PMID- 37008182
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20230404
IS  - 2168-0485 (Print)
IS  - 2168-0485 (Electronic)
IS  - 2168-0485 (Linking)
VI  - 11
IP  - 12
DP  - 2023 Mar 27
TI  - Polyethylene-Like Blends Amenable to Abiotic Hydrolytic Degradation.
PG  - 4523-4530
LID - 10.1021/acssuschemeng.2c07537 [doi]
AB  - Long-chain aliphatic polyester-18,18 (PE-18,18) exhibits high density 
      polyethylene-like material properties and, as opposed to high density 
      polyethylene (HDPE), can be recycled in a closed loop via depolymerization to 
      monomers under mild conditions. Despite the in-chain ester groups, its high 
      crystallinity and hydrophobicity render PE-18,18 stable toward hydrolysis even 
      under acidic conditions for one year. Hydrolytic degradability, however, can be a 
      desirable material property as it can serve as a universal backstop to plastic 
      accumulation in the environment. We present an approach to render PE-18,18 
      hydrolytically degradable by melt blending with long-chain aliphatic 
      poly(H-phosphonate)s (PP). The blends can be processed via common injection 
      molding and 3D printing and exhibit HDPE-like tensile properties, namely, high 
      stiffness (E = 750-940 MPa) and ductility (epsilon(tb) = 330-460%) over a wide range of 
      blend ratios (0.5-20 wt % PP content). Likewise, the orthorhombic solid-state 
      structure and crystallinity (chi  approximately  70%) of the blends are similar to HDPE. Under 
      aqueous conditions in phosphate-buffered media at 25  degrees C, the blends' PP component 
      is hydrolyzed completely to the underlying long-chain diol and phosphorous acid 
      within four months, as evidenced by NMR analyses. Concomitant, the PE-18,18 major 
      blend component is partially hydrolyzed, while neat PE-18,18 is inert under 
      identical conditions. The hydrolysis of the blend components proceeded throughout 
      the bulk of the specimens as confirmed by gel permeation chromatography (GPC) 
      measurements. The significant molar mass reduction upon extended immersion in 
      water (M (n)(virgin blends)  approximately  50-70 kg mol(-1); M (n)(hydrolyzed blends)  approximately  7-11 
      kg mol(-1)) resulted in embrittlement and fragmentation of the injection molded 
      specimens. This increases the surface area and is anticipated to promote eventual 
      mineralization by abiotic and biotic pathways of these HDPE-like polyesters in 
      the environment.
CI  - (c) 2023 The Authors. Published by American Chemical Society.
FAU - Eck, Marcel
AU  - Eck M
AUID- ORCID: 0000-0003-1121-1906
AD  - Department of Chemistry, University of Konstanz, Universitatsstr. 10, 78457 
      Konstanz, Germany.
FAU - Bernabeu, Lea
AU  - Bernabeu L
AUID- ORCID: 0000-0002-0828-4779
AD  - Department of Chemistry, University of Konstanz, Universitatsstr. 10, 78457 
      Konstanz, Germany.
FAU - Mecking, Stefan
AU  - Mecking S
AUID- ORCID: 0000-0002-6618-6659
AD  - Department of Chemistry, University of Konstanz, Universitatsstr. 10, 78457 
      Konstanz, Germany.
LA  - eng
PT  - Journal Article
DEP - 20230313
PL  - United States
TA  - ACS Sustain Chem Eng
JT  - ACS sustainable chemistry & engineering
JID - 101608852
PMC - PMC10052336
COIS- The authors declare no competing financial interest.
EDAT- 2023/04/04 06:00
MHDA- 2023/04/04 06:01
PMCR- 2023/03/29
CRDT- 2023/04/03 04:08
PHST- 2022/12/20 00:00 [received]
PHST- 2023/03/06 00:00 [revised]
PHST- 2023/04/04 06:01 [medline]
PHST- 2023/04/03 04:08 [entrez]
PHST- 2023/04/04 06:00 [pubmed]
PHST- 2023/03/29 00:00 [pmc-release]
AID - 10.1021/acssuschemeng.2c07537 [doi]
PST - epublish
SO  - ACS Sustain Chem Eng. 2023 Mar 13;11(12):4523-4530. doi: 
      10.1021/acssuschemeng.2c07537. eCollection 2023 Mar 27.