Deciphering Siloxane Bond Exchanges: from a Molecular Study to

vitrimerization and recycling of Silicone Elastomers.

Douriya Z. Khedaioui, Camille Tribout, Julie Bratasanu, Franck D’Agosto, Christophe Boisson
and Damien Montarnal*
Univ Lyon, Université Claude Bernard Lyon 1, CPE Lyon, CNRS, UMR 5128, Chemistry, Polymerization, Processes
and Materials, 43 Bvd du 11 Novembre 1918, 69616 Villeurbanne, France.

KEYWORDS: siloxane exchange, dynamic networks, vitrimers, rheological model

ABSTRACT: The activity of various additives promoting siloxane equilibration reactions is examined and quantified on
model compounds. We found in particular that the “superbase” phosphazene derivative P4tBu can promote very fast ex-
changes (a few seconds at 90 °C) even at low concentration (<0.1 wt%). We demonstrate that permanent silicone networks
can be transformed into reprocessable and recyclable dynamic networks by mere introduction of such additives. Annealing
at high temperature degrades the additives and deactivates the dynamic features of the silicone networks, reverting them
back into permanent networks. A simple rheological experiment and the corresponding model allow to extract the critical
kinetic parameters to predict and control such deactivations.

INTRODUCTION This silanolate moiety is further involved and regenerated

Silicone elastomers feature high flexibility, high thermal through nucleophilic attacks on other Si-O-Si bonds. This
stability, and both hydrophobic and oleophobic surface equilibration reaction is also at the core of the equilibrium
properties. They are used in a vast range of applications between rings and linear chains in PDMS polymers that oc-
such as heat-resistant sealants or encapsulants, moulds, curs to a certain extent in anionic ring-opening polymeri-
cosmetics, drug delivery or bio-implants1,2 While recent ac- zation (ROP) of silicones, and that started to be studied by
ademic and industrial developments have led to silicone Wright and Semlyen in the 70’s.33,34 Exploitation of such
thermoplastic elastomers (SiTPEs), such as segmented equilibration reactions in dynamic crosslinked silicone
block copolymers3–5 or thermoplastic vulcanizates (SiT- networks was however only brought up by McCarthy and
PVs),6,7 the vast majority of silicone elastomers are still ob- Zheng in 2012.35 They conducted an anionic ROP of oc-
tained through conventional cross-linking methods such tamethyl tetrasiloxane (D4) in presence of a bis-D4 cross-
as hydrosilylation, hydrolysis-condensation or radical re- linker initiated by an oligosiloxane functionalized with tet-
actions (essentially peroxides- or UV-induced)8. Unlike ramethylammonium silanolate endgroups (TMA2-PDMS).
conventional cross-linked elastomers, recycling routes for In absence of quenching, the living silanolate group ena-
silicone elastomers is practically and economically feasible bles dynamic chain exchange and welding of fractured
through chemical depolymerization with acids, bases or parts at 90°C for 24h. Although precise measurement of ex-
fluorides9, which is particularly favored in the case of change dynamics or network relaxation times were not car-
poly(dimethyl siloxane) by the equilibration between ried out, these materials were further studied by Seiffert
(macro)cyclic and linear forms and the high volatility of and coworkers, using this time as catalyst tetrame-
the smaller cyclic species (D4 to D6) that can be recovered thylammonium hydroxide (TMAOH) at higher concentra-
by distillation and repolymerized.10–13 Alternatively, cova- tions than McCarthy.36 Using home-made piercing experi-
lent adaptable network (CAN) strategies14–21 have been re- ments that monitor the flow of dynamic networks, they
cently applied to silicone materials with the prospect of di- found very fast relaxations, typically in the 1-2 s range, with
rectly healing cracks or reprocessing the materials by only weak dependencies to catalyst concentrations or to
grinding and molding steps. Three approaches can be dis- temperature in the 5-60°C range. Exciting benefits of mal-
tinguished: i) the use of dissociative crosslinks such as leable silicone networks have also been explored by Xie
Diels-Alder adducts22 or borate esters (the original “silly and coworkers, who combined plastic deformation of mi-
putty” formulation23) that provide viscoelastic or TPE ma- cropatterned silicones with pyrolysis to obtain well defined
terials, ii) the use of associative exchanges: UV-induced di- silicon oxycarbide ceramics.37 The malleable silicone net-
sulfide exchanges,24 heat-activated transesterifications,25,26 work was obtained this time directly by adding sodium oc-
imine exchange,27 vinylogous urethanes28 or derivatives of tanoate (NaOct) from a commercial two-component for-
Meldrum’s acids29 and iii) the direct and controlled cataly- mulation undergoing platinum-catalyzed hydrosilylation
sis of siloxane exchanges. (Sylgard 184 from Dow Corning). Much higher tempera-
tures were however required for malleability, typically be-
The latter has been known for over 70 years, with the pio- tween 180 and 200°C. More recently, the group of Terentjev
neering work on siloxane bond equilibration of Osthoff in has also investigated the use of siloxane crosslinks for the
the 1950s.30–32 The underlying admitted mechanism for ba- reprocessing of liquid crystalline elastomers obtained after
ses or fluorides is the cleavage of the Si-O-Si bond by nu- thiol-acrylate Michael addition between mesogenic diacry-
cleophilic displacement, which forms a silanolate anion. lates and isotropic dithiols.38 Several additives were found
to induce relaxations in these networks, such as TMA2- within all these studies of the effect of network composi-
PDMS, triphenylphosphine (TPP), triazobicyclodecene tion and the nature or concentration of catalysts on the ex-
(TBD) and NaOct. TBD, also known to ring-open and pol- change dynamics of siloxanes prompted us for a more thor-
ymerize effectively cyclic siloxane,39 was found very effec- ough comparison of various catalysts using model com-
tive. In this case also, very high temperatures from 190°C to pounds. Recognizing the importance of the effective solu-
210°C were required, even in the case of tetramethylammo- bility of catalysts in highly apolar environments and the
nium-based catalysts that are yet known to degrade above economical necessity to use catalytic amounts of additives,
150 °C.40,41 Last, Du Prez and coworkers recently investi- we ensured in particular to study purely siloxane environ-
gated epoxy resins containing bisamine disiloxane harden- ments, either as small model molecules or as target dy-
ers and various catalysts (strong organic bases and si- namic networks.
lanolates). While studies of siloxane exchanges on disilox- While we found unexpectedly that several additives men-
ane model molecules barely showed any effect of TBD (5 tioned above do not promote sizeable siloxane exchanges,
mol%) over 16 h at 120 °C, the addition of alcohols slightly we also discovered that a phosphazene derivative, P4tBu
accelerated the exchange. Mechanical relaxation of the (please see full name in the Materials section in SI), is ex-
epoxy networks containing 10 mol% TBD/Si and a large tremely effective. Incorporation of this additive in both
amount of hydroxyls issued from the epoxy-amine reaction model and commercial silicone networks proved a highly
showed however dramatically faster relaxations, down to efficient way to transform them into malleable dynamic
about 5 s at 220°C which eventually enabled reprocessing networks. Last, we also discovered that at temperatures
and thermoforming of composites.42 higher than 130°C thermal degradation of P4tBu effectively
Given the historical and technological relevance of dy- deactivates the dynamic siloxane exchanges and the net-
namic siloxane exchanges, the apparent discrepancy works are reverted to non-dynamic networks. We empha-

Figure 1. a) Molecular study of the siloxane bond exchange. b) Library of additives used to induce the dynamic ex-
change. c) Kinetic study at 90 °C in presence of 100 ppm of additive. d) Mechanism involved for the siloxane bond
exchange.
size that proper control of such deactivation and corre- pairing is critical for the reactivity of silanolates. This
sponding predictive mathematical modelling opens excit- prompted us to test bases with highly delocalized charge
ing perspectives for dynamic networks in general, and may and excellent solubility in apolar media. In this regard, the
solve the difficult compromise that must be made between P4tBu “superbase” is known to form phosphazenium hy-
fast dynamics required for (re)processing the networks at droxide [HP4tBu]+[HO]- or alcoxides in presence of adven-
high temperatures and very slow dynamics required for ef- titious water or alcohols (See Scheme 1), 44–46 and is also
fective creep-resistance at service temperatures.43 amongst the most efficient known initiators for ROP of D4
cyclic siloxanes. 7,41–45 P4tBu was indeed found extremely ef-
RESULTS AND DISCUSSION
ficient for these siloxane equilibrations, with ca. 3 min of
Molecular study of catalyzed siloxane exchanges. While exchange time at 0.1 wt% and 90°C (Figure 1c). We assume
the equilibration of siloxanes has been studied as early as that the traces of water enables the in situ formation of
the 1950s the kinetics of these reactions was never, to the [HP4-tBu]+[HO]- initiator.
best of our knowledge, studied explicitly with model com-
As expected, increasing the amount of additives and heat-
pounds. We chose short disiloxane compounds bearing
ing accelerates the exchanges kinetics. The corresponding
different substituents (hexamethyldisiloxane - HMDS and
mastercurve of exchange kinetics at different temperatures
divinyltetramethyldisiloxane - DVTMS). The expected
for TMA2-PDMS (Figure S2) demonstrates the absence of
cross-exchange product (vinylpentamethyldisiloxane -
latent effects in these reactions (e.g. sudden increase of re-
VPMDS) is also commercially available and can be easily
activity above a temperature threshold) and allows to de-
quantified by gas chromatography (GC, Figure S1 in SI).
termine for 0.1 wt% additive an exchange time about 900 s
The established exchange mechanism involves the for-
at 90°C and an activation energy Ea, of 92 kJ mol-1. The ex-
mation of a silanolate ion pair as the active catalytic center
change kinetics also depend on the concentration, with a
(See Figure 1d). In practice, the various molecules added to
10-fold acceleration from 0.05 wt% to 5 wt% of additive
accelerate the siloxane exchanges may only be precursors
(Figure S3).
(e.g. organic bases, hydroxides) to the silanolates species.
For clarity throughout the manuscript we will refer to them Above 110°C, however, the reaction becomes slower, which
as additives. HMDS and DVTMS were mixed in equimolar might be related to the thermal decomposition of the tet-
ratios in presence of various additives (Figure 1b) at low ramethylammonium silanolate in trimethylamine and
concentration (0.1 wt%) and in absence of any additional methoxysilane, or its subsequent condensation products as
solvents. Samples withdrawn at different times from the reported in the literature.35 No clear evidence of such de-
reaction medium were analyzed by GC to quantify the evo- composition products were however identified on the gas
lution of the fractions of HDMS, DVTMS and VPDMS dur- chromatograms as trimethylamine is highly volatile.
ing the reaction. The resulting equilibration kinetics is dis- TMSOMe and DVSOMe might also condense readily to re-
played in Figure 1c. Surprisingly, no formation of VPMDS form HMDS, DVTMS and VPMDS.45 The deactivation of
was observed after 24 hours of reaction when TPP, NaOct TMA2-PDMS at 120°C was further verified by pre-equili-
and TBD were used as additives. Widely used tetramethyl brating the additive with HMDS for 2h before adding 1 eq.
ammonium basic salts, TMAOH and TMA2-PDMS display of VDTMS. In this case, no cross-exchanged VPDMS could
characteristic equilibration times of ca. 2 h and 1 h, respec- be detected after 2h.
tively, while CsOH is much slower (ca. 150 h). Such differ- In comparison, the P4tBu additive at 0.1 wt% shows much
ences are significant given that TMA2-PDMS and TMAOH faster exchanges, ca. 75 s at 90°C (Figure S4) with compa-
involve the same counter ions (tetramethylammonium) rable activation energy about 100 kJ mol-1.
and should lead to the same silanolate active species after Silicone vitrimers. Model polysiloxane networks were
the first exchange with disiloxanes (see Figure 1d). We at- prepared to further study the effect of these siloxane ex-
tribute thus the significant induction time with TMAOH changes on relaxations. Liquid silicone resins (LSR)-like
to a poor solvatation of this salt in the apolar disiloxanes formulations have been implemented using divinyl-termi-
and correspondingly to a slow conversion in tetramethyl nated poly(dimethylsiloxane) (Mw = 25 000 g mol-1),
ammonium silanolate. The same reasoning might also ex- polymethylhydrosiloxane crosslinker (Mw = 1900 g mol-1,
plain the lower activity of CsOH. SiH/Vinyls=2) and a Pt-based NHC derivative (300 ppm/vi-
Further investigation about the nature of the silanolate ac- nyls)47,48 that allows a complete curing within 15h at 75°C
tive center was obtained by directly using lithium, sodium, (please see complete description in the SI). The resulting
or potassium silanolates. In the three cases no VPDMS was networks do not display any detectable extractible fraction
observed, thus demonstrating that highly dissociated ion ; they are permanent networks (see stress relaxations be-
low) and relatively brittle (εbreak about 100%) given the rel-
atively low molar mass of the divinyl PDMS precursors.
All additives accelerating siloxane exchanges are bases and
thus incompatible with the crosslinking reaction by Pt-cat-
alyzed hydrosilylation. The additives were thus post-added
in the PDMS networks by solvent-assisted diffusion in tol-
uene. To ensure homogeneous dispersion, 8 mm x ca. 1.5
Scheme 1 Activation of P4tBu by the adventitious pres- mm disks of the PDMS networks were impregnated with
ence of water in HMDS and DVTMS
the exact amount of additive solution in toluene required controlled amounts of benzyl alcohol (BzOH, 0.5 and 1 eq.
for swelling to the equilibrium (e.g. a 1:1 weight ratio of so- to P4tBu); the corresponding deactivations proceed to
lution to PDMS sample), and left to dry at 40°C overnight. much larger extents, effectively yielding kinetics compara-
As P4tBu shows promising results in terms of solubility and ble to networks initially loaded with ca. 33 ppm of P4tBu/Si.
equilibration times in the above study involving molecular
compounds, we focused our study on its use to induce si-
loxane bond exchanges in PDMS networks. A control ex-
periment on the pristine PDMS rubber (Figure 2) demon-
strates the absence of any relaxation at 90 °C.

Figure 3. Evolution of relaxation times at 90°C in model

silicone networks containing various amounts of
P4tBu/Si and BzOH.
Extended uses of such exchange deactivations can be
found at elevated temperatures, when thermal degradation
of the silanolate salts occurs. A rapid screening of the time-
Figure 2. Stress relaxation at 90°C (1% strain) of model sil- and temperature-evolution of deactivation was found by
icone networks containing 0-100 ppm P4tBu/Si. monitoring the creep behavior while applying a heating
Adding P4tBu to the networks in amounts from 16 to 100 ramp to the material (Figure 4). While the viscosity is ex-
ppm to Si atoms (e.g. from 0.01 wt% to 0.09 wt%) induces pected to continuously decrease upon heating, temporary
stress relaxation (Figure 2 – The corresponding frequency idleness around 80-100°C corroborates a partial deactiva-
sweeps are shown in Figure S5 in SI), with corresponding tion. A subsequent dramatic increase of viscosity above
characteristic times from 1700 to 3 s. Notably, these dy- 140°C indicates a second and total deactivation, which
namic exchanges are complemented by a decrease in the would effectively transform the highly dynamic networks
plateau moduli (from about 350 kPa for the initial network into quasi-permanent networks.
to about 100 kPa for the highest P4tBu loading) that sub-
stantiates the expected mechanism of this additive. First,
Si-O-Si chains are cleaved by the phosphazenium hydrox-
ides to yield phosphazenium silanolates acting as persis-
tent active centers. Further exchanges within the network
allow strand exchanges and stress relaxation. It should be
noted that such reorganizations also trigger the formation
of volatile cyclic siloxanes by back-biting reactions. Conse-
quently, the crosslinked samples gradually depolymerize
and evaporation takes place over time at 90°C. Figure S6
shows the weight loss of ca. 70 mg disks after annealing in
open air at 90°C for 6h: significant losses > 25wt% are ob-
served for P4tBu concentrations above 100 ppm /Si. This
limited stability illustrates a major drawback of fast dy-
namics in silicone networks and prompted us to character-
ize the time-dependent evolution of exchange dynamics.
Deactivation of exchange reactions. We carried out re- Figure 4. Evolution of apparent creep viscosity in model
peated stress relaxations (1% strain) to measure the evolu- network containing 100 ppm P4tBu during a 1°C min-1
tion of characteristic relaxation times (Figure 3). The net- heating ramp.
work containing 100 ppm P4tBu displays an initial increase Deactivation dynamics and modelling. Further analysis
of relaxation times that levels off to about 30 s after 1h. We of thermal deactivation in the 130-170°C range was carried
hypothesized that this change is due to slow and partial out on networks containing 33 ppm of P4tBu/Si using re-
deactivation of the silanolate groups due to impurities in peated stress relaxation cycles (Figure 5). While relaxations
the network, probably water.49 We verified this by adding at 130°C are slow (ca. 4000 s) but relatively reproducible
Figure 5. Repeated stress relaxations (normalized) of model networks containing 33 ppm P4tBu/Si at 130, 150 and 170°C.
The total heating time for each series is represented by the color scale. Black lines are fits corresponding to a) individual
stretched exponential decays, and b,c) general model (eq. 1) accounting for repeated deactivating relaxations.
over 5h, relaxations at 150 and 170°C are initially consider- G0 is the network modulus, τ0 and τd are the initial relaxa-
ably faster, but slow down significantly over time. Delayed tion time and the characteristic deactivation time of the
relaxations at 170°C are clearly not representative of classi- relaxation, respectively, Δt is the time-delay between the
cal mono- or stretched exponential decays encountered in initial heating of the sample (start of the deactivation) and
dynamic networks,43 but are likely indicative that the de- each successive stress relaxation experiment, β is the
activation occurs over similar timescales as the stress re- stretch parameter characteristic of the breadth of distribu-
laxation. tion of relaxation times. Details of derivation of eq 1 and
simulations for different sets of values are represented in
SI. For each temperature, fitting of all successive stress re-
laxation data is carried using a single set of τ0, τd and β val-
ues and fixed Δt parameters using the “Global fit” feature
of Origin software (Figure 5). The G0 parameters are indi-
vidualized during the fitting to account for small variations
of initial moduli.
Given the low amount of fitting parameters (τ0, τd, β) for
such multiple datasets, the fit quality is remarquable and
substantiates the validity of the model. As expected, the re-
sults indicate that initially, the relaxation times are signif-
icantly faster at 170°C than at 130°C. Yet, degradation oc-
curs more significantly at higher temperatures and the sit-
uation becomes reversed after about 2h of heating (Figure
6).
In line with initial studies on model compounds, the deac-
tivation was also studied by rheology for PDMS networks
Figure 6. Evolution of relaxation times at different tem-
containing 33 ppm/Si of TMA2PDMS and CsOH additives.
peratures in model silicone networks containing 33 ppm
(See Figure 6 and corresponding sets of stress relaxation in
of additives. Dots correspond to individual fits while
continuous lines correspond to first-order deactivation Figure S8) It was found that the TMA additive was initially
models (eq 1). moderately efficient, but degraded very quickly at 150°C
(deactivation time τd about 20 min). In accordance with the
Thus, we derived a low-parameter model for stress relaxa- above studies on model compounds, CsOH shows initially
tions that takes into consideration a first-order deactiva- a much lower activity but also deactivates much more
tion, i.e. that effective relaxation times are increasing ex- slowly (τd about 1.5 h at 160°C).
ponentially with time: Reprocessability of PDMS elastomers. The maximal
𝝉 −
𝜟𝒕
−
𝒕+𝜟𝒕 𝜷 stress relaxation expected during a single step before the
− ( 𝒅 [𝒆 𝝉𝒅 − 𝒆 𝝉𝒅 ]) deactivation completely transforms the dynamic network
𝝉𝟎
𝑮(𝒕) = 𝑮𝟎 . 𝒆 (eq. 1)
into a permanent network can be determined from eq 1 us- P4tBu recovers most of the elongation at break at the ex-
ing Δt = 0 s and is strongly driven by the ratio τd/τ0. Figure pense of a 70% decrease in modulus (Figure 8). In contrast,
7 gives in this way an estimation of the processability win- the sample containing 30 ppm P4tBu suffers from a signifi-
dow after 30 min of deformation. The values obtained for cant decrease of elongation at break and a lower decrease
the different additives at 33 ppm are reported, and indicate in modulus (-55%).
clearly that with such concentrations, proper reprocessing In view of the very low amount of additives used, such im-
within 30 min could only be expected with P4tBu at 170°C. portant changes are strongly driven by the topology of the
model PDMS networks chosen that feature mainly long
linear chains (99 wt%) anchored at extremities by poly-
functional crosslinkers. It would be interesting in future
developments of siloxane dynamic networks to either pro-
mote recoupling of cleaved chains in such topologies, or to
focus on different topologies featuring permanent polymer
backbones equipped with dynamic siloxane crosslinks.

CONCLUSIONS
We showed using model compounds that the dynamics of
siloxane exchanges are extremely dependent on the envi-
ronment of the silanolate living chain-ends, and that
highly delocalized and hydrophobic cations such as the
P4tBu phosphazene derivative are extremely active even in
low amounts (below 0.1 wt%). When implemented in
crosslinked PDMS networks, such siloxane exchanges pro-
mote dynamic strand exchanges and stress relaxation. We
also show that the silanolate active centers can be lost by
two distinct phenomena: i) a partial deactivation around
Figure 7. Diagram of processability window, displaying 90°C that we attribute to reactions with impurities and ii)
the expected amount of relaxed stress after deforming a a complete thermal deactivation that occurs above 120°C
sample for 30 min, depending on the corresponding ini- depending on the additive.
tial relaxation time τ0 and the deactivating time τd. The
The understanding at the molecular level of such thermal
calculation was made with β = 0.66. Experimental values
deactivations remains unclear and challenging given the
obtained for PDMS samples loaded with 33 ppm of addi-
tives are reported.
low concentrations of additives involved. We show how-
ever that simple rheological experiments (e.g. repeated
stress relaxations) and a low-parameter model enables to
quantify very easily both the initial dynamics of exchange
and the corresponding deactivation time.
In the scope of CANs and more specifically vitrimers, such
deactivating relaxations could constitute an interesting al-
ternative against the problematic tradeoff between creep
resistance at low temperatures and processability at high
temperatures. Activation of the relaxations could for in-
stance be triggered only when needed (e.g. during the re-
cycling or reshaping of the materials by locally adding the
additives) and further deactivated by annealing at high
temperatures to yield permanent networks.

ASSOCIATED CONTENT
Supporting Information. Experimental details on materials,
instrumentation and synthetic procedures of model networks,
Additional experimental results and derivation of deactivating
Figure 8. Tensile testing of PDMS elastomers after repro- stress relaxation models. This material is available free of
cessing for 30 min at 170°C using 30 & 50 ppm P4tBu /Si. charge via the Internet at http://pubs.acs.org.
Young moduli are reported next to each curve.
AUTHOR INFORMATION
The effectiveness of the reprocessing was evaluated by im-
Corresponding Author
pregnating shredded PDMS elastomer with 30 and 50 ppm
P4tBu/Si, and mold-pressing the fragments under 40 MPa, * damien.montarnal@univ-lyon1.fr
for 30 min at 170°C. In absence of additive, only non-cohe- Author Contributions
sive powder is obtained. The sample containing 50 ppm
The manuscript was written through contributions of all au- 9682–9695. DOI 10.1002/anie.201813525.
thors. All authors have given approval to the final version of (15) Elling, B. R.; Dichtel, W. R. Reprocessable Cross-Linked
the manuscript. Polymer Networks: Are Associative Exchange Mechanisms
Desirable? ACS Cent. Sci. 2020, 6 (9), 1488–1496. DOI
Funding Sources 10.1021/acscentsci.0c00567.
(16) Zheng, N.; Xu, Y.; Zhao, Q.; Xie, T. Dynamic Covalent
Polymer Networks: A Molecular Platform for Designing
DM gratefully acknowledges funding from ANR (grant
Functions beyond Chemical Recycling and Self-Healing.
AEROLEFIN, ANR-17-CE07-0006) for financial support. Chem. Rev. 2021, 121 (3), 1716–1745. DOI
10.1021/acs.chemrev.0c00938.
ACKNOWLEDGMENT (17) Scheutz, G. M.; Lessard, J. J.; Sims, M. B.; Sumerlin, B. S.
We are indebted to Vincent Monteil, Jean Raynaud and Adaptable Crosslinks in Polymeric Materials: Resolving the
Intersection of Thermoplastics and Thermosets. J. Am.
Nam Vu for stimulating discussions. Chem. Soc. 2019, 141 (41), 16181–16196. DOI
10.1021/jacs.9b07922.
REFERENCES (18) Cuminet, F.; Caillol, S.; Dantras, E.; Leclerc, E.; Ladmiral, V.
(1) Shit, S. C.; Shah, P. A Review on Silicone Rubber. Natl. Acad. Neighboring Group Participation and Internal Catalysis
Sci. Lett. 2013, 36 (4), 355–365. DOI 10.1007/s40009-013-0150- Effects on Exchangeable Covalent Bonds: Application to the
2. Thriving Field of Vitrimer Chemistry. Macromolecules 2021.
(2) Mazurek, P.; Vudayagiri, S.; Skov, A. L. How to Tailor DOI 10.1021/acs.macromol.0c02706.
Flexible Silicone Elastomers with Mechanical Integrity: A (19) Van Zee, N. J.; Nicolaÿ, R. Vitrimers: Permanently
Tutorial Review. Chem. Soc. Rev. 2019, 48 (6), 1448–1464. Crosslinked Polymers with Dynamic Network Topology.
DOI 10.1039/c8cs00963e. Prog. Polym. Sci. 2020, 104, 101233. DOI
(3) Yilgör, I.; Riffle, J. S.; Wilkes, G. L.; McGrath, J. E. Siloxane- 10.1016/j.progpolymsci.2020.101233.
Urea Segmented Copolymers - 1. Synthesis and (20) Guerre, M.; Taplan, C.; Winne, J. M.; Du Prez, F. E. Vitrimers:
Characterization of Model Polymers from MDI and α, ω- Directing Chemical Reactivity to Control Material
Bis(Aminopropyl)Polydimethylsiloxane. Polym. Bull. 1982, 8 Properties. Chem. Sci. 2020, 11 (19), 4855–4870. DOI
(11–12), 535–542. DOI 10.1007/BF00262932. 10.1039/d0sc01069c.
(4) Falco, G.; Simonin, L.; Pensec, S.; Dalmas, F.; Chenal, J. M.; (21) Winne, J. M.; Leibler, L.; Du Prez, F. E. Dynamic Covalent
Bouteiller, L.; Chazeau, L. Linear and Nonlinear Viscoelastic Chemistry in Polymer Networks: A Mechanistic Perspective.
Properties of Segmented Silicone-Urea Copolymers: Polym. Chem. 2019, 10 (45), 6091–6108. DOI
Influence of the Hard Segment Structure. Polymer 2020, 186 10.1039/c9py01260e.
(December 2019). DOI 10.1016/j.polymer.2019.122041. (22) Gou, Z.; Zuo, Y.; Feng, S. Thermally Self-Healing Silicone-
(5) Zhu, B.; Grassman, M. Silicone Urethane Urea Copolymer Based Networks with Potential Application in Recycling
and Preparation and Use Thereof. WO2018151780, 2017. Adhesives. RSC Adv. 2016, 6 (77), 73140–73147. DOI
(6) Mani, S.; Cassagnau, P.; Bousmina, M.; Chaumont, P. 10.1039/c6ra14659g.
Morphology Development in Novel Composition of (23) McGregor, R. R.; Warrick, E. L. Treating Dimethyl Silicone
Thermoplastic Vulcanizates Based on PA12/PDMS Reactive Polymer with Boric Oxide, US Patent 2,431,878. 2431878,
Blends. Macromol. Mater. Eng. 2011, 296 (10), 909–920. DOI 1947.
10.1002/mame.201000406. (24) Xiang, H. P.; Rong, M. Z.; Zhang, M. Q. A Facile Method for
(7) Gornowicz, G.; Zhang, H. THERMOPLASTIC SILICONE Imparting Sunlight Driven Catalyst-Free Self-Healability and
VULCANIZATES PREPARED BY CONDENSATION CURE. Recyclability to Commercial Silicone Elastomer. Polymer
6,153,691, 2000. 2017, 108, 339–347. DOI 10.1016/j.polymer.2016.12.006.
(8) Stark, F. O.; Falender, J. R.; Wright, A. P. Silicones. Compr. (25) Zhang, H.; Cai, C.; Liu, W.; Li, D.; Zhang, J.; Zhao, N.; Xu, J.
Organomet. Chem. 1982, 2, 305–363. DOI 10.1016/B978- Recyclable Polydimethylsiloxane Network Crosslinked by
008046518-0.00016-7. Dynamic Transesterification Reaction. Sci. Rep. 2017, 7 (1), 1–
(9) Rupasinghe, B.; Furgal, J. C. Full Circle Recycling of 9. DOI 10.1038/s41598-017-11485-6.
Polysiloxanes via Room-Temperature Fluoride-Catalyzed (26) Tran, T. N.; Rawstron, E.; Bourgeat-Lami, E.; Montarnal, D.
Depolymerization to Repolymerizable Cyclics. ACS Appl. Formation of Cross-Linked Films from Immiscible
Polym. Mater. 2021, 3 (4), 1828–1839. DOI Precursors through Sintering of Vitrimer Nanoparticles. ACS
10.1021/acsapm.0c01406. Macro Lett. 2018, 7 (3), 376–380. DOI
(10) Okamoto, M.; Suzuki, S.; Suzuki, E. Polysiloxane 10.1021/acsmacrolett.8b00173.
Depolymerization with Dimethyl Carbonate Using Alkali (27) Feng, Z.; Yu, B.; Hu, J.; Zuo, H.; Li, J.; Sun, H.; Ning, N.; Tian,
Metal Halide Catalysts. Appl. Catal. A Gen. 2004, 261 (2), 239– M.; Zhang, L. Multifunctional Vitrimer-Like
245. DOI 10.1016/j.apcata.2003.11.005. Polydimethylsiloxane (PDMS): Recyclable, Self-Healable,
(11) Chang, C. L.; Lee, H. S. J.; Chen, C. K. Nucleophilic Cleavage and Water-Driven Malleable Covalent Networks Based on
of Crosslinked Polysiloxanes to Cyclic Siloxane Monomers: Dynamic Imine Bond. Ind. Eng. Chem. Res. 2019, 58 (3), 1212–
Mild Catalysis by a Designed Polar Solvent System. J. Polym. 1221. DOI 10.1021/acs.iecr.8b05309.
Res. 2005, 12 (6), 433–438. DOI 10.1007/s10965-004-1871-1. (28) Stukenbroeker, T.; Wang, W.; Winne, J. M.; Du Prez, F. E.;
(12) Julian, D. J.; Katsoulis, D.; Link, B. A.; Peitz, T. A.; Zhu, B. Nicolaÿ, R.; Leibler, L. Polydimethylsiloxane Quenchable
METHOD OF RECYCLING SILICONE WASTE WITH THE Vitrimers. Polym. Chem. 2017, 8 (43), 6590–6593. DOI
USE OF ORGANIC POLYMER AND DEPOLYMERIZATION 10.1039/c7py01488k.
CATALYST. WO 2014/130948, 2014. (29) Ishibashi, J. S. A.; Kalow, J. A. Vitrimeric Silicone Elastomers
(13) Fouquet, T.; Bour, J.; Toniazzo, V.; Ruch, D.; Charles, L. Enabled by Dynamic Meldrum’s Acid-Derived Cross-Links.
Characterization of Ethanolysis Products of ACS Macro Lett. 2018, 7 (4), 482–486. DOI
Poly(Dimethylsiloxane) Species by Electrospray Ionization 10.1021/acsmacrolett.8b00166.
Tandem Mass Spectrometry. Rapid Commun. Mass (30) Hurd, D. T.; Osthoff, R. C.; Corrin, M. L. The Mechanism of
Spectrom. 2012, 26 (17), 2057–2067. DOI 10.1002/rcm.6317. the Base-Catalyzed Rearrangement of Organopolysiloxanes.
(14) Chakma, P.; Konkolewicz, D. Dynamic Covalent Bonds in J. Am. Chem. Soc. 1954, 76 (1), 249–252. DOI
Polymeric Materials. Angew. Chemie - Int. Ed. 2019, 58 (29), 10.1021/ja01630a064.
(31) Osthoff, R. C.; Bueche, A. M.; Grubb, W. T. Chemical Stress-
 Relaxation of Polydimethylsiloxane Elastomers. J. Am. Chem. Du Prez, F. E. Covalent Adaptable Networks with Tunable
Soc. 1954, 76 (18), 4659–4663. DOI 10.1021/ja01647a052. Exchange Rates Based on Reversible Thiol–Yne Cross-
(32) Kantor, S. W.; Grubb, W. T.; Osthoff, R. C. The Mechanism Linking. Angew. Chemie - Int. Ed. 2020, 59 (9), 3609–3617.
of the Acid- and Base-Catalyzed Equilibration of Siloxanes. J. DOI 10.1002/anie.201912902.
Am. Chem. Soc. 1954, 76 (20), 5190–5197. DOI (42) Debsharma, T.; Am, V.; Alicja, A.; Baere, I. De; Paepegem, W.
10.1021/ja01649a076. Van; Prez, F. E. Du. Fast Dynamic Siloxane Exchange
(33) Wright, P. V. Cyclization Equilibrium Constants and the Mechanism for Reshapable Vitrimer Composites. 2022. DOI
Conformations of Polydimethylsiloxane Chains. J. Polym. 10.1021/jacs.2c03518.
Sci. Part A-2 Polym. Phys. 1973, 11 (1), 51–64. DOI (43) Jourdain, A.; Asbai, R.; Anaya, O.; Chehimi, M. M.;
10.1002/pol.1973.180110106. Drockenmuller, E.; Montarnal, D. Rheological Properties of
(34) Wright, P. .; Semlyen, J. . Equilibrium Ring Concentrations Covalent Adaptable Networks with 1,2,3-Triazolium Cross-
and the Statistical Conformations of Polymer Chains: Part 3. Links: The Missing Link between Vitrimers and Dissociative
Substituent Effects in Polysiloxane Systems. Polymer 1970, 11 Networks. ACS Appl. Mater. Interfaces 2020, 53, 1884–1900.
(9), 462–471. DOI 10.1016/0032-3861(70)90051-0. DOI 10.1021/acs.macromol.9b02204.
(35) Zheng, P.; McCarthy, T. J. A Surprise from 1954: Siloxane (44) Boileau, S.; Illy, N. Activation in Anionic Polymerization:
Equilibration Is a Simple, Robust, and Obvious Polymer Self- Why Phosphazene Bases Are Very Exciting Promoters. Prog.
Healing Mechanism. J. Am. Chem. Soc. 2012, 134 (4), 2024– Polym. Sci. 2011, 36 (9), 1132–1151. DOI
2027. DOI 10.1021/ja2113257. 10.1016/j.progpolymsci.2011.05.005.
(36) Schmolke, W.; Perner, N.; Seiffert, S. Dynamically Cross- (45) Köhler, T.; Gutacker, A.; Mejía, E. Industrial Synthesis of
Linked Polydimethylsiloxane Networks with Reactive Silicones: Reaction Mechanisms and Processes.
Ambienterature Self-Healing. Macromolecules 2015, 48 (24), Org. Chem. Front. 2020. DOI 10.1039/d0qo01075h.
8781–8788. DOI 10.1021/acs.macromol.5b01666. (46) Hupfield, P. C.; Taylor, R. G. Ring-Opening Polymerization
(37) Zheng, N.; Hou, J.; Zhao, H.; Wu, J.; Luo, Y.; Bai, H.; Rogers, of Siloxanes Using Phosphazene Base Catalysts. J. Inorg.
J. A.; Zhao, Q.; Xie, T. Mechano-Plastic Pyrolysis of Dynamic Organomet. Polym. 1999, 9 (1), 17–34. DOI
Covalent Polymer Network toward Hierarchical 3D 10.1023/A:1021429320083.
Ceramics. Adv. Mater. 2019, 31 (11), 1–6. DOI (47) Markó, I. E.; Stérin, S.; Buisine, O.; Berthon, G.; Michaud, G.;
10.1002/adma.201807326. Tinant, B.; Declercq, J. P. Highly Active and Selective
(38) Saed, M. O.; Terentjev, E. M. Catalytic Control of Plastic Flow Platinum(0)-Carbene Complexes. Efficient, Catalytic
in Siloxane-Based Liquid Crystalline Elastomer Networks. Hydrosilylation of Functionalised Olefins. Adv. Synth. Catal.
ACS Macro Lett. 2020, 9 (5), 749–755. DOI 2004, 346 (12), 1429–1434. DOI 10.1002/adsc.200404048.
10.1021/acsmacrolett.0c00265. (48) Khedaioui, D.; Boisson, C.; D’Agosto, F.; Montarnal, D.
(39) Fuchise, K.; Igarashi, M.; Sato, K.; Shimada, S. Polyethylene Aerogels with Combined Physical and
Organocatalytic Controlled/Living Ring-Opening Chemical Crosslinking: Improved Mechanical Resilience and
Polymerization of Cyclotrisiloxanes Initiated by Water with Shape-Memory Properties. Angew. Chemie - Int. Ed. 2019, 58
Strong Organic Base Catalysts. Chem. Sci. 2018, 9 (11), 2879– (44), 15883–15889. DOI 10.1002/anie.201908257.
2891. DOI 10.1039/c7sc04234e. (49) Cazacu, M.; Marcu, M. Silicone Rubbers. Ix. Contributions to
(40) Jehanno, C.; Flores, I.; Dove, A. P.; Müller, A. J.; Ruipérez, F.; Polydimethylsiloxane-α,ω-Diols Synthesis by
Sardon, H. Organocatalysed Depolymerisation of PET in a Heterogeneous Catalysis. J. Macromol. Sci. Part A 1995, 32
Fully Sustainable Cycle Using Thermally Stable Protic Ionic (7), 1019–1029. DOI 10.1080/10601329508019142.
Salt. Green Chem. 2018, 20 (6), 1205–1212. DOI
10.1039/c7gc03396f.
(41) Van Herck, N.; Maes, D.; Unal, K.; Guerre, M.; Winne, J. M.;
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