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Polyethylene (PE) is the most widely produced synthetic polymer. By installing chemically cleavable bonds into the backbone of PE, it is possible to produce chemically deconstructable PE derivatives; to date, however, such designs have primarily relied on carbonyl‐ and olefin‐related functional groups. Bifunctional silyl ethers (BSEs; SiR₂(OR′₂)) could expand the functional scope of PE mimics as they possess strong Si−O bonds and facile chemical tunability. Here, we report BSE‐containing high‐density polyethylene (HDPE)‐like materials synthesized through a one‐pot catalytic ring‐opening metathesis polymerization (ROMP) and hydrogenation sequence. The crystallinity of these materials can be adjusted by varying the BSE concentration or the steric bulk of the Si‐substituents, providing handles to control thermomechanical properties. Two methods for chemical recycling of HDPE mimics are introduced, including a circular approach that leverages acid‐catalyzed Si−O bond exchange with 1‐propanol. Additionally, despite the fact that the starting HDPE mimics were synthesized by chain‐growth polymerization (ROMP), we show that it is possible to recover the molar mass and dispersity of recycled HDPE products using step‐growth Si−O bond formation or exchange, generating high molecular weight recycled HDPE products with mechanical properties similar to commercial HDPE.

 

Polyethylene (PE) is the most widely produced synthetic polymer. By installing chemically cleavable bonds into the backbone of PE, it is possible to produce chemically deconstructable PE derivatives; to date, however, such designs have primarily relied on carbonyl‐ and olefin‐related functional groups. Bifunctional silyl ethers (BSEs; SiR₂(OR′₂)) could expand the functional scope of PE mimics as they possess strong Si−O bonds and facile chemical tunability. Here, we report BSE‐containing high‐density polyethylene (HDPE)‐like materials synthesized through a one‐pot catalytic ring‐opening metathesis polymerization (ROMP) and hydrogenation sequence. The crystallinity of these materials can be adjusted by varying the BSE concentration or the steric bulk of the Si‐substituents, providing handles to control thermomechanical properties. Two methods for chemical recycling of HDPE mimics are introduced, including a circular approach that leverages acid‐catalyzed Si−O bond exchange with 1‐propanol. Additionally, despite the fact that the starting HDPE mimics were synthesized by chain‐growth polymerization (ROMP), we show that it is possible to recover the molar mass and dispersity of recycled HDPE products using step‐growth Si−O bond formation or exchange, generating high molecular weight recycled HDPE products with mechanical properties similar to commercial HDPE.

 

While Si-containing polymers can often be deconstructed using chemical triggers such as fluoride, acids, and bases, they are resistant to cleavage by mild reagents such as biological nucleophiles, thus limiting their end-of-life options and potential environmental degradability. Here, using ring-opening metathesis polymerization, we synthesize terpolymers of (1) a “functional” monomer ( e.g. , a polyethylene glycol macromonomer or dicyclopentadiene); (2) a monomer containing an electrophilic pentafluorophenyl (PFP) substituent; and (3) a cleavable monomer based on a bifunctional silyl ether . Exposing these polymers to thiols under basic conditions triggers a cascade of nucleophilic aromatic substitution (S N Ar) at the PFP groups, which liberates fluoride ions, followed by cleavage of the backbone Si–O bonds, inducing polymer backbone deconstruction. This method is shown to be effective for deconstruction of polyethylene glycol (PEG) based graft terpolymers in organic or aqueous conditions as well as polydicyclopentadiene (pDCPD) thermosets, significantly expanding upon the versatility of bifunctional silyl ether based functional polymers. 

Weak cross-linkers can improve the ultimate strength and tear resistance of polymer networks. 

Small angle neutron scattering was used to measure single chain radii of gyration of end-linked polymer gels before and after cross-linking to calculate the prestrain, which is the ratio of the average chain size in a cross-linked network to that of a free chain in solution. The prestrain increased from 1.06 ± 0.01 to 1.16 ± 0.02 as gel synthesis concentration decreased near the overlap concentration, indicating that the chains are slightly more stretched in the network than in solution. Dilute gels with higher loop fractions were found to be spatially homogeneous. Form factor and volumetric scaling analyses independently confirmed that elastic strands stretch by 2–23% from Gaussian conformations to create a space-spanning network, with increased stretching as network synthesis concentration decreases. Prestrain measurements reported here serve as a point of reference for network theories that rely on this parameter for the calculation of mechanical properties. 

The mechanical properties of a polymer network reflect the collective behavior of all of the constituent strands within the network. These strands comprise a distribution of states, and a central question is how the deformation and tension experienced by a strand is influenced by strand length. Here, we address this question through the use of mechanophore force probes with discrete molecular weights. Probe strands, each bearing a mechanochromic spiropyran (SP), were prepared through an iterative synthetic strategy, providing uniform PDMS-functionalized SP force probes with molecular weights of 578, 1170, and 2356 g/mol. The probes were each doped (9 mM) into the same silicone elastomer matrix. Upon stretching, the materials change color, consistent with the expected conversion of SP to merocyanine (MC). The critical strain at which measurable mechanochromism is observed is correlated with the strain hardening of the matrix, but it is independent of the molecular length of the probe strand. When a network with activated strands is relaxed, the color dissipates, and the rate of decoloration varies as a function of the relaxing strain ((ε_r ) ̅); faster decoloration occurs at lower (ε_r ) ̅. The dependence of decoloration rate on (ε_r ) ̅ is taken to reflect the effect of residual tension in the once-activated strands on the reversion reaction of MC to SP, and the effect of that residual tension is indistinguishable across the three molecular lengths examined. The combination of discrete strand synthesis and mechanochromism provides a foundation to further test and develop molecular-based theories of elasticity and fracture in polymer networks. 

The cis- and trans-isomers of a silacycloheptene were selectively synthesized by the alkylation of a silyl dianion, a novel approach to strained cycloalkenes. The trans-silacycloheptene (trans-SiCH) was significantly more strained than the cis isomer, as predicted by quantum chemical calculations and confirmed by crystallographic signatures of a twisted alkene. Each isomer exhibited distinct reactivity toward ring-opening metathesis polymerization (ROMP), where only trans-SiCH afforded high-molar-mass polymer under enthalpy-driven ROMP. Hypothesizing that the introduction of silicon might result in increased molecular compliance at large extensions, we compared poly(trans-SiCH) to organic polymers by single-molecule force spectroscopy (SMFS). Force-extension curves from SMFS showed that poly(trans-SiCH) is more easily overstretched than two carbon-based analogues, polycyclooctene and polybutadiene, with stretching constants that agree well with the results of computational simulations.