Microstructure effect in the coupling reactions of polymeric organolithium compounds using chlorosilanes

Cho, Jae Cheol; Kim, Keon Hyeong; Kim, Kwang Ung; Kwak, Sang Hyun; Kim, Jungahn; Jo, Won Ho; Chun, Moon Seok; Lee, Chan Hong; Yeo, Jong Ki; Quirk, Roderic P.

doi:10.1002/(sici)1099-0518(199808)36:11<1743::aid-pola7>3.0.co;2-s

Cited by 4 publications

(1 citation statement)

References 15 publications

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“…The coupling efficiency results in approximately 80 wt% of triblock copolymer as determined using SEC, as shown in SI Appendix, Fig. S2 , consistent with literature values ( 35 – 37 ). 1 H NMR and SEC traces of the saturated products ( SI Appendix, Figs.…”

Section: Resultssupporting

confidence: 88%

Threading-the-Needle: Compatibilization of HDPE/ i PP blends with butadiene-derived polyolefin block copolymers

Shen

Gorbea

Cui

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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Management of the plastic industry is a momentous challenge, one that pits enormous societal benefits against an accumulating reservoir of nearly indestructible waste. A promising strategy for recycling polyethylene (PE) and isotactic polypropylene ( i PP), constituting roughly half the plastic produced annually worldwide, is melt blending for reformulation into useful products. Unfortunately, such blends are generally brittle and useless due to phase separation and mechanically weak domain interfaces. Recent studies have shown that addition of small amounts of semicrystalline PE- i PP block copolymers (ca. 1 wt%) to mixtures of these polyolefins results in ductility comparable to the pure materials. However, current methods for producing such additives rely on expensive reagents, prohibitively impacting the cost of recycling these inexpensive commodity plastics. Here, we describe an alternative strategy that exploits anionic polymerization of butadiene into block copolymers, with subsequent catalytic hydrogenation, yielding E and X blocks that are individually melt miscible with PE and i PP, where E and X are poly(ethylene- ran -ethylethylene) random copolymers with 6 wt% and 90 wt% ethylethylene repeat units, respectively. Cooling melt blended mixtures of PE and i PP containing 1 wt% of the triblock copolymer EXE of appropriate molecular weight, results in mechanical properties competitive with the component plastics. Blend toughness is obtained through interfacial topological entanglements of the amorphous X polymer and semicrystalline i PP, along with anchoring of the E blocks through cocrystallization with the PE homopolymer. Significantly, EXE can be inexpensively produced using currently practiced industrial scale polymerization methods, offering a practical approach to recycling the world’s top two plastics.

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Section: Resultssupporting

confidence: 88%

Threading-the-Needle: Compatibilization of HDPE/ i PP blends with butadiene-derived polyolefin block copolymers

Shen

Gorbea

Cui

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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Precise Block‐Copolymers by Efficient Coupling of End‐Functionalized Polymers Using Phosgene

Cotiuga

Picchioni

Agarwal

et al. 2006

Macromol. Rapid Commun.

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Summary: We report the synthesis of well‐defined block copolymers by covalent coupling of hydroxy end‐functionalized polymers. Using the high volatility of the coupling agent phosgene as compared to the solvent, very high conversion (up to 96%) is obtained in a one‐pot reaction with as little as 10−5 moles of each of the reacting polymers, even without prior purification of the as‐received reagents. This has potential as an alternative to the currently practiced method of sequential living polymerization of constituent monomers, with the added advantage of direct knowledge and control over the length distribution of each block.Coupling of end‐functionalized polymers using phosgene to form block copolymers of controlled composition.magnified imageCoupling of end‐functionalized polymers using phosgene to form block copolymers of controlled composition.

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Recent synthetic uses of functionalised aromatic and heteroaromatic organolithium reagents prepared by non-deprotonating methods

2003

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Microstructure effect in the coupling reactions of polymeric organolithium compounds using chlorosilanes

Cited by 4 publications

References 15 publications

Threading-the-Needle: Compatibilization of HDPE/ i PP blends with butadiene-derived polyolefin block copolymers

Threading-the-Needle: Compatibilization of HDPE/ i PP blends with butadiene-derived polyolefin block copolymers

Precise Block‐Copolymers by Efficient Coupling of End‐Functionalized Polymers Using Phosgene

Recent synthetic uses of functionalised aromatic and heteroaromatic organolithium reagents prepared by non-deprotonating methods

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