Abstract Polyolefins with periodic unsaturation in the backbone chain are sought after for synthesizing chemically recyclable polymers or telechelic polyolefin macromonomers. Here we introduce a bottom‐up synthesis of unsaturated high‐density polyethylene (HDPE) via copolymerization of ethylene with dimethyl 7‐oxabicyclo[2.2.1]hepta‐2,5‐diene‐3,5‐dicarboxylate followed by post‐polymerization retro‐Diels–Alder to unveil hidden double bonds in the polymer backbone. The incorporation of this “Trojan Horse” comonomer was varied and a series of unsaturated HDPE polymers with block lengths of 1.2, 1.9, and 3.5 kDa between double bonds was synthesized. Cross metathesis of unsaturated HDPE samples with 2‐hydroxyethyl acrylate yielded telechelic ester terminated PE macromonomers suitable for the preparation of ester‐linked PE. These materials were depolymerized and repolymerized, making them suitable candidates for chemical recycling. The ester‐linked PE displayed thermal and mechanical properties comparable to commercial HDPE. 
                        more » 
                        « less   
                    
                            
                            Chemically Recyclable Linear and Branched Polyethylenes Synthesized from Stoichiometrically Self-Balanced Telechelic Polyethylenes
                        
                    
    
            High-density polyethylene (HDPE) is a widely used commercial plastic due to its excellent mechanical properties, chemical resistance, and water vapor barrier properties. However, less than 10% of HDPE is mechanically recycled, and the chemical recycling of HDPE is challenging due to the inherent strength of the carbon–carbon backbone bonds. Here, we report chemically recyclable linear and branched HDPE with sparse backbone ester groups synthesized from the transesterification of telechelic polyethylene macromonomers. Stoichiometrically self-balanced telechelic polyethylenes underwent transesterification polymerization to produce the PE-ester samples with high number-average molar masses of up to 111 kg/mol. Moreover, the transesterification polymerization of the telechelic polyethylenes and the multifunctional diethyl 5-(hydroxymethyl)isophthalate generated branched PE-esters. Thermal and mechanical properties of the PE-esters were comparable to those of commercial HDPE and tunable through control of the ester content in the backbone. In addition, branched PE-esters showed higher levels of melt strain hardening compared with linear versions. The PE-ester was depolymerized into telechelic macromonomers through straightforward methanolysis, and the resulting macromonomers could be effectively repolymerized to generate a high molar mass recycled PE-ester sample. This is a new and promising method for synthesizing and recycling high-molar-mass linear and branched PE-esters, which are competitive with HDPE and have easily tailorable properties. 
        more » 
        « less   
        
    
                            - Award ID(s):
- 1901635
- PAR ID:
- 10492430
- Publisher / Repository:
- ACS Publications
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 146
- Issue:
- 7
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 4771 to 4782
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
- 
            
- 
            Abstract 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.more » « less
- 
            Polymer blend compatibilization is an attractive solution for mechanical recycling of mixed plastic waste because it can result in tough blends. In this work, hydroxy-telechelic polyethylene (HOPEOH) reactive additives were used to compatibilize blends of polyethylene terephthalate (PET) and linear low-density polyethylene (LLDPE). HOPEOH additives were synthesized with molar masses of 1–20 kg/mol by ring-opening metathesis polymerization of cyclooctene followed by catalytic hydrogenation. Melt-compounded blends containing 0.5 wt % HOPEOH displayed reduced dispersed phase LLDPE particle sizes with ductilities comparable to virgin PET and almost seven times greater than neat blends, regardless of additive molar mass. In contrast, analogous blends containing monohydroxy PE additives of comparable molar masses did not result in compatibilization even at 2 wt % loading. The results strongly suggest that both hydroxy ends of HOPEOH undergo transesterification reactions during melt mixing with PET to form predominantly PET–PE–PET triblock copolymers at the interface of the dispersed and matrix phases. We hypothesize that the triblock copolymer compatibilizers localized at the interface form trapped entanglements of the PE midblocks with nearby LLDPE homopolymer chains by a hook-and-clasp mechanism. Finally, HOPEOH compounds were able to efficiently compatibilize blends derived solely from postconsumer PET and PE bottles and film, suggesting their industrial applicability.more » « less
- 
            Chain-transfer ring-opening metathesis polymerization (CT-ROMP) previously provided a route to carboxytelechelic polyethylene (PE) of controlled molecular weight; however, the incorporation of oligomeric PE into segmented copolymers remains unexplored. Herein, CT-ROMP afforded carboxytelechelic polycyclooctene segments, and subsequent reduction generated well-defined carboxytelechelic PE with M n = 3900 g mol −1 . Solvent-free melt polycondensation of neopentyl glycol and adipic acid with varying wt% telechelic PE oligomers yielded mechanically durable segmented copolyesters. The thermal and thermomechanical properties of the segmented copolyesters correlated with PE segment content, and high PE content copolymers exhibited remarkably similar morphologies and thermomechanical performance to conventional HDPE. The segmented copolyesters displayed advantageous physical properties while introducing susceptibility to chemo- and bio-catalytic depolymerization through periodic ester linkages, thus providing valuable fundamental understanding of an alternative route to HDPE.more » « less
- 
            Abstract Reported herein is a continuous one‐step melt extrusion approach for high‐density polyethylene (HDPE) vitrimers. A grafting agent and a coagent were used to produce high‐performing vitrimers. Maleic anhydride (MA) served as a reactive agent to facilitate crosslinking, while dimethyl maleate (DM) acted as a grafting enhancer by reducing the surface energy of HDPE grafted with MA. For comparison, MA alone was also tested as a grafting agent. The vitrimers obtained displayed superior mechanical properties compared with HDPE. The storage modulus, as well as crystallinity, were determined for the HDPE vitrimers. These vitrimers are reprocessable, thus supporting recycling efforts despite their crosslinked nature, owing to very fast relaxation due to low activation energy for the transesterification reaction. Consequently, these vitrimers are not only recyclable but also exhibit enhanced thermal and mechanical properties compared with conventional HDPE.more » « less
 An official website of the United States government
An official website of the United States government 
				
			 
					 
					
 
                                    