3 research outputs found
Nanoporous Poly(3,4-ethylenedioxythiophene) Derived from Polymeric Bicontinuous Microemulsion Templates
Nanoporous Poly(3,4-ethylenedioxythiophene)
Derived
from Polymeric Bicontinuous Microemulsion Template
Stress Relaxation in Epoxy Thermosets via a Ferrocene-Based Amine Curing Agent
Physical
stress relaxation in rubbery, thermoset polymers is limited
by cross-links, which impede segmental motion and restrict relaxation
to network defects, such as chain ends. In parallel, the cure shrinkage
associated with thermoset polymerizations leads to the development
of internal residual stress that cannot be effectively relaxed. Recent
strategies have reduced or eliminated such cure stress in thermoset
polymers largely by exploiting chemical relaxation processes, wherein
temporary cross-links or otherwise transient bonds are incorporated
into the polymer network. Here, we explore an alternative approach,
wherein physical relaxation is enhanced by the incorporation of organometallic
sandwich moieties into the backbone of the polymer network. A standard
epoxy resin is cured with a diamine derivative of ferrocene and compared
to conventional diamine curing agents. The ferrocene-based thermoset
is clearly distinguished from the conventional materials by reduced
cure stress with increasing cure temperature as well as unique stress
relaxation behavior above its glass transition in the fully cured
state. The relaxation experiments exhibit features characteristic
of a physical relaxation process. Furthermore, the cure stress is
observed to vanish precipitously upon deliberate introduction of network
defects through an increasing imbalance of epoxy and amine functional
groups. We postulate that these beneficial properties arise from fluxional
motion of the cyclopentadienyl ligands on the polymer backbone
Chemical Recycling of Polybutadiene Rubber with Tailored Depolymerization Enabled by Microencapsulated Metathesis Catalysts
The effective management of plastic waste streams to
prevent plastic
land and water pollution is a growing problem that is also one of
the most important challenges in polymer science today. Polymer materials
that are stable over their lifetime and can also be cheaply recycled
or repurposed as desired could more easily be diverted from waste
streams. However, this is difficult for most commodity plastics. It
is especially difficult to conceive this with intractable, cross-linked
polymers such as rubbers. In this work, we explore the utility of
microencapsulated Grubbs’ catalysts for the in-situ depolymerization and reprocessing of polybutadiene (PB) rubber.
Second-generation Hoveyda-Grubbs catalyst (HG2) contained
within glassy thermoplastic microspheres can be dispersed in PB rubber
below the microsphere’s glass transition temperature (Tg) without adverse depolymerization, evidenced
by rubber with and without these microspheres obtaining similar shear
storage moduli of ≈16 and ≈28 kPa, respectively. The
thermoplastic’s Tg can be used
to tune the depolymerization temperature, via release of HG2 into the rubber matrix. For example, using poly(lactic acid) (PLA)
vs polysulfone results in an 85 and 162 °C depolymerization temperature,
respectively. Liquefaction of rubber to a mixture of small molecules
and oligomers is demonstrated using a 0.01 mol % catalyst loading
using PLA as the encapsulant. At that same catalyst loading, depolymerization
occurs to a greater extent in comparison to two ex-situ approaches, including a conventional solvent-assisted method, where
it occurs at roughly twice the extent at each given catalyst loading.
In addition, depolymerization of the microsphere-loaded rubbers was
demonstrated for samples stored under nitrogen for 23 days. Lastly,
we show that the depolymerized products can be reprocessed back into
solid rubber with a shear storage modulus of ≈32 kPa. Thus,
we envision that this approach could be used to recycle and reuse
cross-linked rubbers at the end of their product lifetime