclic ca bona es ollowed by hei subsequen
aminolysis wi h amines. In 2019, Ca é e al. published a e iew desc ibing all he di e en
ou es owa ds he syn hesis o (gene ally bio-based) 5-membe ed bis-cyclic ca bona es and
hose a e desc ibed in Figu e 2.20 The main goal o his esea ch ield consis s in ge ing id o
he use o phosgene, which is his o ically used in he eac ion wi h a diol moie y o yield he
co esponding cyclic ca bona e. The desc ip ion o he di e en ou es owa ds he o ma ion
o bis-cyclic ca bona es is ou o he scope o his s udy as i has al eady been widely
documen ed in he scien i ic li e a u e.19,20 The ocus will hence be made on o he wo mo e
widely u ilized pa hways, namely he ca bona ion o bis-epoxide compounds and he
es e i ica ion eac ion o diacids (o de i a i es) wi h glyce ol ca bona e.
The ca bona ion o bis-epoxide compounds wi h CO2 ( egula ly used as a sus ainable C1
sou ce o he syn hesis o bio-based monome s) is ca ied ou unde high p essu e and
empe a u e. The ac i a ion o he epoxy moie y has o be pe o med wi h he help o a halide
ca alys .24 B omine-con aining compounds usually a e he ca alys s o choice. This pa hway can
be u ilized o ca bona e a ious ypes o epoxides, anging om mono-epoxide (such as glycidyl
me hac yla es) o mo e complex s uc u es such as epoxidized ege able oils,25 a y-acid
based26 o e pene-based monome s.27

Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
15
The es e i ica ion eac ion o diacids wi h glyce ol ca bona e is ano he in e es ing ou e
owa ds he o ma ion o bis-cyclic ca bona es. This pa hway makes use o a de i a i e o
glyce ol, which is a by-p oduc o he biodiesel p oduc ion indus y ha has s ill no go any
alo iza ion pa h.28 I yields speci ic es e -ac i a ed monome s ha ha e been showed o
exhibi supe io eac i i y as opposed o alipha ic cyclic ca bona es. As e e y es e i ica ion
eac ion, he acid moie ies ha e o be chemically ac i a ed and he equilib ium has o be shi ed
owa ds he o ma ion o he di-es e . This is usually pe o med hough he chlo ina ion
eac ion o he acid moie ies, yielding di-acyl-chlo ide moie ies,29,30 o he use o coupling
agen s. The combina ion o N,N′-Dicyclohexylca bodiimide (DCC) wi h he ca alys 4-
Dime hylaminopy idine (DMAP) (also known as he S eglich es e i ica ion eac ion) is o en
epo ed as i allows o each e y high con e sions using e y mild condi ions hanks o he
p ecipi a ion o he 1,3-Dicyclohexyl u ea (DCU) u ea by-p oduc o med by DCC upon i s
eac ion wi h he acid unc ion.31 Howe e , in bo h cases, he g eenness o he p ocess is
educed due o he o ma ion o e y high amoun s o by-p oduc s.
2.2.2.2. Majo challenges ye o o e come
Apa om he di icul access o monome s, he aminolysis eac ion o cyclic-ca bona e
compounds s ill is a complex eac ion, he limi s o which a e s ill unde in es iga ion. In his
e iew, we will only men ion he majo challenges ha a e summa ized in Figu e 3.
 Enhancing he bis-cyclic ca bona e eac i i y
A emps o enhance o he aminolysis eac ion by imp o ing he eac i i y o he cyclic-
ca bona e moie y ha e been epo ed. This was done by ei he inc easing he ing size o
in oducing speci ic moie ies in alpha- o be a-posi ion o he cyclic ca bona e moie y.14,15,20
The inc ease o he ing size is a syn he ic challenge in i sel , especially i phosgene- ee
pa hways a e desi ed. The mos common moie y is he 5-membe ed cyclic ca bona e, which is
he modynamically e y s able. The scien i ic li e a u e ela es he syn hesis o 6-, 7- and 8-
membe ed ings, he he modynamic s abili y o which is dec eased, hence os e ing hei
eac i i y in pa icula owa ds amines.14,32–34
In o de o inc ease he eac i i y o 5-membe ed cyclic ca bona es, speci ic chemical
unc ions ha e been in oduced in alpha- o be a-posi ion o he ca bona e ing. In mos o he
cases, e he o es e moie ies a e inco po a ed in be a posi ion o he ing.29 Ac ing as an
elec on wi hd awing g oup, hey inc ease he pa ial posi i e cha ge on he ca bonyl ca bon
Chap e 1 – Pa A
16
and making i p one o eac wi h amines. Nume ous o he ac i a ions ha e been exempli ied
as depic ed in Figu e 3.20,35–38
 Playing on he amine s uc u e
The s uc u e o he amine go e ns i s eac i i y, he mo e nucleophilic he highe he eac i i y.
I is a gene al ag eemen ha he eac i i y o he amines ollows he o de e ia y amine <
seconda y amine < p ima y amine.39 The e ia y amines exhibi no eac i i y in he ing opening o
cyclic ca bona es. In he case o p ima y amines, he eac i i y is go e ned by he amine chemical
s uc u e and molecula weigh .14,40–42 A oma ic amines a e no eac i e, and e y subs i u ed
alipha ic amines exhibi poo eac i i y. In addi ion o his, amines wi h s ong elec on-
wi hd awing g oups in alpha o be a posi ion wi h espec o he amino g oup we e ound o be
mo e eac i e. Mo eo e , lowe mola masses o he amines inc eased he chemical eac i i y o
he aminolysis o cyclic ca bona es.14,43
 Polyme iza ion condi ions
The o ma ion o PHUs yields polyme s o e y high iscosi y, which is he esul o a e y high
densi y o hyd ogen bonds.44 To o e come his limi a ion, se e al solu ions can be employed. The
mos ob ious one consis s in inc easing he eac ion empe a u e, bu his inc eases he p obabili y
o side- eac ions o occu . The u ea o ma ion, due o he eac ion o amine wi h he p e- o med
u e hane moie y is known o occu a a empe a u e highe han 100 o 120 °C.20 In he case o es e -
ac i a ed bis-cyclic ca bona es, he amidi ica ion eac ion is also obse ed. Ano he way o b eaking
he densi y o hyd ogen bond consis s in using a p o ic sol en ha p o ides a high deg ee o
eedom in he mo ion o he polyme chain o i o con inue eac ing. This sol en should
p e e ably be o high pola i y o solubilize he monome s and o o m a homogeneous eac ion
medium.
Ca alysis is also impo an . The p ecise desc ip ion o each ca aly ic sys ems is ou o he scope
o his e iew, bu i can be no iced ha signi ican imp o emen s o he kine ics o ing opening
we e achie ed, no ably when iazabicyclodecene (TBD) was used as ca alys . Howe e , p og essi e
con e sion o he o med PHU in o polyu ea was also no iced, sugges ing ha ca e ul a en ion has
o be paid when selec ing a ca aly ic sys em.45 De ailed in o ma ion can be ound in a ecen ly
published e iew om Sa don and cowo ke s.46
 Molecula weigh s p ospec s wi h ega d o PHU syn hesis
Despi e ex ensi e esea ch ac i i ies, and e en i PHU can seem p omising candida es o he
implemen a ion o phosgene- and isocyana e- ee pa hways owa ds PUs, i is no ewo hy o
men ion ha low mola masses a e usually ob ained, which limi s he mechanical p ope ies. I has
also o be poin ed ou ha he solubili y limi s and he use polys y ene based calib a ion make
un eliable he SEC measu emen s o he molecula weigh s complica ing he compa ison be ween
esul s epo ed by di e en g oups.
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
17
Figu e 3: S a egies owa ds an imp o ed aminolysis o cyclic ca bona es – adap ed om Maisonneu e e al.19 Co nille e al.15 and Ca é e al.20
Rep in ed wi h pe mission om Chem. Re . 2015, 115, 22, 12407-12439. Copy igh 2020 Ame ican Chemical Socie y.
Chap e 1 – Pa A
18
2.3. Valo iza ion o NIPUs
In sho , in spi e o being e y a ac i e pa hways, bo h ansu e haniza ion and PHU o ma ion
a e s ill su e ing om limi a ions co ne ing hem a he academic in e es . Ve y ecen esea ch
ha e been ocused on he po en ial use o PHUs as ma e ials, no ably by designing e y speci ic –
and o en bio-based – monome s capable o polyme izing in bulk.6,10,53–61,30,31,47–52 This allowed o
he g owing knowledge o he s uc u e-p ope ies ela ionship o NIPUs ha ha e been
summa ized in a e iew om 2016.62 In his con ex , he e is a g owing in e es in he alo iza ion
o NIPUs ia he design o polyme -polyme hyb ids (also called H-NIPUs) ha will be desc ibed in
he nex sec ion o his e iew – Figu e 4.
Figu e 4: Po en ial alo iza ion pa hways o NIPUs owa ds hei indus ial implemen a ion (adap ed om Caillol
and cowo ke s15)
3. Hyb id-NIPUs: no el ma e ials o a b oad ange o p ope ies
Hyb id-polyme s a e wo o mul iphase composi es in which each phase is o med by a di e en
ma e ial and a leas one o hem is a polyme . Polyme -polyme hyb ids a e o med by di e en
polyme s. The esul ing p ope ies o he inal composi es usually a e a syne gis ic combina ion o
hose o he cons i u ing ma e ials. Polyme -polyme hyb ids can be o med by simply mixing wo
polyme s oge he , bu mo e complex s uc u es can also be achie ed by g a ing. This usually helps
p e en phase sepa a ion ha can occu especially when he wo polyme s ha e a poo
compa ibili y. Qui e a ew examples o hyb id NIPUs (H-NIPUs) ha e been published and a e
summa ized in his e iew as well as he unde lying challenges ha a e ising om such
echnologies.
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
19
3.1. NIPU-Epoxy
The syn hesis o NIPU-epoxy hyb ids is he eldes p ocess o he o ma ion o H-NIPU.63 In ha
wo k NIPUs we e used as modi ie s in o de o imp o e he lexibili y o epoxy esins o lacque s
and adhesi e applica ions.
This pionee ing wo k inspi ed nume ous esea ches, ha we e well desc ibed by Figo sky.64 In
2017, Co nille e al.15 sugges ed a classi ica ion o h ee di e en chemical pa hways owa ds he
o ma ion o a NIPU-Epoxy hyb ids - Scheme 3. The i s ou e consis s in eac ing pa ially
ca bona ed epoxy compounds wi h a polyamine. Polyamines a e able o eac wi h bo h he epoxy
and ca bona e moie ies o yield H-NIPUs. The second al e na i e is a 2-s ep p ocess in which a NIPU-
p epolyme is o med p io o eac ing in a second s ep o o m he inal H-NIPU. Finally, he
o ma ion o so-called Hyd oxy U e hane Modi ie s (HUM) has ecen ly been epo ed as ano he
possibili y. I consis s in o ming a mono-hyd oxy u e hane ha upon eac ion wi h a polyepoxy
yields he inal H-NIPU. In all cases, i can be conside ed ha he polyme -polyme hyb ids o m
in e pene a ing ne wo ks (IPN) in which he NIPU is angled up wi h c osslinked epoxy esin.15,65
Scheme 3: Di e en ou es owa ds he o ma ion o polyme -polyme NIPU-Epoxy hyb ids – adap ed om
Co nille e al.15

Chap e 1 – Pa A
20
3.1.1. Epoxy-NIPUs h ough he eac ion o pa ially ca bona ed epoxy
compounds
The pa ial ca bona ion o epoxidized compounds was he i s app oach o syn hesize epoxy-
NIPU hyb ids, likely due o he ease o access o he aw ma e ials a s ake in his syn he ic p ocess.
Rokicki e al. pionee ed his ype on syn he ic p ocess by pa ially ca bona ing a bisphenol-A
diglycidyl e he (BADGE)-based epoxy esin by ixa ion o CO2.63 Di e en deg ees o modi ica ions
we e achie ed be o e u he cu ing wi h ie hylene e amine (TETA) o o m a 3D ne wo k -
Scheme 4.
Scheme 4: BADGE-based H-NIPU h ough he amine cu ing o a pa ially ca bona ed epoxy esin
The au ho s no iced an inc ease in iscosi y wi h an inc easing deg ee o ca bona ion o he
modi ied epoxy esin, ha was explained by he p esence o a high densi y o H-bonds wi hin he
polyme . La e he e ec o ca bona ion on he iscosi y was ound o be epoxy- esin dependen .66
The eac i i y o he pa ially ca bona ed mac o-monome wi h TETA was hen measu ed by
de e mining he gela ion ime. I was ound ha he gela ion ime dec eased by inc easing he
ca bona e con en , hence sugges ing ha he ene ge ic ba ie o he eac ion was highe o he
epoxy han o he cyclic ca bona e moie ies. In e es ingly, he in oduc ion o ca bona e moie ies
also allowed o dec ease bo h he in ensi y o he eac ion exo he m as well as he ime needed o
each i , making such a p ocess e y in e es ing o sa e y pu poses should high amoun s o ma e ial
be p oduced. Those indings we e also con i med by he wo k o Bü gel who an a mechanis ic s udy
o his polyme iza ion p ocess.40 T ying o go beyond he use o pa ially ca bona ed BADGE- esin,
hey pe o med ano he s udy by syn hesizing linea elechelic oligome s.67 I was ound ha bo h
he deg ee o ca bona ion oge he wi h he unc ionali y o he cu ing amine we e playing a ole in
he p e e ence o he amine o eac ei he wi h he cyclic ca bona e o wi h he epoxy moie y. Mo e
p ecisely, p ima y amines would a he eac wi h ca bona e moie ies whe eas seconda y amines
would eac wi h bo h ca bona e and epoxy moie ies.40,65,67 A lowe deg ee o co alen c osslinking
in he inal IPN was hen ob ained. The eac ion empe a u e was also ound o play a c ucial ole in
he chemical p ocess. Indeed, inc easing he eac ion empe a u e led o highe con e sions,67,68
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
21
sho e gela ion imes,63,66,68 lowe iscosi y,63,68 be e homogeniza ion o he mix u e, and
p omo ed eac ion wi h he epoxy moie y o a highe ex en .63,68 Howe e , side eac ions we e also
no iced s a ing a 100 °C, sugges ing ha he e is oom o op imiza ion o he eac ion
empe a u e, which can be e y sys em-dependen .40 When conside ing he mo-mechanical
p ope ies o he o med H-NIPUs, supe io p ope ies we e ob ained o he modi ied epoxy esins,
especially in e ms o impac esis ance, ha dness, and comp essi e s eng h.66 Good ensile
p ope ies could also be ob ained , ha we e a ibu ed o a physical c osslinking ha occu s in he
ob ained IPN which can s ill be explained by he p esence o un eac ed cyclic ca bona e moie ies
o ming H-bonds wi h he –NH- unc ions o he hyd oxyu e hanes moie ies o med upon
polyme iza ion - Scheme 5. As an ou come, syne ge ic e ec s we e also ob ained when
hyd oxyu e hane-con aining polyamines we e syn hesized and inco po a ed in o NIPU-Epoxy
hyb ids.68–71
Scheme 5: Physical c osslinking by H-bonding in Epoxy-NIPU hyb ids
Figo sky e al. (Polyma e L d) pa en ed a p ocess in which pa ially epoxidized compounds we e
cu ed wi h an epoxy esin and oligome ic amines o he p epa a ion o H-NIPUs o be used o
p epa ing cons uc i e glues, sealan s, coa ings, cons uc ion ma e ials among o he s.72
3.1.2. Epoxy-NIPUs h ough he eac ion o homo elechelic p epolyme s
wi h cu ing agen s
This chemical pa hway elies on a 2-s ep p ocess in which an amino- elechelic NIPU p epolyme
is i s o med by eac ion be ween a bis-cyclic ca bona e and an excess o diamine monome . The
amino- elechelic NIPU (and mo e speci ically in his case a PHU) p epolyme is subsequen ly cu ed
Chap e 1 – Pa A
22
wi h an epoxy compound – Scheme 6.61,73,74 This echnology is pa icula ly appealing o he design
o ma e ials wi h de ined sequences o so and ha d segmen s wi hin he inal 3D-hyb id ne wo k.
Scheme 6: NIPU-Epoxy H-NIPU o ma ion h ough he p epa a ion o poly(p opylene oxide) bis-cyclic ca bona e
amino homo elechelic p epolyme p io o u he cu ing wi h a bis-epoxy compound61,73,74
Mos published occu ences ely on he p epa a ion o poly(p opylene oxide) bis-cyclic
ca bona e-based amino- elechelic p epolyme s. The challenge in his eac ion is o o m
p epolyme s o su icien ly high chain leng h while limi ing side- eac ions. To do so, se e al ypes
o diamines61,74 we e u ilized in he syn he ic p ocess, and p ocess pa ame e s such as he eac ion
ime,73,74 he eac ion empe a u e74 and ca alysis74 we e in es iga ed. In gene al, low molecula
weigh s we e ob ained due o he excess o diamine used.
When unning model eac ions be ween poly(p opylene oxide) bis-cyclic ca bona e and
e hylene diamine (EDA),74 i appea ed ha he selec ion o he eac ion empe a u es was a
comp omise be ween se e al pa ame e s. I was ound ha a empe a u e o 90°C allowed as
kine ics (a ound 100 min o he eac ion o each i s maximum con e sion, gene ally eaching a
alue o 90°-95°C), coun e -balanced he high iscosi y o he eac i e mix u e and a oided he
ex en o oo many side eac ions (such as u ea o ma ion by he eac ion o he amine moie ies on o
he o ming hyd oxyu e hanes).The use o ie hylenediamine as ca alys imp o ed he kine ics o
he eac ion bu could no diminish he ex en o hose side- eac ions. Mo eo e , ace o un eac ed
ca bona e could s ill be obse ed.
When cu ing he amino- elechelic p epolyme s wi h bisphenol-A diglycidyl e he (BADGE),74 he
a io be ween he amine and epoxy moie ies played an impo an ole in he de e mina ion o he
mic os uc u e o he inal hyb id ma e ials. When oo low NH2/Epoxy a ios we e used, ca bona e
moie ies could s ill be obse ed by in a ed spec oscopy (FTIR) and scanning elec on mic oscopy
(SEM) analyses e ealed non-homogeneous mic os uc u es, ha we e a ibu ed o an incomple e
c osslinking o he ma e ial.
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
23
Inc easing he NH2/Epoxy a ios led o a be e c osslinking o he ma e ial as shown by ensile
and swelling es s, and SEM analyses (con inuous mo phologies we e obse ed).
Finally, when oo high amoun s o diamine we e inco po a ed in o he o mula ion, mo e linea
s uc u e o H-NIPUs we e ob ained and highe elonga ions a b eak could be ob ained h ough
ensile es s. Simila ends we e ob ained wi h o he diamines e en i sho e gela ion imes we e
ob ained.
Sho ening o he gela ion imes we e obse ed when seconda y amines diamines - namely
die hylene iamine (DETA), ie hylene e amine (TETA) and e ae hylene pen amine (TEPA) -
we e used in he cu ing p ocess wi h BADGE. This was a ibu ed o he eac ion be ween he inne
seconda y amines and BADGE, hus imp o ing he c osslinking deg ee o he inal ma e ials.61,74 The
impac o he NH2/Epoxy was ound o ha e a simila end on all kind o p ope ies: mechanical
( ensile, ha dness), he mo-mechanical (by dynamic mechanical he mal analysis - DMTA) and
swelling abili y in sol en s – namely, he e is an in e media e alue a which he H-NIPUs a e ha de ,
exhibi highe Young’s moduli, ensile s eng h, and lowe elonga ion a b eak.74
In a e y ecen s udy, Ke e al. s udied he in luence o he syn he ic p ocess o he NIPU on o
he p ope ies o he inal H-NIPUs.75 They in es iga ed he in luence o me hanol as a sol en o
ci cum en he H-bonding o ma ion as well as he in oduc ion mode o he eagen s while o ming
amino- elechelic NIPUs (in his case also, a poly(p opylene oxide)-de i ed bis-cyclic ca bona e was
eac ed wi h e hylene diamine – EDA). D ama ic impac s on he molecula weigh s o he NIPUs
oligome s, and hei beha io s when cu ing wi h BAGDE we e obse ed. In pa icula , hey showed
ha he highe he molecula weigh s o NIPU oligome s, he highe he gel con en (>90 %) and he
highe he Young’s modulus and he ensile s eng h.
The in oduc ion mode o he NIPU monome s was o ex eme impo ance, especially when using
me hanol as he sol en . The au ho s compa ed he ob ained NIPUs ob ained when adding bo h he
monome s a he same ime, ha ing a p og essi e addi ion o he diamine on o he bis cyclic
ca bona e (bisCC) p e-dissol ed in me hanol o ha ing a p og essi e addi ion o he bisCC on o he
diamine p e-dissol ed in me hanol. In he i s case, a apid eac ion a e was obse ed, bu u ea
o med (due o he eac ion be ween he o med u e hane moie ies and he un eac ed amine). This
esul was e en wo se wi h he egula addi ion o bisCC in o an EDA solu ion, due o he highe
concen a ion o he diamine in he eac i e mix u e. The las mode o in oduc ion yielded a NIPU
wi h bo h he highes molecula weigh o all as well as a lowe kine ics o o ma ion o u ea as
opposed o ba ch mode. I was ound ha i in luenced he
Co nille e al. exempli ied an in e es ing example o c osslinking wi h a i- unc ional epoxy
compound.73 Qui e logically, ha de ma e ials exhibi ed a lowe swelling index and a highe deg ee
o c osslinking was ob ained when using such a cu ing agen .
In he case o cyclic ca bona e- elechelic oligo NIPUs  e e o he case excess ca bona e in
Scheme 3), he majo challenge consis s in he high iscosi y a ising om he p esence o he
Chap e 1 – Pa A
30
Kalinina e al. epo ed he copolyme iza ion o 3-(2- inyloxye hoxy)-1,2 p opylene ca bona e
(VEOPC) and N-phenyl maleimide (a ound equimola composi ion) in me hyle hylke one (MEK)
using azobisisobu y oni ile (AIBN) as he mal ini ia o .86 The ob ained copolyme s we e pos -
unc ionalized wi h e hylene diamine (EDA) and hexame hylenediamine (HMDA) o o m H-NIPUs
ha we e used as coa ings. They exhibi ed good sol en esis ance, low mois u e abso p ion bu
poo adhesion o me al and poo impac s eng h. Webs e and C ain s udied he copolyme iza ion
o inyl e hylene ca bona e (VEC) wi h inyl es e s.42 Fu he ca bona e-amine pos -
unc ionaliza ion s udies we e pe o med in p opylene glycol monome hyl e he . P ima y amines
bo n on o p ima y ca bons we e p e e ed. I was shown ha he s oichiome ic a io be ween he
cyclic ca bona e moie ies and he amine was o g ea impo ance o he sol en esis ance, namely,
he less amine was inco po a ed in o he o mula ion, he lowe he sol en esis ance. This esul
was howe e balanced by he ac ha he e was a limi ing alue abo e which no u he
imp o emen was obse ed. This was co ela ed wi h he ac ha he c osslinking eac ion eaches
a maximum con e sion, which is a classical esul in PHU chemis y. O he wise, good gloss,
pendulum ha dness and impac esis ance we e obse ed o he o med coa ings.
Cyclic ca bona e (me h)ac yla e (CC(M)A) polyme iza ion has been ex ensi ely s udied and
epo ed in he scien i ic li e a u e.84 Cyclic ca bona e me hac yla e (CCMA) can be syn hesized
h ough many eac ions pa hways ha ha e been summa ized by Webs e 95 and Caillol.84 Howe e ,
he ca bona ion eac ion by ca aly ic ixa ion o CO2 on o glycidyl me hac yla e (GMA) emains he
main pa hway. I is impo an o men ion ha pu e CCMA alone is uns able, bu s able up o 100 °C
when unpu i ied acco ding o Endo e al.99 This ins abili y can s ill be an issue a e polyme iza ion.
The e o e, he e is a gene al ag eemen on he ac ha he adical polyme iza ion o glycidyl
me hac yla e – GMA – ollowed by i s ca bona ion eac ion wi h CO2 p esen s ad an ages wi h
espec o he di ec polyme iza ion o CCMA - Scheme 10.100–102
Scheme 10: Di e en syn he ic pa hways owa ds he o ma ion o poly(CCMA) – adap ed om Endo and
cowo ke s103

Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
31
Some esea ch eams ied o make CCMA-con aining oligome s eac wi h amine-con aining
compounds o yield hyd oxyu e hane. Kiha a e al. hus unc ionalized CCMA-con aining oligome s
wi h bu ylamine, benzylamine, cyclohexylamine and dibu ylamine.99 The au ho s showed ha an
excess o amine as opposed o he CCMA uni s was necessa y o eaching ull con e sion. Seconda y
amines ba ely eac ed due o s e ic hind ance. Finally, when a diamine such as hexame hylene
diamine (HMDA) was in oduced wi h a 1:1 a io, gela ion occu ed a e 1.5 h in dime hylsul oxide
(DMSO). The in a ed (IR) analysis e ealed ha he eac ion was no comple e since aces o cyclic
ca bona e and amine could be obse ed, apped in he polyme ne wo k. The ob ained ilm was
epo ed as bo h ha d and lexible. The same eam published100 he pos - unc ionaliza ion o a
copolyme o CCMA and GMA 0:70, Mn=000 g/mol, Ɖ=.5 ia an aminolysis eac ion wi h
bu ylamine. In his case, ca e ul a en ion be ween he eac i i y o he oxi ane and he ca bona e
moie ies should be paid. I an acidic ea men was pe o med p io o aminolysis, hen he oxi ane
moie ies would open and he amine would selec i ely eac on o he ca bona e moie ies. The
ob ained polyme s displayed inc eased solubili y in wa e and me hanol, which was no he case
be o e unc ionaliza ion wi h he amine. When he aminolysis was pe o med be o e he acidic
ea men , c osslinking h ough an epoxy-like mechanism occu ed and made he inal polyme
insoluble. Finally, in 2010, Jana e al. used a om ans e adical polyme iza ion (ATRP) in o de o
syn hesize homopolyme s, iblock copolyme s and e polyme s bea ing CCMA moie ies in pendan
chains.96 They pos - unc ionalized he CCMA moie ies wi h 2-phenyle hylamine in o de o modi y
he solubili y and we abili y p ope ies o he ob ained polyme s. The eac ion was ca ied ou in
dime hyl o mamide (DMF) and di e en deg ees o unc ionaliza ion we e achie ed. Only 40 % o
unc ionaliza ion was enough o make he polyme s soluble no only in pola ap o ic sol en s such
as DMF and DMSO bu also in mo e common sol en s such as ace oni ile (ACN) and
e ahyd o u an (THF). Highe ex en s o unc ionaliza ion (~90 %) allowed solubilizing he
polyme s in sol en s such as chlo o o m. Finally, he ilms’ p ope ies we e s udied, and i was
ound ha unc ionalizing he CCMA-con aining polyme s helped ansi ioning om a qui e b i le
o uni o m, anspa en and con inuous ilms when cas ing hem on o glass subs a e using DMF as
sol en . The wa e con ac angle, while s ongly depending on he polyme composi ion, was shown
o con inuously inc ease wi h he deg ee o unc ionaliza ion in spi e o he concomi an appea ance
o hyd oxyl g oups. This was a ibu ed o he e ec o he hyd ophobic side g oup o he 2-
phenyle hyl amine used. This sugges s ha uning o he hyd ophilic/hyd ophobic balance o he
inal polyme could p obably be achie ed by changing he amine.
Such echnologies we e also pa en ed, no ably by Figo sky e al.104,105 who claimed he o ma ion
o coa ings based on he cu ing eac ion be ween cyclic ca bona e me hac yla e (CCMA) and amines.
They also mixed hose echnologies wi h he p e iously desc ibed Epoxy-NIPUs ob aining
in e es ing mechanical p ope ies wi h an a e age ensile s eng h o 40 MPa and an a e age
elonga ion a b eak o 55 % depending on he o mula ion.104 Iwamu a and cowo ke s also pa en ed
aminolysis o cycloca bona e-based oligome o p oduce coa ing o au omo i e applica ions.106
Chap e 1 – Pa A
32
In e es ingly, CCMA has been inco po a ed in o o mula ions o emulsion copolyme iza ion.
Yang e al.107 pa en ed an in e es ing p ocess in which di e en la exes we e p epa ed, some
bea ing CCMA moie ies and o he s bea ing amines. I was shown ha hose la exes we e able o
c osslink. The CCMA- unc ionalized la exes we e capable o o ming ilms and u he addi ion o
polyamine induced c osslinking. When he CCMA- unc ionalized and amine- unc ionalized la exes
we e blended oge he , he o med ilm could be c osslinked by cu ing a oom empe a u e du ing
24 h. These ilms exhibi ed gel con en s a ound 60 % in ace one, as well as good wa e esis ance.
O he pa en s om BASF disclosed he use o CCMA- unc ionalized coa ings ha we e able o
c osslink acco ding o he same mechanisms desc ibed be o e using p ima y amine agen o pain
applica ions.108–110
Finally, he case o cyclic ca bona e ac yla e (CCA) has also been s udied, al hough o a lesse
ex en han o CCMA. The syn he ic ou es owa ds he o ma ion o CCA a e e y simila o hose
o syn hesize CCMA.111–114 Yields o 85% we e ob ained h ough he ca bona ion o glycidyl ac yla e
wi h CO2 a 60°C in he p esence o inhibi o s (4-me hoxyphenol).114 The eac ion condi ions as well
as he pu i ica ion s eps a e o ex eme impo ance since he monome can su e om side-
eac ions o e en s a polyme izing a empe a u es as low as 40 °C. Homopolyme iza ion o CCA
in solu ion usually led o insoluble polyme s, which was explained because o he ans e eac ion
om he ca bona e ing wi h p o on emo al and adical ecombina ion.99,115 The copolyme iza ion
wi h 2-e hylhexyl ac yla e was ound o be a solu ion o yield soluble polyme s in benzene,
chlo ina ed sol en such as dichlo ome hane and e ahyd o u an.115 Pho opolyme iza ion was also
implemen ed.116,117 To he bes o ou knowledge, only one example has been epo ed in which he
ca bona e moie ies we e unc ionalized wi h bu ylamine.115 Kine ic s udies on model molecules
showed ha bulk p ocesses we e as e han solu ion p ocesses.115
3.2.2. (Hyd oxy)u e hane me hac yla es – (H)UMAs
(Hyd oxy)u e hane me hac yla es ((H)UMAs) a e sho oligome s (usually dime s o ime s)
syn hesized by aminolysis o a cyclic ca bona e and an amine, one o hem bea ing a leas one
me hac yla e moie y. A ypical isocyana e- ee syn he ic app oach consis s in he o ma ion o a diol,
which is subsequen ly unc ionalized in o a dime hac yla e componen (Scheme 11), bu mo e
complex s uc u es ha e also been designed.21,118,119
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
33
Scheme 11: Fo ma ion o UMAs ia he aminolysis o e hylene ca bona e ollowed by subsequen unc ionaliza ion
(H)UMAs we e o iginally designed o be used as eac i e diluen s. Such compounds can o
example be employed in ul a iole (UV)-cu able coa ings, which a e gaining in e es o hei as
cu ing and low ene gy consump ion.120 Figo sky e al. epo ed UV-cu able conc e e loo coa ings
able o cu e ins an ly.64 A gene al composi ion o a UV-cu able coa ing is a mix u e o pho oini ia o ,
oligome and eac i e diluen , he la e being used o dec ease he iscosi y o he global mix u e,
while polyme izing in he c osslinking eac ion o o m a 3D-ne wo k. Acco ding o Wang and
Soucek, mono- unc ional eac i e diluen s usually lead o a dec eased modulus and inc eased
duc ili y whe eas bi- and/o mul i- unc ional eac i e diluen s
ha e he opposi e e ec .118 I was also ound ha he in oduc ion o ac ylic moie ies in o he
(H)UMAs was a sui able me hod o o e coming he yellowing e ec o he PHU caused by
sunligh .105 Due o hei e sa ile composi ion, and he di e si y o componen s ha can be used o
copolyme iza ion pu poses, UV-cu able o mula ions can ind o he applica ions such as
biomedical, o ins ance ia he de elopmen o injec able liquids, pas e o gels (den al composi e
applica ions being a po en ial example).119,121
Assump ion and Ma hias published in 2003 a me hod o syn hesizing isocyana e ee u e hane
me hac yla es UMAs ia he ing opening aminolysis o e hylene ca bona e wi h a ious amines.119
Hexame hylene Diamine (HMDA), 3-amino-1-P opanol and 2,2-dime hyl-1,3-p opanediamine we e
used, and me hac ylic anhyd ide was u ilized in he unc ionaliza ion s ep in o de o ca aly ically
eac wi h all he hyd oxyl g oups - Figu e 7. The kine ics o he adical pho opolyme iza ion o he
o med UMAs was measu ed and ex emely as polyme iza ion a es (pla eauing con e sion a e
100 s eac ion ime) we e ob ained. An immedia e au o-accele a ion was no iced and he as es
polyme iza ion a es we e eached a e 4 o 5s. The eac ion a e was ound o s ongly depend on
he monome s uc u e o he UMA. In pa icula , he p esence o H-bonding, allowing p e-
associa ion e ec s be ween he monome s enhanced he polyme iza ion a es, which is in
acco dance wi h he wo k o Jansen e al.92 Wang and Soucek118 syn hesized a se ies o simila
eac i e diluen s ollowing a simila p ocedu e. They a ied he s uc u e o he cyclic ca bona e
Chap e 1 – Pa A
34
compound o in oduce an addi ional me hyl moie y. 2-(me hac yloyloxy)e hyl 2-
(me hac yloyloxy)e hylca bama e (EOAED), 2-(me hac yloyloxy)e hyl 3-
(me hac yloyloxy)p opylca bama e (POAED), and 1-(me hac yloyloxy)p opan-2-yl 3-
(me hac yloyloxy)p opylca bama e (POAPD) we e hence syn hesized by unc ionaliza ion wi h
me hac ylic anhyd ide - Figu e 7. The o med eac i e diluen s we e es ed in a o mula ion
con aining an oligo polyes e . I was obse ed a gene al inc ease o ensile s eng h and elonga ion
a b eak when using he non-isocyana e e sion o he eac i e diluen s. In mo e de ails, and as
al eady obse ed in he case o Epoxy-NIPUs, he e was an op imum concen a ion o eac i e
diluen o be in oduced in he o mula ion. Below his alue, ensile s eng h and elonga ion a
b eak inc eased wi h he eac i e diluen con en . Abo e i , hey usually dec eased. Glass ansi ion
empe a u es (Tgs), - ansi ion empe a u es Ts and gel con en s also inc eased wi h he eac i e
diluen con en , due o he highe c osslinking densi y. One d awback is he wa e sensi i i y since
he wa e abso p ion was ound o inc ease wi h he inc ease in eac i e diluen con en . This was
a ibu ed o he inc ease o es e -u e hane g oup concen a ion, a pola g oup capable o
in e ac ing wi h wa e . Finally, he eac i e diluen s inc eased he impac esis ance.
Figu e 7: Reac i e diluen s p epa ed by Assump ion e al.119 and Wang e al.118
Simila ypes o mul i- unc ional hyd oxyu e hane me hac yla es (HUMAs) we e p oposed by
Bie na and Rokicki in 2005.21 The syn he ic app oach elies on he aminolysis eac ion o glyce ol
ca bona e wi h a diamine. The o med hyd oxyu e hane quad iols (3 isome s can be ob ained) we e
subsequen ly modi ied by eac ing wi h me hac yloyl chlo ide o me hac ylic anhyd ide o o m he
co esponding quad ime hac yla e - Scheme 12. Va ious amines could be used o he syn hesis,
including 1,3-diaminop opane, 1,2-diaminoe hane and isopho one diamine (IPDA). Amino-alcohols
we e also used and yielded i unc ional u e hane me hac yla es.
Scheme 12: Mul i unc ional HUMAs ia unc ionaliza ion o glyce ol ca bona e-based quad iols by me hac yloyl
chlo ide acco ding o Bie na and Rokicki.21 (No e ha DMAP s ands o 4-Dime hylaminopy idine)
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
35
Following a simila app oach, he same au ho s21 used ca bona ed- Bisphenol-A Diglycidyl E he
(BADGE) in o de o syn hesize mul i unc ional HUMAs. This p ocess was di e en om he
p e iously desc ibed one in he sense ha a bis cyclic ca bona e compound was used ins ead o a
mono cyclic ca bona e. The quad i- unc ionali y was b ough h ough he eac ion wi h an amino-
alcohol ha was u he modi ied wi h me hac yloyl chlo ide o yield he inal p oduc s - Scheme
13.
Scheme 13: Mul i unc ional HUMAs ia unc ionaliza ion o ca bona ed-BADGE-based quad iols by me hac yloyl
chlo ide acco ding o Bie na and Rokicki.21 (No e ha DMAP s ands o 4-Dime hylaminopy idine)
The syn hesized esins exhibi ed high lexu al s eng h a e cu ing. The BADGE-based esins
had supe io oughness han a e e ence esin o den al composi ions. This high lexu al s eng h
in combina ion wi h a low iscosi y make such componen s ex emely in e es ing eac i e diluen s.
Due o he high c osslinking densi y, a high ha dness is usually ob ained.
A en ion has ecen ly been paid owa ds he de elopmen o new kinds o ma e ials o 3D –
p in ing pu poses.122 The abili y o (Hyd oxy)u e hane Me hac yla es - (H)UMAs o
pho opolyme ize makes hem pe ec candida es o such applica ion. To he bes o ou knowledge,
wo esea ch eams ha e ecen ly published isocyana e- ee pa hways o de elop 3D-p in able
esins. The eam o Chen p oposed wo possible polyme iza ion pa hways o he design o 3D-
p in able esins based on he o ma ion o a diu e hane adduc ia he aminolysis o a inylic- (o
me hac ylic-) 6-membe ed cyclic ca bona e monome wi h a diamine. The au ho s sugges ed wo
polyme iza ion pa hways: a i s gene a ion o adduc s eac ing in a adical pho oinduced p ocess
whe eas a second gene a ion which p oceeded h ough a hiol-ene ou e - Scheme 14. 123,124

Chap e 1 – Pa A
36
Scheme 14: 3D-p in able HUMAs based on a 6-membe ed cyclic ca bona e diu e hane adduc s, u he
polyme ized ei he by adical pho opolyme iza ion (1s gene a ion)123 o ia hiol-ene chemis y (2nd
gene a ion)124 – adap ed om Pyo e al.
In he i s gene a ion, he diu e hane adduc con aining me hac ylic moie ies was o med i s
and hen c osslinked ia an ul a iole (UV)-induced p ocess o yield he inal ma e ial. The ob ained
p oduc s we e amo phous and s able up o empe a u es highe han 200 °C. They we e 3D-p in ed
in a con inuous op ical p in ing sys em using a laye by laye polyme iza ion me hodology.
Ma e ials o unable s i ness wi h smoo h con ou s could hus be designed. In he second
gene a ion, a inylic cyclic ca bona e was copolyme ized also in a UV-induced p ocess wi h bi- o
quad i- unc ional hiols. The biocompa ibili y o hese ma e ials o po en ial biomedical
applica ions was also e alua ed. (Hyd oxy)u e hane Me hac yla es - HUMAs syn hesized h ough
he eac ion o a se ies o diamines wi h wo equi alen s o cyclic ca bona e me hac yla e (CCMA)
in a bulk p ocess o 3D-p in ing pu poses.125 . The HUMAs we e u he copolyme ized wi h 4-
me hac yl-oylmo pholine (ACMO) wi h he help o a pho o-ini ia o . The s uc u e o he diamine
was ound o ha e a g ea in luence on he iscosi y o he esul ing ac ylic esin o mula ion, bu all
o hem emained wi hin indus ially accep able iscosi y anges. Sho and lexible e he amines
we e highligh ed as p e e able eac i e diluen s since hey o e ed a comp omise be ween low
iscosi y and e y good mechanical pe o mance (Young modulus o 3600 MPa, and ensile s eng h
o 85 MPa we e measu ed in he case o 1,8-diamino-3,6-dioxaoc ane-based HUMAs).
Mul i unc ional HUMAs ob ained by unc ionaliza ion o he pendan OH g oups wi h me hac yla e
anhyd ide we e also used leading o an inc ease in he mo-mechanical p ope ies (Young modulus
o 4200 MPa ins ead o 3600 MPa and a Tg o 173 °C ins ead o 86 °C we e ob ained).
The e a e wo examples o he use o u e hane me hac yla es (UMAs) in wa e bo ne
sys ems.126,127 The UMAs we e p epa ed ia he aminolysis eac ion o e hylene ca bona e wi h a
se ies o alipha ic amines p io o he unc ionaliza ion wi h me hac ylic anhyd ide - Scheme 15.126
This p ocess allowed o a ge di e en hyd ophobici y le el o he eac i e diluen , ha we e
subsequen ly copolyme ized wi h MMA/BA in a seeded semiba ch emulsion polyme iza ion in
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
37
monome s a ed condi ions, wi h a solids con en o 30 w %. The same yea , he same eam
in es iga ed mo e deeply he case o BEM (bu yl-based UMA, a=3 in Scheme 15).127 The emulsion
polyme iza ion p ocess (ba ch S semiba ch mode) as well as he pa icle mo phology
(homogeneous S co e-shell) and he loca ion and concen a ion o BEM wi hin he pa icle (in he
co e o in he shell) in e ms o ilm p ope ies we e he ocus o he s udy. Those wo ks a e
e iewed in mo e de ails in he Pa B o his Chap e dealing wi h wa e -based NIPUs.
Scheme 15: P epa a ion o mono- unc ional UMAs o di e en hyd ophobici y acco ding o Meng e al.126
3.2.3. Unsa u a ed NIPU-p epolyme s: Poly(hyd oxy)u e hane
me hac yla es – P(H)UMAs
3.2.3.1. H-NIPUs ia adical polyme iza ion
 Radical eac i e elechelic polyu e hanes
Longe isocyana e- ee u e hane me hac yla es UMAs (oligoUMA) we e designed by Ochiai and
U suno by unc ionalizing oligome ic polyu e hane diols wi h glycidyl me hac yla e (GMA).128 The
polyu e hanes (PUs) o igina e om a ansu e haniza ion p ocess yielding he OH- elechelic
oligome s. The ing opening o GMA did no p oceed o ull con e sion so ha an excess was
employed o maximizing he ex en o unc ionaliza ion. The oligoUMAs we e u he
copolyme ized wi h me hyl ac yla e (MA) (in a a io 50:50 in eac i e moie ies) in
dime hyl o mamide (DMF) a 60 °C using AIBN as he mal ini ia o o 24 h - Figu e 8. The o med
polyme almos ins an aneously became a gel, which was insoluble in any o ganic sol en . The
o med polyme was composed o a ha d PU segmen and so poly(me hyl me hac yla e) segmen s.
A e he mal ea men in he DSC, he PU and he ac yla e phase became miscible and a single Tg
o 34 °C was ob ained. The Tg was ound o be highe han bo h he na i e PU and poly(MA), a
phenomenon ha was a ibu ed o he es ic ed mo ion o he polyme chains in he 3D ne wo k.
Chap e 1 – Pa A
38
Figu e 8: Copolyme om oligoUMA and MA acco ding o Ochiai e al.128
The g owing in e es in he de elopmen o a mo e sus ainable chemis y is pushing he esea ch
communi y o de elop mo e en i onmen al iendly p oduc s. In his pu pose, Han e al. de eloped
a new kind o poly(es e -u e hane)s ha we e unc ionalized wi h he bio-based i aconic acid -
Scheme 16.129 NIPU p e-polyme s we e syn hesized by ing opening o e hylene ca bona e wi h
a ious diamines. The o med diols we e hen eac ed wi h an excess o i aconic acid and
subsequen polycondensa ion led o adical eac i e elechelic oligo(Es e -U e hane)s. The la e
we e u he cu ed by a UV-induced p ocess wi h dime hylp opionic acid (DMPA). Gel con en s in
he ange 80 o 88 % we e ob ained in ace one. The ensile s eng h depended on bo h he chain
leng h o he diamine and he c osslinking densi y, wi h he bes mechanical p ope ies ob ained in
he case o pu escine-based oligo(Es e -U e hane) (Young modulus o 52 MPa, a ensile s eng h o
2.5 MPa and an elonga ion a b eak o 33 %).
Scheme 16: Fully-bio-based HUMAs unc ionalized by i aconic acid acco ding o Han e al.129
 Hyd oxyl-g oup unc ionaliza ion
The g oup o Endo unc ionalized he pendan OH g oups o isocyana e- ee
oligo(hyd oxyu e hane)s (oligoPHUs)130 by eac ing 2-me hac yloyloxye hyl isocyana e wi h a
ca bona ed Bisphenol-A Diglycidyl E he (BADGE)-based oligoPHU - Scheme 17. The empe a u e
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
39
o he u e haniza ion should be con olled o a oid polyme iza ion o he me hac yla e moie ies.
The e o e, oom empe a u e was p e e ed and a ull con e sion could be ob ained. . The
ad an age o unc ionalizing pendan OH g oups elies on he ac ha he deg ee o
unc ionaliza ion can be con olled. When unc ionalizing he oligoPHU wi h 1 eq. o he isocyana e
compound wi h espec o he hyd oxyl g oups in he oligome , success ul copolyme iza ion wi h
Hyd oxye hylme hac yla e (HEMA), me hyl me hac yla e (MMA) and N-isop opylac ylamide
(NIPAM) was achie ed in dioxane. In all cases, he iscosi y o he polyme iza ion mix u e inc eased
du ing he eac ion un il he o ma ion o insoluble gels. Tgs lowe han o iden ical o ha he
co esponding polyme hacyla es we e measu ed, sugges ing ha he dis ance be ween c osslinking
nodes was su icien ly long o allow mobili y o he inco po a ed PHU chains. I should howe e be
men ioned ha his syn he ic p ocess, despi e being ex emely in e es ing, is un o una ely no ully
isocyana e- ee, which can seem coun e balancing he isocyana e- ee p ocess o ma ion o he
na i e oligoPHU.
Scheme 17: Func ionaliza ion o he pendan OH-g oups o ca bona ed BADGE-based oligoPHUs acco ding o Endo
and cowo ke s130
A e y ecen example, om Caillol and cowo ke s, desc ibes he syn hesis o
hyd oxyu e hane Me hac yla e (HUMA) capable o c osslinking in a he mal pa hway only,
wi hou using any ini ia o .131 A ca bona ed poly(p opylene oxide) diglycidyl e he (sho ened
PPOBC) was eac ed wi h e hylene diamine (EDA) o wi h (e hylenedioxy)die hylamine (EDR)
o o m a diamino- elechelic compound, which was u he unc ionalized wi h he help o
e hylene ca bona e. The o med diol was hen modi ied wi h me hac ylic anhyd ide in o he
co esponding HUMA as desc ibed in Scheme 18. The o med HUMAs we e u he
homopolyme ized o c osslinked wi h ei he benzyl me hac yla e o poly(e hylene oxide)
bisphenol A dime hac yla e.
Chap e 1 – Pa A
46
3.3. O he Hyb id-NIPUs
In addi ion o epoxy and (me h)ac ylic NIPUs, new ypes o hyb ids ha e appea ed in he
scien i ic li e a u e. He ein silicon con aining H-NIPUs and hyb ids combining biopolyme s wi h
NIPUs a e discussed.
3.3.1. Si-con aining H-NIPUs
Silicon and mo e speci ically siloxane con aining H-NIPUs ha e been p epa ed in o de o con e
new kinds o p ope ies o he hyb ids. Siloxane moie ies can be inco po a ed h ough a ious
syn he ic means, ei he in he inne backbone o he inal linea NIPU o by ac ing as c osslinking
agen s bea ing cyclic ca bona e o amine moie ies, hence yielding a b anched o c oss-linked
a chi ec u e. Bo h ou es will be desc ibed.
3.3.1.1. Si- con aining linea H-NIPUs wi h inne siloxane backbones
Endo and cowo ke s and Hanada e al. in oduced in 2014 a PHU con aining siloxane in he inne
backbone o he polyme ma e ial.133,134 Thei pu pose was o achie e imp o ed wa e esis ance
and lexibili y. They designed a 1 po -2 s eps p ocess in which Bisphenol-A Diglycidyl E he
(BADGE) was ca bona ed by CO2 ixa ion p io o eac ing wi h he siloxane con aining diamine -
Scheme 21. P opylene glycol me hyle he ace a e (PGMAC) was a sui able sol en o ob ain he inal
PHU in high yields. When compa ing he siloxane con aining NIPUs wi h a classical NIPU made o
ca bona ed BADGE and dodecanediamine, i was ound ha he highe he siloxane con en , he
highe he solubili y o he o med p oduc s in sol en s o low pola i y such as E 2O. Wa e con ac
angle and lexibili y inc eased as he siloxane con en inc eased. The ma e ials had low glass
ansi ion empe a u es (1 and 26 °C as opposed o 40 °C wi h dodecanediamine).

Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
47
Scheme 21: PHU con aining siloxane-based inne backbone acco ding o Endo and cowo ke s133
As a as we know, only one example o siloxane-con aining bis-cyclic ca bona e compounds has
been pa en ed. This wo k was pe o med by he eam o Hanada135 and p eceded he pa en on
diamino-polysiloxane mac omome s.133 An example o he syn hesized bis-cyclic ca bona e
compounds in p o ided is Figu e 10. The au ho s a ge ed applica ions such as he mal eco ding
medium, a i icial lea he , he moplas ic polyole in esin skin ma e ial and wea he s ip ma e ial.
The ob ained bis-cyclic ca bona es we e u he con e ed by eac ing wi h diamines
(hexameh hylene diamine (HMDA), bis-aminop opylpipe azine, and xylylenediamine we e used).
The numbe a e age molecula weigh s we e in he ange 30000-40000 g/mol depending on he
siloxane-con aining bis-cyclic ca bona e and he diamine used. Tensile s eng hs o a ound 24 o 35
MPa and elonga ions a b eak in he ange o 15 o 83 % we e ob ained, wi nessing he possible
uning o he ma e ial p ope ies.
Figu e 10: Example o a siloxane-con aining bis-cyclic ca bona e mac omonome as pa en ed by Hanada e al.135
Figo sky e al. used a siloxane-con aining mac omonome in hei Epoxy-Amine H-NIPU
sys ems.136 They claimed he syn hesis o nanos uc u ed H-NIPUs ha we e cons i u ed by epoxy-
unc ion, cyclic ca bona e, amine- unc ional and (me h)ac yla e componen s. Among hem, a leas
one epoxy, amine o (me h)ac yla e con ained alkoxysilane moie ies. The o med polyme s
c osslink upon cu ing a ambien condi ions by means o a mosphe ic mois u e, yielding
nanos uc u ed ma e ials wi hou he need o using wa e embedding o addi ion o nano ille s. The
ma e ials exhibi ed imp o ed ab asion esis ance and highe impac esis ance and lexibili y
compa ed wi h a con en ional epoxy esin siloxane based ma e ial ha was used as a e e ence.
Chap e 1 – Pa A
48
3.3.1.2. Si- con aining b anched o c osslinked H-NIPUs wi h ou e siloxane
backbones
Ano he impo an pa hway is he eac ion o siloxane o Si-con aining eagen s bea ing cyclic
ca bona e o amine moie ies.
 Si-con aining eagen s bea ing amine moie ies
Figo sky and cowo ke s de eloped he mos able esins wi h Si-con aining amine componen s
using mul iaminosilane agen s as ha dene s in he cu ing p ocess o hei Epoxy-PHU H-NIPU
p ocess.137 The comme cially a ailable -aminop opyl ie hoxy silane was hyd olyzed o yield he
mul iaminosilane cu ing agen . Simila dend o-silanes con aining a oma ic uni s we e in oduced
in o epoxy and cycloca bona e esins. Once in oduced in o he esins, he alkoxy g oups we e
hyd olysed by he humidi y o ei he he ai o ha o he su ace o he subs a e. The newly buil
silanol-hyd oxyl g oups eac ed wi h he su ace hyd oxyl g oups and o ms s ong bonds, making
hem good adhesion p omo e s.136
Scheme 22: Mul iaminosilane syn hesis acco ding o Figo sky and cowo ke s137
Ano he example is he wo k Na ayan and cowo ke s138 who syn hesized oligo(siloxane-
u e hane) h ough he eac ion o 3-amino-p opyldime hyle hoxysilane (MEC), 3-
aminop opyldie hoxyme hylsilane (DEC) and (3-amino-p opyl ie hoxysilane) (TEC) wi h e hylene
ca bona e. The o med adduc s unde wen a spon aneous ea angemen by condensa ion o he
alkoxysilane g oups wi h he hyd oxyl unc ions esul ing om he ing opening o he e hylene
ca bona e as depic ed in Scheme 23.
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
49
Scheme 23: Oligo(siloxane-u e hane) o ma ion om aminop opyl alkoxysilanes acco ding o Na ayan e al.138
The same eam epo ed he possibili y o une he condensa ion p ocess o hose siloxane-
u e hane adduc s con aining wo alkoxy g oups.139 In anhyd ous condi ion, he monome o med a
hype b anched s uc u e s a ing om an AB2- ype uni . This was no he case unde acidic
condi ion in which a linea s uc u e was o med.
Scheme 24: Condensa ion p ocess o he DEC-p opylene ca bona e adduc acco ding o Ne ayan e al.139
Chap e 1 – Pa A
50
 Si-con aining eac an s bea ing cyclic ca bona e moie ies
Ea ly wo k in his ield was published by Wnek and cowo ke s in 1994, whe e hey epo ed he
syn hesis o polysiloxane polyme s bea ing cyclic ca bona e side chains140 and s udied he in luence
o he p esence o he side ca bona e on he dielec ic p ope ies and ion conduc i i y o ba e y
applica ions. No pos - unc ionaliza ion o he ca bona e moie ies was ca ied ou . Liu e al.141
published in 2017 he syn hesis o cyclic ca bona e con aining polysiloxane compounds o he
p oduc ion o coa ings wi h imp o ed wa e esis ance. Those adduc s we e u he eac ed wi h a
s oichiome ic amoun o diamines, a 100 °C in a mold o 10 h o yield polysiloxane-PHU. Di e en
deg ees o ca bona ion we e es ed in o de o une he concen a ion o hyd oxyu e hane moie ies
in he inal ma e ial - Scheme 25. Di e en ial scanning calo ime y (DSC) analyses e ealed only a
single glass ansi ion empe a u e ha anged om 3 o 60°C depending on he amine and he
deg ee o ca bona ion o he polysiloxane, indica ing ha no phase sepa a ion occu ed. The deg ee
o ca bona ion, namely he ex en o c osslinking, in luenced he mechanical p ope ies by
inc easing he ensile s eng h and Young modulus, bu lowe ing he elonga ion a b eak. The same
beha io was obse ed when inc easing he amoun o cycloalipha ic moie ies o he diamine.
Scheme 25: Polysiloxane-PHU H-NIPUs om cyclic ca bona e-con aining polysiloxanes acco ding o Liu e al.141
Howe e , and despi e he accep able swelling indexes in wa e ( om 3 o 22 w %), he wa e
esis ance dec eased wi h he deg ee o c osslinking. This was a ibu ed o he inc ease in hyd oxyl
moie y concen a ion wi hin he o med ma e ial. In his ega d, in oducing mo e hyd ophobic
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
51
diamines (especially hose con aining cycloalipha ic ings) was a sa is ac o y solu ion o bo h
dec ease he swelling in wa e as well as ob aining ma e ials wi h highe Young moduli and ensile
s eng hs.
 Si- elechelic PHU p epolyme s
To he bes o ou knowledge, only one example o eac i e elechelic-oligoPHUs, in ol ing Si-
con aining chain ends, has been epo ed in he scien i ic li e a u e. This is no su p ising as he
o ma ion o well-de ined eac i e elechelic PHUs is s ill one o he majo unsol ed issues in his
chemis y. This wo k was unde aken by he eam o Caillol who published in 2018 he syn hesis o
sol-gel hyb id-poly(hyd oxyu e hane)s.142 Thei syn he ic p ocess consis s in end-capping
di unc ional PHU monome (namely bis cyclic ca bona es o diamines) wi h siloxane-con aining
amine o mono cyclic ca bona e. A subsequen sol-gel p ocess allowed o he la e c osslinking o
he siloxane homo elechelic PHU chains - Figu e 11. A e y high he mal esis ance, wi h Td5% highe
han 300 °C was ob ained. The p esence o a ubbe y pla eau wi h a modulus in he o de o
magni ude o 107 Pa a e he alpha ansi ion in he Dynamic Mechanical The mal Analysis (DMTA)
measu emen s showed ha he polyme was c osslinked, which was con i med by he gel con en
(90 %) measu ed by ex ac ion o he soluble polyme wi h THF.
Figu e 11: Fo ma ion o Hyb id PHU-siloxane he mose s ia he syn hesis o siloxane homo- elechelic oligoPHUs
– adap ed om Caillol and cowo ke s142

Chap e 1 – Pa A
52
3.3.1.3. POSS-con aining H-NIPUs
Ano he possibili y o in oduce Si-con aining compounds in o NIPUs is h ough he use o
polyhed al oligome ic silsesquioxanes (POSS). This compound has been used o p o ide no el
p ope ies in o ma e ials.143,144 Mechanical p ope ies, he mal s abili y, wa e ole ance o
dielec ic p ope ies we e shown o be posi i ely in luenced when POSS was inco po a ed in o
polyme ma ixes. Liu e al. inco po a ed POSS in o PHU coa ings con aining gallic acid145 o osin143
- Scheme 26. In he i s example, gallic acid-based epoxy esin was ea ed by ca aly ic ixa ion o
CO2 o o m he e aca bona e. The ca bona e was eac ed wi h a ious diamines and also modi ied
wi h epoxidized-POSS componen s in a simila p ocess han he Epoxy-NIPU H-NIPU. The
in oduc ion o POSS inc eased he wa e esis ance o he NIPUs, wi hou being de imen al o
o he p ope ies such as impac esis ance, pencil ha dness o lexibili y. In gene al, he inc ease o
he POSS loading induced an inc ease in he igidi y o he ma e ial (some we e mo e b i le) and
he mal p ope ies (Td50% o e 300 °C by he mo g a ime uc analyses - TGA), which was a ibu ed
o he inc ease in he c osslinking densi y. A simila s udy was pe o med wi h osin-based
ca bona e compounds, wi h a sligh di e ence consis ing in he ac ha bo h epoxidized-POSS and
ca bona ed-POSS we e used in he o mula ion while eac ing wi h a diamine. Simila
enhancemen s in he p ope ies o he composi es we e obse ed upon in oduc ion o POSS in o
he NIPU o mula ions. Fo simila POSS con en s, he epoxy-POSS yielded ma e ials wi h be e
wa e esis ance han he ca bona ed-POSS, which was a ibu ed o he o ma ion o u e hane
linkages. This posi i e impac o he inco po a ion o POSS in o NIPU o mula ions on he
mechanical p ope ies was con i med by Bla mann and Mülhaup .146 They a ge ed he
de elopmen o a sol en - ee p ocess o he p oduc ion o POSS-con aining NIPUs and
in es iga ed he po li e and gel imes o di e en o mula ions while inco po a ing ca bona ed-
POSS. Due o he e y high unc ionali y, he cu ing wi h diamine led o ex emely sho po li e and
gel ime (hund eds o seconds). Because o he imp o emen in p ocessabili y, wi hou being oo
de imen al o mechanical p ope ies, eac i e diluen s based on ca bona ed glycidyl e he s we e
u ilized - Figu e 12. Supe io mechanical p ope ies, wi h Young moduli o excep ional alues (un il
4000 MPa) could hus be ob ained. Un o una ely, no enhancemen in e ms o wa e esis ance was
obse ed, which can be explained by he p esence o hyd ophilic hyd oxyu e hane moie ies.
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
53
Scheme 26: POSS-con aining NIPUs om gallic acid (le ) and osin ( igh ) acco ding o Liu e al.143,145
Figu e 12: POSS-con aining NIPUs acco ding o Bla mann and Mülhaup 146
Chap e 1 – Pa A
54
3.3.2. Biopolyme -con aining NIPUs
Biopolyme s, de ined as na u ally occu ing polyme s, a e gaining an inc easing in e es because
hey a e enewable compounds leading owa ds mo e sus ainable and en i onmen al- iendly
ma e ials. These polyme s do no need o be syn hesized, as opposed o he epoxy and ac ylic esins
desc ibed abo e. By means o wise chemical modi ica ion, he inco po a ion o such compounds can
signi ican ly b oaden he inal p ope ies o he o med ma e ials. The biopolyme s inco po a ed in
NIPUs include na u al ubbe , and de i a i es o wood esou ces, namely annin, lignin and
cellulose.
3.3.2.1. Na u al Rubbe H-NIPUs
In 2017, he eam o Pila d epo ed on he use o na u al ubbe (NR) o he syn hesis o
NIPUs.147 Thei p ocess consis ed in deg ading NR in oligo-isop ene, ha we e u he
unc ionalized in diamino- o bis cyclic ca bona e compounds - Scheme 27. Di e en chain leng hs
o he unc ional oligo-isop ene we e a ge ed (1000 and 2000 g/mol) and es ed in a subsequen
polyme iza ion wi h bis-cyclic ca bona es o diamines. The ad an age o deg ading he NR was no
only o ge a be e con ol o he chain leng h, bu also o ha e oligo-isop ene ha can be dissol ed
in sol en s such as THF and dioxane, hus allowing eac ions in solu ion o o m NIPUs. Dioxane was
ound o be he mos sui able sol en since empe a u es as high as 100 °C we e necessa y o he
eac ion o p oceed. Bulk polyme iza ion was also pe o med. No o ma ion o by-p oduc s such as
u ea o amides was obse ed. In e es ingly, by playing wi h he p ocess’ condi ions and he
ca bona e o amine a io, a 100 % con e sion could be achie ed in he case o ca bona e- elechelic
NRs. Un o una ely, solubili y issues made he cha ac e iza ion by SEC di icul . Low glass ansi ion
empe a u es we e ob ained, anging om -58 o -30 °C. No ewo hy, he longe he chain he lowe
he Tg, which was a ibu ed o he highe lexibili y o he polyme chains by he inc easing amoun
o oligo-isop ene inco po a ed.
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
55
Scheme 27: Na u al Rubbe -based NIPUs (NR-based NIPUs) – adap ed om he wo k o Pila d and cowo ke s147
3.3.2.2. Lignin and annin-based H-NIPUs
 Lignin-based H-NIPUs
The use o lignin is gaining momen um in he ield o he de elopmen o no el polyme
ma e ials. Lignin nowadays is conside ed as he main esou ce o he syn hesis o bio-a oma ic
monome s. I cons i u es 20 o 25 w % o wood wi h a wo ld p oduc ion om he pulp indus y
eaching 50 million ons/yea .148 Because his esou ce is low cos and is no in compe i ion wi h
he ood indus y, subs an ial e o s a e di ec ed owa ds i s alo iza ion. This complex biopolyme
howe e has o be deg aded in smalle building blocks p io o using i . Mos ly polyols a e o med,
which made lignin ex emely popula in he PU chemis y since i could di ec ly eac wi h
isocyana e compounds.149–152
Howe e , qui e sca ce examples o he use o lignin can be encoun e ed in he li e a u e. Among
hem, Lee and Deng published in 2014 an example in which he phenolic uni s o lignin we e used
in combina ion wi h a siloxane-modi ied ca bona ed soybean oil o he design o lignin-based
NIPUs -Scheme 28.153 Du ing he polyme iza ion p ocess, he condensa ion o siloxane moie ies,
yielding –Si-O-Si- g oups, occu ed. When cu ing he inal ma e ials, a 60 °C, lignin ac ed as a
c osslinking agen and he esul ing ensile s eng h inc eased wi h he inc ease in lignin con en .
Howe e , when cu ing a oom empe a u e, he ma e ials we e ound o be much mo e lexible,
which migh be due o an ine icien cu ing. The inc ease in lignin con en inc eased he inal
elonga ion a b eak. The au ho s a ibu ed hese indings o he concomi an c osslinking eac ions,
namely he condensa ion o siloxane moie ies on o hemsel es, and he condensa ion o lignin wi h
Chap e 1 – Pa A
62
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Chap e 1 – Pa A
70
6. Sho ened o ms
ACMO: 4-me hac yl-oylmo pholine
ACN: Ace oni ile
AIBN: Azobisisobu y oni ile
ATRP: A om T ans e Radical Polyme iza ion
BADGE: Bisphenol-A Diglycidyl E he
bisCC: bis cyclic ca bona e
CC(M)A: Cyclic ca bona e (me h)ac yla e
CMR: Ca cinogenic, mu agenic, ep o oxic
CO2: Ca bon Dioxide
CSO: Ca bona ed Soybean Oil
DBTDL: Dibu yl in dilau a e
DCC: N,N′-Dicyclohexylca bodiimide
DCU: 1,3-Dicyclohexyl u ea
DEC: 3-aminop opyldie hoxyme hylsilane
DETA: Die hylene iamine
DMAc: Dime hylace amide
DMAP: 4-Dime hylaminopy idine
DMF: Dime hyl o mamide
DMPA: Dime hylp op ionic acid
DMSO: Dime hylsul oxide
DMTA: Dynamic Mechanical The mal Analysis
DSC: Di e en ial Scanning Calo ime y
EDA: E hylene Diamine
EDR: (e hylenedioxy)die hylamine
EDGE: E hylene Glycol Diglycidyl E he
EOAED: 2-(me hac yloyloxy)e hyl 2-(me hac yloyloxy)e hylca bama e
FTIR: Fou ie T ans o med In a ed
GMA: Glycidyl Me hac yla e
HCl: Hyd ochlo ic acid
HEMA: Hyd oxye hylme hac yla e
HMDA: Hexame hylene Diamine
H-NIPU: Hyb id-Non Isocyana e Polyu e hane
HUM: Hyd oxyu e hane Modi ie
HUMA: Hyd oxyu e hane Me hac yla es
IPDA: Isopho one Diamine
IPN: In e pene a ing Ne wo k
IR: In a ed
MA: Me hyl Ac yla e
MEC: 3-amino-p opyldime hyle hoxysilane
MEK: Me hyle hylke one
MMA: Me hyl Me hac yla e
NIPAM: N-isop opylac ylamide
Hyb id – Non Isocyana e Polyu e hanes (H- NIPUs) – A Pa hway owa ds a B oad Range o No el Ma e ials
71
NIPU: Non Isocyana e Polyu e hane
NIPU ea: Non Isocyana e Polyu ea
NMR: Nuclea Magne ic Resonance
NR: Na u al ubbe
oligoPHUs: oligo(hyd oxyu e hane)s
oligoUMA: Oligome s o u e hane me hac yla e
OVE: (2-0xo-1,3-dioxolan-4-yl) me hyl inyl e he
PGMAC: P opylene glycol me hyle he ace a e
PHU: Poly(hyd oxyu e hane)
P(H)UMAs: Poly(hyd oxyl)u e hane me hac yla es
POAED: 2-(me hac yloyloxy)e hyl 3-(me hac yloyloxy)p opylca bama e
POAPD: 1-(me hac yloyloxy)p opan-2-yl 3-(me hac yloyloxy)p opylca bama e
POSS: Polyhed al oligome ic silsesquioxanes
PPOA: poly(p opylene oxide) bis-ac yla e
PPOBC: poly(p opylene oxide) diglycidyl e he
PU: Polyu e hane
PUU: Polyu e hane-u ea
SEC: Size Exclusion Ch oma og aphy
SEM: Scanning Elec on Mic oscopy
TBD: T iazabicyclodecene
TEC: 3-amino-p opyl ie hoxysilane
TEM: T ansmission Elec on Mic oscopy
TEDA: T ie hylene diamine
TEPA: Te ae hylene pen amine
TETA: T ie hylene e amine
Tg: Glass T ansi ion Tempe a u e
TGA: The mo g a ime ic analysis
TGDEC: Ca bona ed esin based on ie hylene glycol diglycidyl e he
THF: Te ahyd o u an
TMPTA: ime hylolp opane is-ac yla e
TREN: T is(2-aminoe hyl)amine
Tα: - ansi ion empe a u es
VEC: Vinyl e hylene ca bona e
VEOPC: 3-(2- inyloxye hoxy)-1,2 p opylene ca bona e
UMAs: U e hane me hac yla es
UV: Ul a iole
Chap e 1 – Pa B
78
Scheme 2: Homogeneous wa e -based sys ems acco ding o Sa don e al.49
The copolyme s uc u e (balance be ween ha d and so segmen s) was uned by
a ying he monome a io. High con e sions (>98%) and polyme s wi h molecula weigh s
anging om 15 o 16 kDa we e ob ained. In e es ingly, he polyme s exhibi ed mel ing
beha io s in DSC in he ange om 27 o 33°C. The ex en o c ys allini y was ound o be
dependen on he a io be ween he PEG-based ca bona e (c ys alline) and he hexanediol-
based monome . The glass ansi ion empe a u es we e ound o lie a ound -55°C.
2.2. Modi ica ion o NIPUs syn hesized in o ganic sol en s
De embleu e al. also played on he chemical s uc u e o he NIPU o in luence i s inal
hyd oly ic beha io . They in oduced imine linkages wi hin he polyme backbone in o de
o induce acid-sensi i i y.50 To do so, hey eac ed p opa gylic alcohol wi h ca bon dioxide
o ob ain an unsa u a ed cyclic ca bona e. The subsequen aminolysis o his monome wi h
a diamine in DMF yielded a diu e hane p e-polyme ha u he eac ed wi h a diamine
yielding he co esponding poly(u e hane–co–imine), also sho ened PUIs –Scheme 3.
Scheme 3: Imine-con aining NIPUs – adap ed om De embleu e al.50

Wa e -based Non Isocyana e Polyu e hanes-Polyu eas (NIPUUs)
79
The success ul syn hesis o he PUIs was ound o highly ely on he use o a good Lewis
acid ha no only ca alyzes he polyme iza ion, bu also ac s as a dehyd a ing agen , hus
shi ing he chemical equilib ium owa ds he o ma ion o he imine by apping wa e
upon i s o ma ion du ing he imina ion p ocess. The low cos , low oxic and comme cially
a ailable i anium-based Ti(OE )4 was ound o be a sui able ca alys o he polyme iza ion.
A e op imizing he eac ion condi ions, good con e sions (>95%) o he monome s we e
achie ed, o ming oligome s wi h molecula weigh s anging om 3000 o 8500 g/mol a e
quenching and emo al o he Lewis acid. The low molecula weigh s ob ained can be
explained by he dynamic na u e o he imine bond ha may ha e hyd olyzed du ing he
quenching s ep. The au ho s in e es ingly demons a ed he pH- esponsi eness o he
o med p oduc s; he lowe he pH, he as e he hyd olysis occu ed. No ably a pH 1, some
polyme s could be ully hyd olyzed wi hin a single day, whe eas no polyme deg ada ion
was no iced a e 24h a pH 7.
PHUs can be made soluble in wa e h ough eac ion o he pendan OH-g oups wi h
succinic anhyd ide ollowed by neu aliza ion wi h sodium bica bona e - Scheme 4.51 . The
au ho s in oduced ca bona e, es e and e he g oups in he PHUs and explo ed hei
hyd oly ic beha io inding ha chemical composi ion o he bis cyclic ca bona e a ec ed
he hyd oly ic beha io unde basic condi ions pH = 8 – 10,6. Ca bona e-con aining PHUs
hyd olyze as e han es e -con aining PHUs, which in u n hyd olyze as e han e he -
con aining ones. Hyd olysis a e inc eased as he pH inc eased. A pH = 8, i was a he slow
(less han 15 % o he ca bona e con aining PHUs), bu i accele a ed a highe pHs
(comple e hyd olysis o he ca bona e con aining PHUs in only 7 days). This deno es he
unabili y o he sys em depending on he monome and hus on he polyme s uc u e. The
au ho s chain-ex ended he wa e soluble ca bona e-based PHUs wi h he help o α,α-
diiso hiocyana e-p-xylene, o ming hio-u ea b idges52 and obse ed ha he longe he
PHU chain, he be e he hyd oly ic esis ance o he polyme unde alkaline condi ions.
The au ho s a ibu ed his beha io o he p esence o a highe H-bond densi y ha
hinde ed he wa e in luence on he polyme chain. Mo eo e , he xylene moie y o he chain
ex ende , b inging a highe hyd ophobici y, was assumed o play also a ole in his educed
wa e sensi i i y.
Chap e 1 – Pa B
80
Scheme 4: P epa a ion o wa e -soluble PHUs ia pos - unc ionaliza ion o pendan OH g oups – adap ed om
Ma sukizono and Endo51
The same esea ch eam demons a ed ha unc ionalizing he pendan OH-g oups in o
qua e na y ammonium chlo ide moie ies also ga e wa e -soluble PHU sal s.53 The pos -
unc ionaliza ion o he hyd oxyl moie ies was pe o med wi h chlo oace yl chlo ide p io
o eac ing wi h N,N-dime hyl-n-oc ylamine o yield he co esponding sal - Scheme 5.
Some chlo oace yl-de i ed PHUs exhibi ed wa e -solubili y depending on he polyme
s uc u e. The syn hesis howe e yielded e y sho oligome s, wi h molecula weigh s
anging om 3800 o 6300 g/mol depending on he diamine used. Good yields o
unc ionaliza ion wi h he amine we e ob ained (a ound 80% in e e y case). C oss-linked
polyme s we e ob ained by eac ing he unc ionalized PHUs wi h e ia y diamines leading
o good sel -suppo ed ilms.
Scheme 5: Qua e na y ammonium chlo ide PHUs – adap ed om Ma sukizono and Endo53
Wa e -based Non Isocyana e Polyu e hanes-Polyu eas (NIPUUs)
81
3. Hyd ogels
Hyd ogels can be de ined as 3D c oss-linked hyd ophilic ne wo ks. Thei a ini y o
wa e p o ides hem wi h he abili y o swell and e ain 10 o 1000 imes hei d y weigh
in wa e .54
Segmen ed PUs can be used o hyd ogel o ma ion because o hei pa icula
mechanical p ope ies and capabili y o in e ac ing wi h wa e h ough he addi ion o
hyd ophilic monome s (e.g. poly e hylene glycol – PEG).55,56 To he bes o ou knowledge,
only one example o poly(hyd oxyu e hane)-based hyd ogel has been published.57 The
syn hesis consis ed in ha ing a ca bona ed polye hylene glycol diglycidyle he eac ing
wi h a ious polyamines in bulk. Th ee diamines we e es ed: ,-(e hylenedioxy)die hyl-
amine (EDDA), m-xylylenediamine (m-XDA) and 1.8-diaminooc ane (ODA) and a iamine,
ac ing as c osslinking agen : is(2-aminoe hyl)amine (TAEA) - Scheme 6. Subsequen
swelling in wa e allowed he abso p ion o wa e and he o ma ion o he inal hyd ogel.
The c oss-linking deg ee o he inal ma e ial (con olled by he amoun o iamine
in oduced) in luenced he heology o he ma e ial: a minimum o 0.2 eq. o iamine wi h
espec o he biscyclic ca bona e was necessa y o a oid ee lowing. On he o he hand,
0.33 eq. yielded e y b i le ma e ials, sugges ing a highe c osslinking deg ee, as con i med
by measu emen o he gel con en in wa e ( om 67.5 ± 1.2% o 80.7 ± 1.5% when going
om 0.2 o 0.33 eq.). Be ween hese wo limi s, he wa e up ake o he inal ma e ial
inc eased as he amoun o c oss-linking agen dec eased (equilib ium wa e abso p ion up
o 500% we e ob ained). Mo eo e , comp ession es s in he swollen s a e showed ha a
highe con en in iamine led o highe comp ession moduli ( om 19.1 ± 0.7 o 185.5 ±
36.7 kPa when going om 0.2 o 0.33 eq.), lowe s ains a b eak ( om 61.0 ± 3.4 o 43.6 ±
5.1% when going om 0.2 o 0.33 eq.) and highe s esses a b eak ( om 43.4 ± 5.4 o 170.0
±44.7 kPa when going om 0.2 o 0.33 eq.). Those p ope ies we e also ound o s ongly
depend on he ype o diamine used. Fo ins ance, he mos hyd ophilic EDDA ga e he
highes equilib ium wa e abso p ion (967 ± 9 %) whe eas mXDA and ODA ga e lowe
alues (505 ± 54% and 214 ± 2% espec i ely). The di e ence he las wo was a ibu ed
o he lowe dis ance be ween c osslinking poin s in he case o mXDA, inc easing i s
hyd ophilici y. Mo eo e , he dec ease in he equilib ium wa e abso p ion (EWA) induced
ha mo e s ess was needed o comp ess he hyd ogel. This inc eased he esul ing
comp ession moduli ( om 37.1 ± 4.3 kPa o 125.3 ± 5.6 kPa o EWA o 967 ± 9% and 214
± 2%, espec i ely) and s ess a b eak ( om 22.4 ± 8.4 kPA o 830 ± 140 kPa o EWA o
967 ± 9% and 214 ± 2%, espec i ely). No in luence o he in oduc ion o nanoclay (in his
case Mon mo illoni e) on he gel con en was obse ed in he copolyme made o 1eq. o he
PEG bis ca bona e, 0.2 eq. o he iamine and 0.7 eq. o mXDA, (loading om 1w % up o
15w % o clay we e s udied). I was howe e demons a ed ha i had an e ec on he
mechanical p ope ies in e ms o comp ession p ope ies. When he nanoclay loading was
a ied om 2 and 5w %, he equilib ium wa e abso p ion emained a ound 400%, bu he
Chap e 1 – Pa B
82
comp ession moduli a ied be ween 15.7 ± 0.2 kPa and 23.9 ± 1.4kPa, he s ain a b eak
be ween 68.0 ± 0.7 and 79.3 ± 1.6% and he s ess a b eak also a ied be ween 60.0 ± 4.0
and 157.2 ± 4.7 kPa. Highe loadings ga e hyd ogels wi h lowe equilib ium wa e
abso p ion (down o 56.9 ± 0.7% a 15w % loading o nanoclay).
Scheme 6: P epa a ion o c oss-linked PHUs o he o ma ion o hyd ogels – adap ed om De embleu and
cowo ke s57
4. Wa e -bo ne Dispe sions
4.1. Ace one-like p ocess
Dispe sions o polyu e hanes a e e y impo an p oduc s in he coa ing and adhesi e
ma ke s due o he ela i ely easy syn hesis and good pe o mance. PUs a e usually
syn hesized h ough he so-called ace one p ocess- Scheme 7.15,58. In his p ocess, he PU
p epolyme s a e syn hesized in a wa e miscible low boiling poin sol en , commonly
ace one. An in e nal dispe sing agen such as dime hylolp opionic acid (DMPA) is usually
added in o he o mula ion and allows o dispe sion in he wa e phase upon neu aliza ion
(usually pe o med wi h he help o ime hylamine). The PU is hen chain-ex ended wi h a
sho diol o diamine and a e ace one is emo ed, he PU dispe sion is inally ob ained.
Mos o he published examples o isocyana e- ee PUs o PU eas dispe sions a e
inspi ed in he ace one p ocess, namely he copolyme iza ion o h ee monome s, including
an in e nal dispe sing agen is done in a low boiling poin sol en . The subsequen
neu aliza ion o he o med polyme chains allows he dispe sion upon wa e addi ion. The
emo al o he low boiling poin sol en leads o he inal wa e bo ne dispe sion.
Wa e -based Non Isocyana e Polyu e hanes-Polyu eas (NIPUUs)
83
Scheme 7: Wa e -bo ne PUs h ough he ace one p ocess
4.1.1. NIPUs dispe sion by ace one-like anses e i ica ion p ocesses
The e y i s example o NIPU wa e -based dispe sion was published in 1996 by Blank
e al.,59 who in es iga ed he p ope ies o c oss-linked polyu e hane dispe sions. They used
he ansu e haniza ion p ocess o he o ma ion o NIPUs om polyes e polyols (wi h an
acid numbe o 1-2) and bis-hyd oxyp opylca bama es and a iol, using a
anses e i ica ion ca alys (dibu yl in oxide). The eac ion was ca ied ou unde acuum
wi h a p og essi e inc ease in he empe a u e up o 175°C. The amoun o he o med
dis illa e (1,2-p opylene glycol) as well as he inc ease in iscosi y helped moni o ing he
ex en o polyme iza ion. Ca boxyl unc ionali y was b ough by eac ing an anhyd ide on o
he OH chain-ends. 35 and 41w % dispe sion we e p epa ed wi hou any co-sol en (which
is a di e ence wi h he ace one-p ocess), wi h a neu aliza ion s ep by means o
diisop opanolamine and/o ie hylamine. The c oss-linking was pe o med by addi ion o
wa e dispe sible hexa(me hoxyme hyl)melamine. The dispe sions we e used in coa ing
applica ions and pain s.

Chap e 1 – Pa B
84
In 2018, Ma e al. published a se ies o s udies explo ing non-isocyana e s a egies o
he p oduc ion o wa e bo ne polyu ea dispe sions o coa ings.60,61 Thei app oach
consis ed in u ilizing a ansu e haniza ion-like p ocess in bulk unde acuum. To do so,
hey copolyme ized a bis-alkylca bama e monome wi h wo diamines, one o hem playing
he ole o in e nal dispe sing agen (IDA) o o m a p e-polyme , ha was u he dissol ed
in me hnaol. A e neu aliza ion, usually wi h he help o ace ic acid, he mix u e was slowly
added in o wa e . The emo al o me hanol ga e he inal dispe sion - Scheme 8. The
au ho s demons a ed ha du ing he p e-polyme iza ion s ep, he na u e o he alkyl-
lea ing g oup o he bis-ca bama e as well as he p ocess condi ions (such as high
acuum)we e ound o be o ou mos impo ance o he eac ion o gi e polyu eas wi h
high enough molecula weigh s.60,61
Scheme 8: P epa a ion o wa e -bo ne non-isocyana e polyu eas – adap ed om Ma e al60,61
The success ul implemen a ion o his p ocess s ongly depends on he abili y o he
ansu e haniza ion eac ion o p oceed wi hou oo many side- eac ions. The nucleophilic
a ack o he diamine on o he bis-ca bama e o yield he co esponding u ea moie y is in
compe i ion wi h he N-alkyla ion eac ion ha can p oceed h ough a deca boxyla ion
mechanism – Scheme 9. This eac ion is undesi able since i would lead o a de ia ion om
he s oichiome ic a io, and hence o lowe molecula weigh s.
Wa e -based Non Isocyana e Polyu e hanes-Polyu eas (NIPUUs)
85
Scheme 9: N-alkyla ion eac ion in compe i ion wi h he ansu e haniza ion in he eac ion be ween a bis-
ca bama e and a diamine – adap ed om Ma e al.60
The au ho s demons a ed ha he N-alkyla ion eac ion could be mi iga ed by changing
he alkyl moie y loca ed on he bis-ca bama e compound60,61. Bulkie alkyl-g oups educed
he a e o he deca boxyla ion p ocess, hus a o ing he polyu ea o ma ion. Indeed, he
e -bu oxyl moie y was mo e selec i e owa ds u ea o ma ion han he e hyl g oups,
which i sel was mo e selec i e han me hyl g oups. The alkyl moie y on he bis-ca bama e
also a ec ed kine ics and i was ound ha he u ea o ma ion was as e in he ollowing
o de : e -bu oxyl > me hyl > e hyl. In he case o me hyl- and e hyl-g oup, he bulkie
e hyl-g oup s e ically hinde ed he nucleophilic addi ion o he diamine on o he bis-
ca bama e moie y. The case o e -bu oxy g oup was mo e in iguing, since as e kine ics
was obse ed despi e he bulkiness. The au ho s explained his as kine ics by he
mechanism o he eac ion p oceeding ia he in si u o ma ion o an isocyana e moie y. The
ype o diamine used, and he e iciency o he emo al o he gene a ed alcohol also played
a e y impo an ole in he mi iga ion o N-alkyla ion. Rega ding he diamines, s e ically
less hinde ed p ima y diamines had as e a es o N-alkyla ion han he bulkie ones
(seconda y diamines o p ima y amines a ached o a e ia y ca bon). Remo al o he
alcohol a o ed he ansu e haniza ion eac ion and he gene a ion o highe molecula
weigh polyu eas. In gene al, ela i ely high molecula weigh s (16 o 65 kDa) we e
ob ained.60,61
In o de o dispe se he o med polyu ea chains, in e nal dispe sing agen s (IDA) we e
used. Thei subsequen neu aliza ion allowed o he polyme chains o o m nanopa icles
in wa e . The highe mola pe cen ages ( a ied om 10 o 30 mol.% in diamine) o IDA
we e used.60,61 The highe su ace-cha ge densi y on he pa icles led o smalle pa icles
( o example, in he case o a se ies o copolyme s composed o isopho one
dime hylca bama e, 4,7,10- ioxa-1,13- idecanediamine and ,-diamino-N-
me hydip opylamine – used as IDA – he pa icle diame e s a ied om 280 nm o 10
mol% IDA in diamine o 44 nm o 30mol% IDA in diamine).60 The coa ings cas om hese
dispe sions exhibi ed pencil ha dness anging be ween HB and 2B (e en B o 6B when
changing he diamine) and good esis ance o ace one. The molecula weigh s o he
polyme in luenced he en anglemen densi ies o he polyme chains and i was obse ed
ha polyu ea coa ings wi h molecula weigh s lowe ham 30 kDa exhibi ed poo e impac
esis ance han coa ings wi h highe molecula weigh s. Mo eo e , longe monome s ha
Chap e 1 – Pa B
86
inc ease he dis ance be ween u ea moie ies ended o dec ease he H-bond densi y
esul ing in so e coa ings.
In 2018, he same esea ch eam demons a ed ha e hylenediamine e aace ic
dianhyd ide (EDTAD) could be success ully inco po a ed as an IDA in o he NIPU ea
o mula ion,62 Fo ming wo penden ca boxylic acid moie ies upon opening o he
anhyd ide opening – Scheme 10.
Scheme 10: Wa e -bo ne NIPU eas using EDTAD as in e nal dispe sing agen – adap ed om Ma e al62
The e y high densi y o H-bonds in his sys em induced gela ion, which was also a o ed
by he ionic in e ac ions p o ided by he zwi e ionic o m o he amic acid – Scheme 11.
The use o an asymme ic isopho one-based bis-ca bama e dis up ed he es ablishmen o
H-bonds be ween he u ea moie ies and educed he ex en o gela ion.62
Scheme 11: Zwi e ionic o m o he amic acid a e aminolysis o EDTAD – adap ed om Ma e al62
Wa e -based Non Isocyana e Polyu e hanes-Polyu eas (NIPUUs)
87
The ad an age o such an in e nal dispe sing agen is he e y ine unabili y o he
neu aliza ion s ep. The concomi an ioniza ion o he amic acid in i s zwi e ionic o m as
well as he neu aliza ion by means o adding ie hylamine (NE 3, TEA) allows o a ine
uning o he pa icle size o he dispe sion (pa icles diame e anging om 900 o 8 nm
we e ob ained depending on he condi ions). Howe e , he o ma ion o he zwi e ionic
moie y alone was no enough o s abilizing he dispe sion since he polyu ea p ecipi a ed
i no NE 3 was added p io o dispe sion. When inc easing he TEA/COOH a io, he pa icle
size d ama ically dec eased and he iscosi y o he la ex inc eased, which abo e a ce ain
alue can be de imen al o coa ing applica ions. As an example, he pa icle size as
measu ed by dynamic ligh sca e ing (DLS) dec eased om 900 nm o 14 nm when he
a io was a ied om 0.1 o 1.0. In o de o ci cum en his e ec , he au ho s ied o
educe he concen a ion o ionic g oups in he inal polyu ea while a ge ing 100%
neu aliza ion o he penden acidic moie ies. This was done by inc easing he diamino-
p epolyme /EDTAD a io and neu alizing he ca boxyl g oups wi h a s oichiome ic
amoun o ime hylamine. The au ho s also educed he ionic con en in he inal polyme
by inc easing he molecula weigh o he diamino p epolyme . P epolyme molecula
weigh s anging om 950 Da o 4750 Da we e p epa ed a ying he diamine/ca bama e
a io om 2 o 1. Using hese p epolyme s, he pa icle size inc eased om 8 nm (Mnp epolyme
= 950 Da) o 61 nm (Mnp epolyme = 4750 Da). Mos o he polyme s had a ela i ely high Tg
and he e o e no ilm could be cas a oom empe a u e. Coa ings could be o med by
cas ing a 50°C o 6 h ollowed by a he mal ea men a 110-150°C o 24 h. Mo eo e ,
hese polyme s did no o m coa ings wi h in e es ing p ope ies since hey we e b i le and
ce ainly did no ge chain ex ended enough o each he minimum en anglemen molecula
weigh , which is needed o ob ain polyme s wi h in e es ing mechanical p ope ies. The
coa ings we e p epa ed a 50°C on aluminum panels. The cu ing empe a u e was ound o
be e y impo an since highe empe a u es led o coa ing wi h highe ha dness, be e
adhesion p ope ies as well as be e sol en esis ance. This was a ibu ed o a non cyclic
imidiza ion c osslinking mechanism – namely he eac ion be ween penden COOH moie ies
wi h amides om he polyu eas. This esul was con i med by an inc ease in he gel ac ion
o he ob ained ma e ials.
4.1.2. NIPUs dispe sion by ace one-like aminolysis p ocesses
Only wo examples o poly(hyd oxy u e hane) dispe sions ha e been epo ed. The i s
example da es back o 2008 wi h a pa en om Rhodia.63 The pa en discloses he PHU
syn hesis and he o ma ion o aqueous dispe sions o be used as coa ings and adhesi es.
Mos o he examples a e in eali y hyd o-o ganic solu ions and he ob ained la exes a e no
o ganic sol en - ee. In hese cases, PHUs we e syn hesized in an o ganic sol en such as
e hanol o Highlink W (Cla ian ™). Dihyd oxyu e hane adduc s o isopho one diamine and
Chap e 1 – Pa B
94
6. Conclusions
This wo k e iews he wa e -based non-isocyana e polyu e hane-u eas (NIPUUs), a new
class o ma e ials ha a e a g eene al e na i e o he adi ional isocyana e-based
polyu e hane-u eas.
NIPUUs can be o med by ei he he ansu e haniza ion p ocess, yielding
polyu e hane/u eas, and he aminolysis o biscyclic ca bona es, yielding
poly(hyd oxyu e hane)s (PHUs). Nei he o he wo app oaches is ee om p oblems. N-
alkyla ion side- eac ion can occu du ing he ansu e haniza ion p ocess. This side
eac ion can be mi iga ed by changing he alkyl moie y loca ed on he bis-ca bama e
compound. Bulky g oups such as e -bu oxyl-, phenyl-, ni ophenyl- and
pen a luo ophenyl-moie ies educe he side eac ion, bu he pu i ica ion o he a oma ic
moie ies emains challenging, and e -bu oxyl-g oups wo k h ough he o ma ion o an in
si u isocyana e moie y in hei mechanism, which can seem ques ionable i a ull isocyana e-
ee p ocess is desi ed. On he o he hand, he use o aminolysis in aqueous media is
challenging because cyclic ca bona es a e p one o su e hyd olysis.
Bo h wa e -soluble NIPUUs and wa e bo ne NIPUU dispe sions can be p epa ed by
a ying he hyd ophilici y o he monome s.
In p inciple, bo h aminolysis and ansu e haniza ion can be used o di ec ly syn hesize
wa e -soluble NIPUUs in wa e . Howe e , he use o aminolysis is p ecluded by he
p opensi y o he cyclic ca bona es o su e hyd olysis. T ansu e haniza ion using
unc ional bis-ca bona es allowed ob aining wa e -soluble NIPUs. A likely easie o apply
app oach is he modi ica ion o NIPUs syn hesized in o ganic sol en s. Imines, neu alized
ca boxyl g oups and qua e na y ammonium chlo ide moie ies ha e been used o ende he
p e o med NIPUs soluble in wa e .
Some widely di e en me hods ha e been used o syn hesize wa e bo ne NIPUU
dispe sions. A me hod ha looks p omising is he ace one-like p ocess. In his p ocess,
NIPUUs con aining in e nal dispe sing moie ies (e.g. ca boxyl o zwi e ionic) a e
syn hesized in a low boiling poin o ganic sol en such as ace one using ei he
ansu e haniza ion o aminolysis. The polyme solu ion is hen dispe sed in wa e and he
sol en emo ed by e apo a ion. NIPUU dispe sions can also be syn hesized by in e acial
ansu e haniza ion wi h he ca bama e in he o ganic phase and he diamine in he
aqueous phase. Miniemulsion polyme iza ion has been used o syn hesize NIPU dispe sions
by he aminolysis p ocess. Poly(hyd oxyu e hane)s syn hesized by aminolysis ha e been
used o p epa e NIPU dispe sions by nanop ecipi a ion.

Wa e -based Non Isocyana e Polyu e hanes-Polyu eas (NIPUUs)
95
As in he case o classical PUs, i is expec ed ha hyb ids composed by NIPUs and o he
polyme s yield ma e ials wi h syne gis ic p ope ies. The e o e, NIPU-ac ylics and NIPU-
epoxy hyb ids ha e been syn hesized showing syne gis ic imp o emen o he
pe o mance.
Subs an ial ad ances in he de elopmen o wa e -based NIPUs ha e been done in he
las yea s. These s udies show ha he s uc u e o he monome s plays a c i ical ole in
bo h he easibili y o he syn he ic p ocess and he ype o polyme ob ained. Fu he
de elopmen s will equi e easie me hods o he syn hesis and pu i ica ion o he
monome s, o unde s and he e ec o he polyme iza ion me hod on he polyme
mic os uc u e and ha o he mic os uc u e on he pe o mance. I is hoped ha hese
de elopmen s will b ing wa e -based NIPUUs close o indus ial implemen a ion.
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Bo ne PHU Coa ings. Ind. Eng. Chem. Res. 2017, 56 (47), 14089–14100.

Chap e 1 – Pa B
100
8. Sho ened o ms
BA: Bu yl Ac yla e
BADGE: Bisphenol-A Diglycidyl E he
CMR: Ca cinogenic, mu agenic, ep o oxic
CO2: Ca bon Dioxide
DCM: Dichlo ome hane
DLS : Dynamic Ligh Sca e ing
DMF: Dime hyl o mamide
DMPA: Sime hylolp opionic Acid
DMSO: Dime hylsul oxide
DPA: Diphenolic Acid
DSC : Di e en ial Scanning Calo ime y
EDDA : ,-(e hylenedioxy)die hyl-amine
EDTAD: E hylenediamine e aace ic Dianhyd ide
HMDA: Hexame hylene Diamine
IDA: In e nal Dispe sing Agen
IPDA: Isopho one Diamine
MFFT: Minimum Film Fo ma ion Tempe a u e
MMA: Me hyl Me hac yla e
m-XDA: m-xylylenediamine
NaHCO3: Sodium Bica bona e
NIPU: Non Isocyana e Polyu e hane
NMP: N-Me hyl py olidone
ODA: 1.8-diaminooc ane
PEG: Poly(e hylene) glycol
PGMAC: P opylene Glycol Me hyl Ace a e
PHU: Poly(hyd oxyu e hane)
PU: Polyu e hane
PUI: Poly(u e hane–co–imine)
SDS: Sodium Dodecyl Sul a e
SEM: Scanning Elec on Mic oscopy
TAEA: T is(2-aminoe hyl)amine
TEA: ie hylamine
TEM: T ansmission Elec on Mic oscopy
Ti(OE )4: Ti anium E hoxide
Tg: Glass T ansi ion Tempe a u e
TMDA: Te ame hylene diamine
UMAs: U e hane me hac yla es
PART C
OBJECTIVES & OUTLINE
Chap e 1 – Pa C
102
F om he s a e-o - he-a , i appea s ha Hyb id-Non Isocyana e Polyu e hanes (H-
NIPUs) a e in e es ing new ma e ials wi h p ope ies a ising om a syne gis ic
combina ion o hose o he cons i u i e uni s. Mo eo e , in only a ew examples he
po en ial o such hyb id ma e ials in wa e -bo ne sys ems has been explo ed.1–3
The e o e, he pu pose o his hesis was o syn hesize no el wa e -bo ne hyb id-NIPU
ma e ials (H-NIPUs) by combining bio-based isocyana e- ee poly(hyd oxy u e hane)s
(PHUs) p e-polyme s wi h (me h)ac yla es. In o de o ul ill his goal, se e al challenges
should be o e come such as he syn hesis o speci ic monome s (in his case bis-cyclic
ca bona es), he bulk polyme iza ion o hese monome s wi h diamines o o m he PHUs,
he selec ion o a sui able ac ylic phase o dissol e hese PHUs and inally he
polyme iza ion o he ac ylic phase in a mini-emulsion p ocess. As he cha ac e is ics and
p ope ies o he hyb ids a e expec ed o depend on he in e ac ion be ween he PHU and
he ac ylic polyme , bo h g a ed and non-g a ed hyb ids we e syn hesized and he
p ope ies o he esul ing coa ings in es iga ed.
The es o his hesis will be di ided in ou chap e s.
Chap e 2 deals wi h he bulk syn hesis o bio-based poly(hyd oxy u e hane)s - PHUs.
The design o es e -ac i a ed bis-cyclic ca bona es o di e en alipha ic chain leng h is
desc ibed, as well as hei polyme iza ion beha io wi h a ious a y acid-based diamines.
The ela ionship be ween he s uc u e o he PHU and he he mal and iscoelas ic
p ope ies is in es iga ed.
Chap e 3 is dedica ed o he design o wa e -bo ne non-c oss-linked PHU-Poly(bu yl
me hac ylic) H-NIPUs using mini-emulsion. In his chap e , a 2-s ep p ocess was
implemen ed. Fa y acid based-PHUs we e i s ly syn hesized in bulk and hen dissol ed in
a mix u e o bu yl me hac yla e and s ea yl ac yla e (BMA + SA). The esul ing mix u e was
hen emulsi ied by sonica ion and he ac ylic phase polyme ized. Di e en la exes, ha ing
composi ions anging om 0 o 30 w .% PHU, we e ob ained, and he polyme iza ion
beha io o he ac ylic phase was s udied, in e ms o kine ics and pa icle size. The
pe o mance o he ilms cas om he hyb id wa e bo ne dispe sions was s udied.
In Chap e 4, wa e bo ne g a ed PHU-poly(me h)ac yla e hyb id dispe sions we e
syn hesized and he e ec o g a ing on he pa icle and ilm mo phologies as well as on he
mechanical p ope ies o he ilms was in es iga ed.
Chap e 5 p o ides he gene al conclusions and pe spec i es o his wo k.
Objec i es & Ou line
103
Re e ences
(1) Ma, Z.; Li, C.; Fan, H.; Wan, J.; Luo, Y.; Li, B. G. Polyhyd oxyu e hanes (PHUs) De i ed
om Diphenolic Acid and Ca bon Dioxide and Thei Applica ion in Sol en - and Wa e -
Bo ne PHU Coa ings. Ind. Eng. Chem. Res. 2017, 56 (47), 14089–14100.
(2) Meng, L.; Wang, X.; Ocepek, M.; Soucek, M. D. A New Class o Non-Isocyana e U e hane
Me hac yla es o he U e hane La exes. Polyme (Guild ). 2017, 109, 146–159.
(3) Meng, L.; Soucek, M. D.; Li, Z.; Miyoshi, T. In es iga ion o a Non-Isocyana e U e hane
Func ional Monome in La exes by Emulsion Polyme iza ion. Polyme (Guild ). 2017,
119, 83–97.
Chap e 2
110
di e en ial e ac i e index de ec o (dRI) om Wya echnology. Polyme s we e
sepa a ed on wo KD803 Shodex gel columns and one KD804 Shodex gel columns (300 x
8 mm) (exclusion limi s om 1000 Da o 700 000 Da) a a low a e o 0.8 mL/min. Column
empe a u e was held a 50°C. Easi ial ki o Polys y ene om Agilen was used as he
s anda d (Mn om 162 o 364 000 Da).
Di e en ial Scanning Calo ime y (DSC) he mog ams we e measu ed using a DSC
Q100-RSC o a DSC Q100-LN2 appa a us om TA Ins umen s. In he DSC Q100-RSC, he
measu emen s we e pe o med o e a empe a u e ange om -80°C o 160°C, wi h a
hea ing cooling a e o 10°C.min-1. The analyses we e ca ied ou in a ni ogen
a mosphe e in aluminum pans. In he DSC Q-100-LN2, he measu emen s we e
pe o med o e empe a u e anging om -150°C o 160°C, wi h a hea ing cooling a e o
10°C.min-1. The analyses we e ca ied ou in a helium a mosphe e wi h aluminum pans.
The glass ansi ion empe a u es (Tgs) we e calcula ed om he second hea ing amp.
The mog a ime ic Analyses (TGA) we e pe o med on a TA-Q500 appa a us om TA
Ins umen s wi h a hea ing a e o 10°C.min-1 unde a ni ogen a mosphe e om oom
empe a u e un il 700°C.
The heology expe imen s we e ca ied ou in a s ess-con olled An on Paa Physica
MCR101 heome e . Small-ampli ude oscilla o y expe imen s we e ca ied ou using 25
mm pa allel pla e geome y. All he expe imen s we e conduc ed in linea iscoelas ic
condi ions o he s udied empe a u e ange (s ain = 0.5% and equency 1 Hz).
Rega ding he heo e ical mechanis ic s udy, all geome y op imiza ions we e ca ied
ou in gas phase wi hin densi y unc ional heo y (DFT), combined wi h he 6-31+G(d,p)
basis se . Ha monic ib a ional equencies we e ob ained by analy ical di e en ia ion o
g adien s, in o de o de e mine whe he he s uc u es ound a e minima o ansi ion
s a es.
The equencies we e hen used o e alua e he ze o-poin ib a ional ene gy (ZPVE)
and he he mal (T = 298 K) ib a ional co ec ions o he en halpy (H) in he ha monic
oscilla o app oxima ion. Single poin calcula ions using he 6-311++G(2d ,2p) basis se
we e pe o med on he op imized s uc u es in o de o e ine he elec onic ene gy, and
he p e iously calcula ed co ec ions o he en halpy we e used o calcula e he H o each
species- All DFT calcula ions we e ca ied ou using he Gaussian 16 package.

Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
111
2.2. S anda d P ocedu e o polyme iza ion
Poly(hyd oxy)u e hanes (PHUs) we e syn hesized using bisCC-C4 and bisCC-C10 wi h
10DA and P1075 as comonome s (Scheme 2). S oichiome ic a ios o he eac i e
moie ies we e a ge ed o maximize he molecula weigh s acco ding o he Ca o he ’s
heo y. The eac ions we e pe o med in bulk a 90°C o 24h in a Schlenk ube using a
helical shaped mechanical s i e speci ically designed o i in he Schlenk essel. No
ca alys was added o he polyme iza ion eac ions. No pu i ica ion o he PHUs was
pe o med a e eac ion. Con e sions we e de e mined by 1H-NMR spec oscopy a e
24h eac ion ime.
Scheme 2: PHU syn hesis h ough copolyme iza ion o bisCC-C4 and bisCC-C10 wi h 10DA and P1075
2.3. Bis-cyclic ca bona e syn hesis
bisCC-C10 syn hesis.
In a h ee-neck ound bo om lask, 2.2 eq. (30 g, 254 mmol) o glyce ol ca bona e and 2.2
eq. (25.707 g, 254 mmol) o ime hylamine we e added o 100 mL o dichlo ome hane
(DCM). This mix u e was cooled down wi h he help o an ice ba h and 1 eq. (27.615 g,
115.5 mol) o sebacoyl chlo ide was added d opwise. The eac ion mix u e was le unde
s i ing o 24 h a oom empe a u e. A e eac ion, he p oduc was pu i ied by means
o he ollowing liquid-liquid ex ac ion s eps: 5 imes wi h 200 mL o an acid solu ion
(5w .% HCl), ollowed by 3 imes wi h a basic ea men (s i ing wi h basic alumina
du ing 1h, ollowed by il a ion o he liquid DCM phase), and inally 1 washing s ep wi h
b ine. The isola ed o ganic phase was hen d ied wi h MgSO4, il e ed o e a sin e ed il e
and he dichlo ome hane was emo ed unde educed p essu e. The ob ained whi e
powde was hen analyzed by 1H-NMR. The whi e powde was d ied in a acuum o en a
40°C o e nigh o emo e any aces o emaining sol en . Yield: 50 %
1H-NMR: δ H (400 MHz, DMSO-d6) 5.10 – 4.97 (2 H, m), 4.57 (2 H, ), 4.43 – 4.17 (6 H, m),
2.33 (4 H, ), 1.51 (4 H, q), 1.25 (8 H, d).
bisCC-C4 syn hesis.
In a h ee-neck ound bo om lask, 1 eq. (2.032 g, 20.33 mmol) o succinic anhyd ide and
0.3 eq. (0.745 g, 6.10 mmol) o 4-dime hylaminopy idine (DMAP) we e added in 30 mL o
ace oni ile (ACN). This mix u e was hea ed up o 70°C wi h he help o an oil ba h un il
Chap e 2
112
solubiliza ion o he eagen s and 2.5 eq. (6.000 g, 50.81 mmol) o glyce ol ca bona e we e
added d opwise. The mix u e was le o eac unde magne ic s i ing du ing 6h and he
con e sion o he succinic anhyd ide in o he mono-ca bona e de i a i e was checked by
1H-NMR analysis. The eac ion mix u e was hen cooled down o oom empe a u e and
hen 1.5 eq. (6.291 g, 30.49 mmol) o N,N'-Dicyclohexylca bodiimide (DCC) was added.
The mix u e was le unde magne ic s i ing o e nigh (16h) and he o ma ion o a whi e
p ecipi a e o dicyclohexylu ea (DCU) was no iced. A e checking ha ull con e sion
was achie ed by 1H-NMR, he eac ion mix u e was il e ed o e a sin e ed il e and he
ACN was emo ed unde educed p essu e. The o ma ion o a whi e powde was no iced.
This powde was hen washed wi h cold DCM (50 mL) in a sin e ed il e o emo e he
excess o glyce ol ca bona e, DCC and DMAP ha a e soluble in i . The pu i y o he
p oduc was checked by 1H-NMR. The inal p oduc was hen d ied in a acuum o en
o e nigh o emo e any ace o emaining sol en . Yield: 40%.
1H-NMR: δ H (400 MHz, DMSO-d6) 5.03 (2 H, m), 4.57 (2 H, ), 4.37 – 4.20 (6 H, m), 2.63 (4
H, d, J 1.0).
3. Resul s and Discussion
3.1. Ac i a ed bio-sou ced bis-cyclic ca bona es (bisCCs)
The syn hesis o he bis cyclic ca bona e om Sebacoyl Chlo ide (bisCC-C10) was
adap ed om Ca é e al. and elies on he es e i ica ion eac ion be ween he a y diacid-
based diacyl chlo ide and glyce ol ca bona e (Scheme 3).54
Scheme 3: Syn hesis o he bis cyclic ca bona e om sebacoyl chlo ide (bisCC-C10).
A e pu i ica ion, he p oduc could be ob ained as a whi e powde wi h a yield o
50%. The o ma ion o he expec ed p oduc was a es ed by 1H-NMR spec oscopy
(Figu e 1).
Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
113
Figu e 1: S acked 1H-NMR Spec a o Sebacoyl Chlo ide in CDCl3 ( op) and bisCC-C10 in CDCl3 (middle) and
in DMSO-d6 (bo om)
Ano he bio-sou ced bis-cyclic ca bona e monome o sho e chain leng h was also
syn hesized. The syn he ic pa hway elies on he ing opening o succinic anhyd ide by
an excess o glyce ol ca bona e (Scheme 4). The eac ion p oceeded in a 1po -2s ep
p ocess in ace oni ile. The i s s ep consis ed in he o ma ion o he mono-ca bona e
de i a i e o succinic acid a e 6h eac ion as e ealed by 1H-NMR spec oscopy (Figu e
2). The eac ion was ca alyzed by 4-dime hylaminopy idine (DMAP). In he second s ep,
he mild S eglich es e i ica ion was employed, namely he addi ion o N,N'-
dicyclohexylca bodiimide (DCC) in combina ion wi h he al eady p esen DMAP and he
un eac ed glyce ol ca bona e allowed he o ma ion o he inal bisCC-C4. Ace oni ile
(ACN) was ound o be a sui able sol en o solubilize bo h he anhyd ide and he glyce ol
ca bona e. I also a o s he p ecipi a ion o he dicyclohexylu ea by-p oduc (DCU) ha
o med upon eac ion o he DCC coupling agen , hence shi ing he equilib ium o he
es e i ica ion eac ion owa ds he comple e o ma ion o he bis-cyclic ca bona e
compound. DMAP was also ound o be a sui able ca alys as i ca alyzes bo h eac ion
s eps. The pu i ica ion p ocess consis ed in a il a ion s ep o emo e he p ecipi a ed
DCU by-p oduc , hen he e apo a ion o ACN, ollowed by a washing s ep wi h cold
dichlo ome hane o emo e he emaining un eac ed species wi hou using any
ch oma og aphic sepa a ion me hod. The inal yield was 40%, yielding 2,57g o p oduc .
The 1H-NMR moni o ing o he eac ion (Figu e 2) and he eac ion was scaled up o he
o ma ion o 16g o bisCC-C4 wi h a good pu i y as exempli ied by 1H-NMR spec oscopy
(Figu e 2).
1
2
3
1
23
3
5
64,6 1
2
3
DMSO
*
*
1
2
4
53
3
6
bisCC-C10
5
6
4,6
1
2
3
CDCl3
1
2
4
53
3
6
bisCC-C10
Chap e 2
114
Scheme 4: Syn hesis o he bis-cyclic ca bona e om succinic anhyd ide (bisCC-C4).
Figu e 2: S acked 1H-NMR Spec a o Succinic Anhyd ide, he eac ion c ude be o e he addi ion DCC and o
bisCC-C4 ( om op o bo om) in DMSO-d6.
Un o una ely, when ying o scale he syn hesis up o he o ma ion o abou 27g o
bisCC-C4 (and ha e enough s a ing ma e ial o pe o m eac ions in bulk condi ions wi h
mechanical s i ing), i was no possible o ob ain bisCC-C4 ha was comple ely pu e. As
can be seen in Figu e 3, aces o glyce ol ca bona e (a ound 5 %) we e s ill obse ed
despi e se e al washing s eps wi h cold dichlo ome hane. Mo eo e , a low yield o 51%
was ob ained. E en i such a pu i y was no sa is ac o y, i was desi ed o know he ange
o p ope ies ha could be ob ained when dec easing he alipha ic chain leng h o he
bisCC monome . bisCC-C4 and bisCC-C10 we e hus copolyme ized wi h an alipha ic and a
b anched a y acid-based diamines (namely 1,10-diaminodecane – 10DA, and he
comme cially a ailable P iamineTM 1075 – P1075).
bisCC-C4
1
1
1
2
3
4
5
1
2
3
41
2,4
4
3
4
’ ’
’
4’5
’ ,,’ 3’
2
1
H2ODMSO
Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
115
Figu e 3: S acked 1H-NMR Spec a o Glyce ol Ca bona e and bisCC-C4 a e scale-up ( om op o bo om) in
DMSO-d6.
3.2. Copolyme iza ion o bisCC-C4 and bisCC-C10 wi h mix u es o
diamines
Achie ing he bulk polyme iza ion o PHUs a o ding su icien ly high molecula
weigh polyme s is o high in e es . To do so, i is needed o bo h o e come he high
iscosi y o he o med PHUs upon syn hesis as well as a oiding side- eac ions.44 On he
one hand, high iscosi y can be impa ed o he o ma ion o hyd ogen bonds be ween he
PHU chains.17 A helical shaped mechanical s i e speci ically designed o i in he used
Schlenk essel was u ilized o p o ide cons an agi a ion h oughou he en i e
polyme iza ion p ocess. On he o he hand, i is known ha es e -ac i a ed bisCCs su e
om side- eac ions.8,33 The o ma ion o u ea and amide by-p oduc s has been epo ed
and also explains he low molecula weigh s gene ally ob ained.
The syn hesized es e -ac i a ed 5-membe ed bis-cyclic ca bona e compounds we e
hus polyme ized o o m poly(hyd oxy u e hane)s (PHUs). To do so, bisCC-C4 and bisCC-
C10 we e copolyme ized wi h a ious a ios o he alipha ic (solid) 1,10-diaminodecane
(10DA) and he comme cially b anched (liquid) P iamine® 1075 (P1075). The
monome s eac ed du ing 24h a 90°C in bulk unde mechanical s i ing - Scheme 2. A
empe a u e o 90°C was chosen since i was high enough o p omo e bo h he mel ing o
he diamine and o he o med PHUs. Table 1 summa izes he eac ions ca ied ou and
he cha ac e is ics o he polyme s ob ained. The pu pose o using P1075 in he
o mula ion was o see whe he any plas iciza ion o he PHU p oduc would be bene icial
o he implemen a ion o he bulk p ocess.
1
3
’ ’
’
’
4
’
,,’
2’
DMSO
3’4’
’
2’
6’
6’
’
6’
’
*
*
bisCC-C4
1
2
3
4
6’
*

Chap e 2
116
Table 1: Chemical composi ion and cha ac e iza ion o he PHUs ob ained by copolyme iza ion o 10DA,
P1075 oge he wi h bisCC-C4 o bisCC-C10, in bulk, a 90°C du ing 24h
Run
Co-monome s [%]
Con .a
[%]
Mn b
[g.mol-1]
Đ b
Appa en
DP c
bisCC-
10DA
P1075
01
C4
100%
87
16 700
1.7
34
02
C4
75%
25%
83
12 500
1.8
21
03
C4
50%
50%
86
11 900
1.5
18
04
C4
25%
75%
79
12 000
1.5
16
05
C4
100%
75
10 400
1.4
12
06
C10
100%
93
33 900
2.2
59
07
C10
75%
25%
88
24 800
2.9
37
08
C10
50%
50%
91
22 700
3.0
30
09
C10
25%
75%
89
19 900
2.9
23
10
C10
100%
70
20 600
2.3
11
a Con e sions o eac i e unc ions we e calcula ed by 1H NMR.
b Mn alues we e ob ained by SEC in DMF wi h LiB sal s, PS calib a ion
c The appa en Deg ee o Polyme iza ion (DP) was calcula ed om he Mn alues ob ained by SEC
Figu e 4: 1H-NMR spec a o PHU 01 (bo om) and PHU 06 ( op)
In he eac ions (Table 1), he o ma ion o he u e hane moie y was checked by 1H-
NMR spec oscopy by ollowing he disappea ance o he signal co esponding o he
qua e na y ca bon o he cyclic ca bona e moie y (in he ange o 5.0 ppm). The
cha ac e is ic signal o he p o ons loca ed in alpha-posi ion o he u e hane moie ies
(CH2-NHC(O)O-) could be iden i ied in he ange 2.8-3.2 ppm (Figu e 4 – Figu e S1 o S10).
In a ed spec oscopy (FTIR, in Figu e S15 and S16) also e ealed he disappea ance o
’
A
’
’
4
’
’
’
’’
’’ ’’
4
5
*
*
’’
’’ ’’ A
B
’
’’
’
’’ U
U
U
U
NH amide
NH amide NH u ea
NH u ea
’’
’’ ’
’ ’
’
’’
’’
’’
’
A
A4
4 + DMSO
DMSO
B
5, B
5, B
’’
’’
’’ ’
**
**
Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
117
he C=O s e ching band o he cyclic ca bona e moie y a 1800 cm-1 and he appea ance
o he C=O s e ching band a ibu ed o he u e hane moie y a 1700 cm-1 as well as OH
moie ies (band a 3330 cm-1). The C=O s e ching band also exhibi ed he p esence o a
shoulde owa ds lowe wa enumbe s, ha could be explained by s e ching o he C=O
unc ion o he u ea side-p oduc .
The eac ion ex en s gauged by 1H-NMR analysis showed ha bisCC-C4 and bisCC-C10
did no exhibi he same beha io upon polyme iza ion. The eac ion ex en s usually we e
highe when bisCC-C10 was used as comonome (app oaching 90%), which can be
explained by he highe pu i y o he s a ing bisCC-C10. As a logical ou come acco ding o
he Ca o he ’s heo y, he molecula weigh s and hus he appa en deg ees o
polyme iza ion eached highe alues in he case o bisCC-C10. As a gene al end, he
molecula weigh s o he PHUs ob ained om bis-CC10 we e ound o be wice as much
g ea e han hose om bisCC-C4 (Table 1). This can ce ainly be explained by he
p esence o some glyce ol ca bona e le in he ba ch o bisCC-C4. Mo eo e , i could also
be no iced ha he highe he con en in 10DA, he highe he eac ion ex en s, and he
highe he esul ing appa en deg ees o polyme iza ion. Indeed, hey we e close o 90%
in he case o 10DA and be ween close o 70% in he case o P1075. The lowe con e sions
wi h P1075 can be explained due o a de ia ion om he s oichiome ic a io explained
by he lowe pu i y o he P1075.
A posi i e ou come conce ns Run 06. P e ious wo ks showed ha same polyme
p epa ed in DMF exhibi ed a Mn o 13700 g.mol-1 (Đ = 3.7) o a eac ion ex en o 93.5%
in 7 days a 70°C.33 In compa ison, we managed o each a signi ican ly highe molecula
weigh o a simila eac ion ex en in only 24h. This could sugges ha a lowe amoun
o side eac ions occu ed. A po en ial explana ion o his ea u e could be he highe
empe a u e, as well as he lowe eac ion ime u ilized in ou p ocess. The highe
empe a u e would inc ease he eac ion kine ics and he lowe eac ion ime would
lea e less ime o he side eac ions o occu .
1H-NMR spec oscopy was used o shed some ligh on he side eac ions by analyzing
he chemical mic os uc u e o he o med PHUs (Figu e 4). I is known ha he amine
unc ion can eac wi h he o ming u e hane and wi h he es e g oups o p oduce u ea
and amide moie ies, espec i ely - Scheme 5.8,33 The quan i ica ion o hose by-p oduc s
is impo an o ge an idea on he inal polyme mic os uc u e and also o explain he
a he low molecula weigh s ob ained. As exempli ied by p e ious wo ks,33 he u e hane
: u ea : amide a ios can be quan i ied by analyzing he labile-p o on zone ( om 6.5 ppm
o 8.0 ppm) p o ided he analyses a e pe o med in DMSO-d6. This was done o bo h
se ies o PHUs as shown in Figu e 5.
Scheme 5: Sugges ed mechanism o he eac ion be ween any NH2- e mina ed compound and he u e hane o he es e moie ies con ained in he backbone o he g owing PHUs o yield
u ea- and amide-con aining side-p oduc s espec i ely.
The chemical mic os uc u e o he PHUs showed di e ences depending on he
u ilized bisCC comonome . Highe a ios o u e hane moie y we e ob ained (mo e han
80%) when high eac ion ex en s (app oaching 90%) we e achie ed, especially when
high a ios o 10DA a e u ilized (Figu e 5). This alue is in acco dance wi h wha is
obse ed in he li e a u e. The o ma ion o up o 10% u ea was no a su p ise since
a oiding his eac ion is known o be e y imp obable.33 Howe e , he amoun o amide
o med was in he ange o 5 o 20%, which can be conside ed as a high ex en o
amidi ica ion as opposed o DMF-based p ocesses.33 This migh be due o he use o bulk
condi ions, in which he eac i e chains a e in a much in ima e con ac han in sol en s.
Mo eo e , he use o es e -con aining bisCCs inc eases he amoun o o med H-bonds in
he eac i e mix u e, yielding highly iscous mix u es. All o hese pa ame e s a o he
neighbo ing o he eac i e unc ions and can explain why a high ex en o amidi ica ion
was obse ed.
When analyzing again he speci ic case o Run 06, he u ea : amide : u e hane a io was
o 10.1 : 5.9 : 84 in he DMF p ocess33 whe eas he a io su p isingly was 4.5 : 0.5 : 95 wi h
he bulk p ocess. This suppo s he p e ious s a emen ha he ex en o side- eac ions
was diminished, hence inc easing he esul ing molecula weigh s. A po en ial
explana ion would be ha , because o he highe pu i y o he monome s (bisCC-C10 and
he alipha ic 10DA), he amoun o added monome s was close o he s oichiome ic
a io). When high amoun s o P1075 we e used, he lowe pu i y o P1075 would inc ease
he de ia ion o his s oichiome ic a io. Highe amoun s o NH2-moie ies would hus
eac on o he g owing PHU chains and yield side- eac ions and he o ma ion o u ea and
amide by p oduc s.
a) Fixed bisCC-C4
b) Fixed bisCC-C10
Figu e 5 : Mic os uc u al Composi ion (Amide : U ea : U e hane Ra io) o he ob ained PHUs by
copolyme iza ion o a) bisCC-C4 and b) bisCC-C10 when copolyme ized wi h a ious a ios o 10DA and
P1075 gauged by 1H-NMR analysis.
020 40 60 80 100
0
10
20
30
40
50
60
70
80
90
100 Amide
U ea
U e hane
Ra io U e h/U ea/Amide (%)
P iamine 1075 (%)
020 40 60 80 100
0
10
20
30
40
50
60
70
80
90
100
Amide
U ea
U e hane
Ra io U e h/U ea/Amide (%)
P iamine 1075 (%)
Chap e 2
126
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(50) Fa hadian, A.; Ahmadi, A.; Om ani, I.; Miya dan, A. B.; Va olomee , M. A.; Nabid, M. R.
Syn hesis o Fully Bio-Based and Sol en F ee Non-Isocyana e Poly (Es e
Amide/U e hane) Ne wo ks wi h Imp o ed The mal S abili y on he Basis o
Vege able Oils. Polym. Deg ad. S ab. 2018, 155, 111–121.
(51) Doley, S.; Dolui, S. K. Sol en and Ca alys -F ee Syn hesis o Sun lowe Oil Based
Polyu e hane h ough Non-Isocyana e Rou e and I s Coa ings P ope ies. Eu . Polym.
J. 2018, 102, 161–168.
(52) Da a, J.; Włoch, M. P og ess in Non-Isocyana e Polyu e hanes Syn hesized om
Cyclic Ca bona e In e media es and Di- o Polyamines in he Con ex o S uc u e–
P ope ies Rela ionship and om an En i onmen al Poin o View. Polyme Bulle in.
Sp inge Ve lag May 1, 2016, pp 1459–1496.
(53) Poussa d, L.; Ma iage, J.; G igna d, B.; De embleu , C.; Jé oîme, C.; Calbe g, C.;
Hein ichs, B.; De Win e , J.; Ge baux, P.; Raquez, J. M.; e al. Non-Isocyana e
Polyu e hanes om Ca bona ed Soybean Oil Using Monome ic o Oligome ic
Diamines o Achie e The mose s o The moplas ics. Mac omolecules 2016.
(54) Ca é, C.; Bonne , L.; A é ous, L. O iginal Biobased Nonisocyana e Polyu e hanes:
Sol en - and Ca alys -F ee Syn hesis, The mal P ope ies and Rheological Beha iou .
RSC Ad . 2014, 4 (96), 54018–54025.
(55) Rix, E.; G au, E.; Cholle , G.; C amail, H. Syn hesis o Fa y Acid-Based Non-Isocyana e
Polyu e hanes, NIPUs, in Bulk and Mini-Emulsion. Eu . Polym. J. 2016, 84, 863–872.
(56) Jan ie , M.; Duc o , P. H.; Allais, F. Isocyana e-F ee Syn hesis and Cha ac e iza ion o
Renewable Poly(Hyd oxy)U e hanes om Sy inga esinol. ACS Sus ain. Chem. Eng.
2017, 5 (10), 8648–8656.
(57) Esmaeili, N.; Zohu iaan-Meh , M. J.; Salimi, A.; Va ayan, M.; Meye , W. Tannic Acid
De i ed Non-Isocyana e Polyu e hane Ne wo ks: Syn hesis, Cu ing Kine ics,
An ioxidizing Ac i i y and Cell Viabili y. The mochim. Ac a 2018, 664, 64–72.
(58) Bäh , M.; Bi o, A.; Mülhaup , R. Cyclic Limonene Dica bona e as a New Monome o
Non-Isocyana e Oligo- and Polyu e hanes (NIPU) Based upon Te penes. G een Chem.
2012, 14 (5), 1447.
(59) Fi daus, M.; Meie , M. A. R. Renewable Polyamides and Polyu e hanes De i ed om
Limonene. G een Chem. 2013, 15 (2), 370–380.
(60) Qué e e, T.; Fleu y, E.; Sin es-Zydowicz, N. Non-Isocyana e Polyu e hane
Nanopa icles P epa ed by Nanop ecipi a ion. Eu . Polym. J. 2019, 114, 434–445.
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(61) Suha a, F.; Ku y, S. K. N.; Nando, G. B. The mal Deg ada ion o Sho Polyes e Fibe -
Polyu e hane Elas ome Composi e. Polym. Deg ad. S ab. 1998, 61 (1), 9–13.
(62) Zabalo , M. V.; Tige , R. P.; Be lin, A. A. Mechanism o U e hane Fo ma ion om
Cycloca bona es and Amines: A Quan um Chemical S udy. Russ. Chem. Bull. 2012, 61
(3), 518–527.
(63) Iwasaki, T.; Kiha a, N.; Endo, T. Reac ion o Va ious Oxi anes and Ca bon Dioxide.
Syn hesis and Aminolysis o Fi e-Membe ed Cyclic Ca bona es. Bull. Chem. Soc. Jpn.
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(64) Ochiai, B.; Sa o, S. I.; Endo, T. C osslinkable Polyu e hane Bea ing a Me hac yla e
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(65) Ochiai, B.; Sa oh, Y.; Endo, T. Nucleophilic Polyaddi ion in Wa e Based on Chemo-
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767.
6. Sho ened o ms
ACN: Ace oni ile
bisCC-C4: bis cyclic ca bona e om succinic anhyd ide
bisCC-C10: bis cyclic ca bona e om sebacic acid
Ɖ: Polydispe si y
DCC: N,N'-Dicyclohexylca bodiimide
DCM: Dichlo ome hane
DCU: Dicyclohexylu ea
DMAP: 4-dime hylaminopy idine
DMF: Dime hyl o mamide
DMSO-d6: deu e a ed dime hylsul oxide
Mn: Molecula weigh (in numbe )
Mw: Molecula weigh (in weigh )
NIPU: Non Isocyana e Polyu e hane
PHU: Poly(hyd oxy)u e hanes
P1075: P iamineTM 1075
Tg: Glass T ansi ion Tempe a u e
10DA: Decane 1,10-diamine
DSC: Di e en ial Scanning Calo ime y
FTIR: Fou ie T ans o med In a-Red-A enua ed To al Re lec ion
NMR: Nuclea Magne ic Resonance
SEC: Size Exclusion Ch oma og aphy
TGA: The mog a ime ic Analyses
Chap e 2
130
7. Suppo ing In o ma ion
7.1. NMR analyses
Run 01
Figu e S1: 1H-NMR spec a o Run 01 in DMSO-d6
Run 02
Figu e S2: 1H-NMR spec a o Run 02 in DMSO-d6
Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
131
Run 03
Figu e S3: 1H-NMR spec a o Run 03 in DMSO-d6
Run 04
Figu e S4: 1H-NMR spec a o Run 04 in DMSO-d6

Chap e 2
132
Run 05
Figu e S5: 1H-NMR spec a o Run 05 in DMSO-d6
Run 06
Figu e S6: 1H-NMR spec a o Run 06 in DMSO-d6
Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
133
Run 07
Figu e S7: 1H-NMR spec a o Run 07 in DMSO-d6
Run 08
Figu e S8: 1H-NMR spec a o Run 08 in DMSO-d6
Chap e 2
134
Run 09
Figu e S9: 1H-NMR spec a o Run 09 in DMSO-d6
Run 10
Figu e S10: 1H-NMR spec a o Run 10 in DMSO-d6
Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
135
S acked 1H-NMR spec a
Fixed bisCC-C4
Figu e S11: S acked 1H-NMR spec a o Run 01, Run 02, Run 03, Run 04 and Run 05 ( om bo om o op)
in DMSO-d6
Fixed bisCC-C10
Figu e S12: S acked 1H-NMR spec a o Run 06, Run 07, Run 08, Run 09 and Run 10 ( om bo om o op)
in DMSO-d6
Chap e 2
142
Figu e S23: DSC ace o Run 07 (Exo up)
Figu e S24: DSC ace o Run 08 (Exo up)
Figu e S25: DSC ace o Run 09 (Exo up)
Figu e S26: DSC ace o Run 10 (Exo up)
O e lay: 1s hea ing amp
a)
-100 -50 0 50 100 150 200
-10
-5
0
5
10
15
20
Hea Flow (W/g) - Exo Up
Tempe a u e - 1s hea ing amp (°C)
0% 10DA
25% 10DA
50% 10DA
75% 10DA
100% 10DA
b)
-100 -50 0 50 100 150
-5
0
5
10
15
20
Hea Flow (W/g) - Exo Up
Tempe a u e - 1s hea ing amp (°C)
0% 10DA
25% 10DA
50% 10DA
75% 10DA
100% 10DA
Figu e S27: DSC aces o he ob ained PHUs by copolyme iza ion o 10DA, P1075 oge he wi h a) bisCC-
C4 o b) bisCC-C10 (1s hea ing amp - 10°C/min)
50°C
37°C
32J/g
-12°C(I)
-1.0
-0.5
0.0
0.5
1.0
Hea Flow (W/g)
-100 -50 0 50 100 150 200 250
Tempe a u e (°C)
Size: 17.2800 mg
Me hod: BB - Hyb ids
DSC File: E: Analyses DSC BB318-DSC01.001
Ope a o : BB
Run Da e: 04-Jun-2018 12:58
Ins umen : DSC Q100 V9.9 Build 303
Exo Up Uni e sal V4.5A TA Ins umen s
45°C
39°C
15J/g
-12°C(I)
-1.0
-0.5
0.0
0.5
1.0
Hea Flow (W/g)
-100 -50 0 50 100 150 200
Tempe a u e (°C)
Sample: BB319-DSC03 (2nd sample)
Size: 8.1000 mg
Me hod: BB
DSC File: E: Analyses DSC BB319-DSC03.001
Ope a o : BB
Run Da e: 11-Jun-2018 15:43
Ins umen : DSC Q100 V9.9 Build 303
Exo Up Uni e sal V4.5A TA Ins umen s
45°C
42°C
1J/g
-17°C(I)
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
Hea Flow (W/g)
-100 -50 0 50 100 150 200
Tempe a u e (°C)
Sample: BB320-DSC01
Size: 13.0200 mg
Me hod: BB
DSC File: E: Analyses DSC BB320-DSC01.002
Ope a o : BB
Run Da e: 11-Jun-2018 17:00
Ins umen : DSC Q100 V9.9 Build 303
Exo Up Uni e sal V4.5A TA Ins umen s
-17°C(I)
-0.5
0.0
0.5
1.0
Hea Flow (W/g)
-100 -50 0 50 100 150
Tempe a u e (°C)
Sample: BB321-DSC02
Size: 9.5000 mg
Me hod: BB
DSC File: E: Analyses DSC BB321-DSC02.001
Ope a o : BB
Run Da e: 12-Jun-2018 09:37
Ins umen : DSC Q100 V9.9 Build 303
Exo Up Uni e sal V4.5A TA Ins umen s

Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
143
7.4. TGA analyses
Figu e S28: TGA ace o Run 01
Figu e S29: TGA ace o Run 02
Figu e S30: DSC ace o Run 03
Figu e S31: DSC ace o Run 04
Figu e S32: TGA ace o Run 05
Figu e S33: DSC ace o Run 06
199.30°C 95.06%
304.49°C 50.00%
297.10°C
452.90°C
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0100 200 300 400 500 600 700
Tempe a u e (°C)
Sample: BB334-TGA01
Size: 9.1230 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB334-TGA01.001
Ope a o : BB
Run Da e: 18-Jun-2018 18:47
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
205.18°C 95.06%
342.89°C 50.00%
295.77°C
339.43°C
476.81°C
-0.2
0.0
0.2
0.4
0.6
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0200 400 600 800 1000
Tempe a u e (°C)
Sample: BB314-TGA01
Size: 12.5100 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB314-TGA01.001
Ope a o : BB
Run Da e: 18-Ap -2018 16:43
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
206.44°C 95.06%
378.19°C 50.00%
321.60°C
409.53°C
476.39°C
-0.2
0.0
0.2
0.4
0.6
0.8
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0200 400 600 800 1000
Tempe a u e (°C)
Sample: BB315-TGA01
Size: 11.8150 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB315-TGA01.001
Ope a o : BB
Run Da e: 18-Ap -2018 19:04
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
199.61°C 95.06%
385.87°C 50.00%
211.90°C
307.97°C
447.40°C
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0100 200 300 400 500 600 700
Tempe a u e (°C)
Sample: BB316-TGA01
Size: 14.8670 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB316-TGA01.001
Ope a o : BB
Run Da e: 19-Jun-2018 09:38
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
201.23°C 95.06%
400.51°C 50.00%
213.72°C
316.88°C
446.81°C
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0200 400 600 800
Tempe a u e (°C)
Sample: BB317-TGA01
Size: 18.3490 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB317-TGA01.001
Ope a o : BB
Run Da e: 19-Jun-2018 11:09
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
250.85°C 95.06%
404.47°C 50.00%
299.23°C
466.73°C
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0200 400 600 800
Tempe a u e (°C)
Sample: BB333-TGA01
Size: 8.0660 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB333-TGA01.001
Ope a o : BB
Run Da e: 18-Jun-2018 10:14
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
Chap e 2
144
Figu e S34: TGA ace o Run 07
Figu e S35: TGA ace o Run 08
Figu e S36: DSC ace o Run 09
Figu e S37: DSC ace o Run 10
O e lays
a)
0200 400 600 800
0
20
40
60
80
100
Weigh (%)
Tempe a u e (°C)
100% 10DA
75% 10DA
50% 10DA
25% 10DA
0% 10DA
b)
0200 400 600 800
0
20
40
60
80
100
Weigh (%)
Tempe a u e (°C)
100% 10DA
75% 10DA
50% 10DA
25% 10DA
0% 10DA
Figu e S38: TGA aces o he ob ained PHUs by copolyme iza ion o a) bisCC-C4 and b) bisCC-C10 oge he
wi h a ious a ios o 10DA and P1075(10°C/min hea ing amp)
267.08°C 95.06%
417.60°C 50.00%
291.19°C
456.69°C
-0.2
0.3
0.8
1.3
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0100 200 300 400 500 600
Tempe a u e (°C)
Sample: BB318-TGA01
Size: 12.6140 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB318-TGA01
Ope a o : BB
Run Da e: 18-Jun-2018 12:04
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
265.72°C 95.06%
419.07°C 50.00%
292.25°C
452.82°C
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0200 400 600 800
Tempe a u e (°C)
Sample: BB319-TGA01
Size: 12.2010 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB319-TGA01.001
Ope a o : BB
Run Da e: 18-Jun-2018 13:22
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
263.58°C 95.06%
426.36°C 50.00%
291.56°C
453.21°C
-0.2
0.3
0.8
1.3
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0100 200 300 400 500 600
Tempe a u e (°C)
Sample: BB320-TGA01
Size: 14.7570 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB320-TGA01.001
Ope a o : BB
Run Da e: 18-Jun-2018 15:09
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
270.96°C 95.06%
428.93°C 50.00%
293.61°C
452.03°C
-0.2
0.3
0.8
1.3
1.8
De i . Weigh (%/°C)
0
20
40
60
80
100
Weigh (%)
0200 400 600 800
Tempe a u e (°C)
Sample: BB321-TGA01
Size: 16.7540 mg
Me hod: TGA Dég N2
TGA File: C:... Analyses TGA BB321-TGA01.001
Ope a o : BB
Run Da e: 18-Jun-2018 16:38
Ins umen : TGA Q500 V20.13 Build 39
Uni e sal V4.5A TA Ins umen s
Bulk Syn hesis o bio-based Poly(Hyd oxy U e hane)s – PHUs
145
7.5. SEC aces
a)
20 30 40
-0,2
0,0
0,2
0,4
0,6
0,8
1,0
1,2
RI (-)
Time (min)
100% 10DA
75% 10DA
50% 10DA
25% 10DA
0% 10DA
b)
20 30 40
-0,6
-0,4
-0,2
0,0
0,2
0,4
0,6
0,8
1,0
1,2
RI (-)
Time (min)
100% 10DA
75% 10DA
50% 10DA
25% 10DA
0% 10DA
Figu e S39 : Size exclusion aces o he ob ained PHUs by copolyme iza ion o a) bisCC-C4 o b) bisCC-C10
wi h a ious a ios o 10DA and P1075 oge he wi h (DMF, LiB , PS S anda ds)
7.6. DFT S udy – S uc u es o he in e media es
In 2, p im – bisCC-C4
In 2, sec – bisCC-C4
In 2, p im – bisCC-C10
In 2, sec – bisCC-C10
Figu e S 40: S uc u es o he In e media es In 2, p im and In 2, sec o bo h bisCC-C4 and bisCC-C10 as
ob ained by means o DFT calcula ions
.
CHAPTER 3
MINIEMULSION OF NON-ISOCYANATE
POLYURETHANE-ACRYLICS HYBRIDS AND
PROPERTIES OF THE CAST FILMS THEREOF
Keywo ds: Poly(Hyd oxy)u e hanes - PHUs
Bio-based Polyme s
NIPUs
PU-Ac ylic Hyb id
Miniemulsion
Coa ings

Chap e 3
148
Table o con en
1. In oduc ion ......................................................................................................................................... 149
2. Expe imen al ........................................................................................................................................ 150
2.1. Ma e ials ...................................................................................................................................... 150
2.2. Expe imen al design ............................................................................................................... 150
2.3. Miniemulsi ica ion and miniemulsion polyme iza ion ............................................ 151
2.4. Film cas ing ................................................................................................................................. 152
2.5. Cha ac e iza ion ....................................................................................................................... 153
3. Resul s and Discussion .................................................................................................................... 155
4. Conclusions ........................................................................................................................................... 165
5. Re e ences ............................................................................................................................................. 166
6. Sho ened o ms ................................................................................................................................. 169
7. Suppo ing In o ma ion................................................................................................................... 170
7.1. Side Reac ions ............................................................................................................................ 170
7.2. Solubili y ...................................................................................................................................... 175
7.3. Miniemulsion polyme iza ion using he mal ini ia o s ........................................... 179
7.3.1. Fo mula ions wi h he mal ini ia o s ......................................................................... 179
7.3.2. Resul s and discussion ...................................................................................................... 182
7.4. Fo mula ions wi h edox ini ia o s................................................................................... 184
7.5. SEC-MALLS T aces ................................................................................................................... 187
7.6. DSC T aces ................................................................................................................................... 188
7.7. Minimum Film Fo ming Tempe a u e (MMFT) .......................................................... 189
Miniemulsion polyme iza ion o Non-Isocyana e Polyu e hane-Ac ylics Hyb ids ia and p ope ies o he
cas ilms he eo
149
1. In oduc ion
Accessing high pe o mance polyme ma e ials wi h sa is ac o y p ope ies and
balanced p oduc ion cos usually equi es he syne gis ic combina ion o polyme s wi h
di e en and e en an agonis p ope ies. Hyb ids o polyu e hanes (PU) and
(me h)ac ylic polyme s is one o hese syne gis ic combina ions. PUs p o ide supe io
mechanical p ope ies such as oughness, lexibili y and ab asion esis ance,1–4 whe eas
poly(me h)ac ylics a e a o ding ma e ials wi h good ou doo and alkali esis ance, as
well as pigmen compa ibili y.4–6 PU-(me h)ac ylic hyb ids a e o en p epa ed as
wa e bo ne dispe sions ha ind applica ions as coa ings and adhesi es. The ield has
been ecen ly e iewed aiming a es ablishing he link be ween syn hesis, s uc u e and
p ope ies.7
The inal ou look o ha e iew poin s ou he challenges c ea ed by he en i onmen al
impac s o bo h he aw ma e ials used in he syn hesis and he need o de eloping low
VOC and p e e ably VOC- ee syn he ic ou es. Cu en ly, di-isocyana es a e used in he
PU syn hesis, bu hey may cause heal h issues such as as hma, de ma i is and e en
poisoning.8–10 In addi ion isocyana es equi e he use o phosgene in hei syn hesis and
his is a highly oxic gas ha can cause dea h by inhala ion. Sol en ee PU-(me h)ac ylic
hyb ids ha e been ob ained by syn hesizing he PU p epolyme using a mix u e o
(me h)ac ylic monome s as diluen s and hen dispe sing he solu ion in wa e .11–17
Howe e , achie ing good colloidal s abili y is challenging and equi es ine uning o he
syn he ic app oach.18
This chap e add esses he challenge o syn hesizing isocyana e- ee, sol en - ee
wa e bo ne PU-(me h)ac ylic dispe sions. The ield o wa e -based non-isocyana e
polyu e hanes (NIPUs) and polyu eas (NIPUUs) has been e iewed in Chap e 1. This
e iew shows ha he e a e only wo publica ions on he syn hesis o wa e bo ne NIPU-
ac ylic dispe sions.19,20 In hese wo ks, mono unc ional u e hane me hac yla es (UMA)
we e p epa ed by aminolysis o e hylene ca bona e and alipha ic amines in me hylene
chlo ide and hen he esul ing p oduc was unc ionalized wi h me hac ylic anhyd ide in
DMF. The UMAs we e copolyme ized wi h MMA/BA in a seeded emulsion polyme iza ion.
The me hod p esen s some d awbacks as i in ol es se e al s eps and uses sol en s.
Fu he mo e, he hyb ids do no con ained poly(u e hane) chains, bu u e hane moie ies.
In o de o o e come hese d awbacks in his chap e wo complemen a y s a egies
we e explo ed. The i s one in ol ed he o ma ion o he isocyana e- ee polyme by
aminolysis o cyclic-ca bona e de i a i es using (me h)ac ylic monome s as eac ing
media. This p ocess leads o poly(hyd oxy u e hane)s – o en called PHU.21–23 The idea
was o dispe se he PHU/(me h)ac yla es solu ion in wa e h ough a miniemulsi ica ion
p ocess, and hen polyme ize he (me h)ac ylic monome s by ee adical polyme iza ion.
Chap e 3
150
I will be shown ha his a i s sigh p omising idea encoun e s se e al se ious
p oblems. The second s a egy explo ed was i s o o m he PHUs by bulk aminolysis o
cyclic-ca bona e de i a i es using bio-sou ced ege able oil-based diamines. Then, he
PHU was dissol ed in (me h)ac yla e monome s and he solu ion used as he o ganic
phase o a miniemulsion. Subsequen polyme iza ion o he (me h)acylic monome s led
o he hyb id PU/(me h)ac yla es wa e bo ne dispe sion. The pe o mance o he ilms
cas om he hyb id wa e bo ne dispe sions was s udied.
2. Expe imen al
2.1. Ma e ials
1,4-bu anediamine (4DA, >98%), decane 1,10-diamine (10DA, >98%) and 1,12-
diaminododecane (12DA, >98%) we e supplied by TCI Eu ope. 1,6-haxanediamine (6DA,
>99%) was ob ained om Acc os. 1,3-cyclohexanebis(me hylamine) (CycloDA, 98%),
bu yl ace a e (BAc, >99%), Bu yl ac yla e (BA, >99%), bu yl me hac yla e (BMA, 99%),
s ea yl ac yla e SA, %, ,-azobis(2-me hylp opioni ile) (AIBN, 98%) and e -bu yl
hyd ope oxide (TBHP, 70% in wa e ) we e ob ained om Sigma. Asco bic acid (o
Vi amin C, AsA, >99.5%) was ob ained om Fluka. C oda kindly p o ided P iamineTM
1075 (P1075). Dow kindly p o ided alkyl diphenyl oxide disul ona e (Dow axTM 2A1,
D2A1, 45w % in wa e ). One cyclic ca bona es, bisCC-C10, was used. The syn hesis o his
ca bona e is de ailed in Chap e 2. All p oduc s and sol en s ( eagen g ade) we e used
as ecei ed unless o he wise men ioned. Deionized wa e was used.
2.2. Expe imen al design
As explained in he in oduc ion wo syn he ic s a egies we e explo ed. The i s one
in ol es he polyme iza ion o he cyclic ca bona es and diamines in (me h)ac ylic
monome s, ollowed by dispe sion in wa e and subsequen ee adical polyme iza ion
o he (me h)ac yla es.
As amines can po en ially eac wi h ac ylic monome s, ypically in an aza-Michael-
ype mechanism, he occu ence o his eac ion was checked. I was ound ha BA
su e ed a signi ican eac ion wi h he amines (Suppo ing In o ma ion – Figu es S1 o
S4). This is a s ong d awback because side eac ions consuming diamines will modi y he
s oichiome y subs an ially educing he molecula weigh o he polyme o med by his
s ep-g ow h polyme iza ion. Al hough BMA was only sligh ly a ec ed by his eac ion
(Suppo ing In o ma ion – Figu es S5 o S6), he s a egy based on he o ma ion o PHU
in (me h)ac yla es was abandoned and e o s we e concen a ed in he second s a egy
ha in ol ed he o ma ion o he PHUs by bulk aminolysis o bis-cyclic-ca bona e
de i a i es using bio-sou ced ege able oil-based diamines ollowed by dissolu ion o he
Miniemulsion polyme iza ion o Non-Isocyana e Polyu e hane-Ac ylics Hyb ids ia and p ope ies o he
cas ilms he eo
151
PHUs in (me h)ac ylic monome s, dispe sion in wa e o o m a miniemulsion, and ee
adical polyme iza ion o he inyl monome s. Miniemulsion polyme iza ion was used
because his p ocess is pa icula ly well sui ed o he syn hesis o hyb id dispe sions.24,25
Poly(hyd oxy)u e hanes (PHUs) we e syn hesized h ough he aminolysis eac ion
be ween bisCC-C10 and P1075 (Figu e 1). The s oichiome ic a io o he eac i e
moie ies was used o a ge high mola masses acco ding o he Ca o he s heo y.26 The
eac ions we e pe o med in bulk a 90°C o 24h in a Schlenk ube using a helical shaped
mechanical s i e speci ically designed o i in he Schlenk essel. No ca alys was added
o he polyme iza ion eac ions. No pu i ica ion o he PHUs was pe o med a e
eac ion.
Figu e 1: PHU p e-polyme u ilized o he syn hesis o PHU-Ac ylics hyb id ma e ials
A necessa y condi ion o he implemen a ion o he second app oach is ha he PHU
should be soluble in he (me h)ac yla es. The e o e, he solubili y o he PHUs ob ained
wi h a se ies o cyclic ca bona es and diamines in bu yl me hac yla e (BMA) was
de e mined. As shown in Suppo ing In o ma ion (Sec ion 6.2), he solubili y o he cyclic
ca bona es and diamines in BMA was low (mos o he diamines checked we e no soluble
o o mula ions a ge ing 10w % o PHU in BMA) al hough he solubili y could be
imp o ed using P1075.
2.3. Miniemulsi ica ion and miniemulsion polyme iza ion
The o mula ions used a e summa ized in Suppo ing In o ma ion (Tables S3 o S8 and
Table S10 o S13). The o ganic phase o he miniemulsion was p epa ed by dissol ing
P1075-based PHU (0 o 30 w .% weigh based on BMA) in a mix u e o BMA and SA (4
w % o SA) a 80°C. The aqueous phase was a 1 w % (based on he o al o ganic phase)
solu ion o Dow ax2A1 in deionized wa e . The o ganic phase was added d op-wise in o
he aqueous phase unde igo ous magne ic s i ing. Then, he miniemulsion was o med
by sonica ing he coa se emulsion o 30 min wi h a Hielsche Ul asonics GmbH ( e
UIS250V) using an ampli ude o 100% and 0.8s du y cycle. A pos -s abiliza ion s ep is
pe o med by adding 1 w .% o Dow ax 2A1 based on he o al o ganic phase dissol ed in
a minimum amoun o deionized wa e .
The miniemulsion was ans e ed o a 3-neck ound-bo om lask and lushed wi h
ni ogen du ing 30 min a 70°C. Then, he ini ia o was added in a way ha depended on
he ype o ini ia o . The pe o mance o he mal ini ia o s was i s checked using AIBN