Chemoselective Alternating Copolymerization of Limonene Dioxide and Carbon Dioxide: A New Highly Functional Aliphatic Epoxy Polycarbonate

Li, C Chunliang; Sablong, RJ Rafaël; Koning, CE Cor

doi:10.1002/ange.201604674

Cited by 39 publications

(13 citation statements)

References 60 publications

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“…The alternating copolymerization of CO 2 with biorenewable limonene dioxide can be catalyzed with a zinc β-diiminate complex. 183 Only the more reactive epoxide group is being converted to provide a linear polycarbonate. The polymer is characterized by a relatively high glass transition temperature of up to 135 °C, consistent with the steric bulk of the chemical entities along the polymer backbone.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

et al. 2017

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CO conversion covers a wide range of possible application areas from fuels to bulk and commodity chemicals and even to specialty products with biological activity such as pharmaceuticals. In the present review, we discuss selected examples in these areas in a combined analysis of the state-of-the-art of synthetic methodologies and processes with their life cycle assessment. Thereby, we attempted to assess the potential to reduce the environmental footprint in these application fields relative to the current petrochemical value chain. This analysis and discussion differs significantly from a viewpoint on CO utilization as a measure for global CO mitigation. Whereas the latter focuses on reducing the end-of-pipe problem "CO emissions" from todays' industries, the approach taken here tries to identify opportunities by exploiting a novel feedstock that avoids the utilization of fossil resource in transition toward more sustainable future production. Thus, the motivation to develop CO-based chemistry does not depend primarily on the absolute amount of CO emissions that can be remediated by a single technology. Rather, CO-based chemistry is stimulated by the significance of the relative improvement in carbon balance and other critical factors defining the environmental impact of chemical production in all relevant sectors in accord with the principles of green chemistry.

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Section: Chemical Reviewsmentioning

confidence: 99%

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

et al. 2017

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“…They show equivalent or better properties than conventional polyether/ester polyols in the manufacturing of rigid and flexible foams, adhesives, elastomers and coatings. [11][12][13][14] Higher molar mass polycarbonates show properties suitable to replace petrochemicals in sectors including packaging, coatings, rigid plastics and medical materials. 11,[15][16][17] For any application sector, the selection of the polymerization catalyst is central to process productivity and selectivity.…”

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confidence: 99%

Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides

et al. 2020

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The copolymerization of carbon dioxide with epoxides is an industrially relevant means to valorize wastes and improve sustainability in polymer manufacturing, and may also provide an economic benefit to CO2 capture and storage technologies. The efficiency of the process depends upon the catalyst used; previously Zn(II)Mg(II) heterodinuclear catalysts showed good performances at low CO2 pressures, which has been attributed to synergic interactions between the metals. Here we report a Mg(II)Co(II) catalyst for the production of polyols by copolymerization of CO2 with cyclohexene oxide that exhibits significantly better activity (turn-over-frequency over 12,000 h-1), high CO2 utilization (over 99 %) and high polymer selectivity (over 99 %). Detailed kinetic investigations show a second-order rate law, independent of CO2 pressure from 1 to 40 bar. Investigations of the synergy between the metal centres showed that epoxide coordination occurs at Mg(II) with reduced transition state entropy, which the carbonate attack step is accelerated at Co(II) through lowering of the transition state enthalpy. functionalization of alternating polyesters: selective patterning of (AB)n sequences.

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“…The synthesis of these CO 2 -PCs was based on the use of various homogenous catalyst systems that were previously reported by us and by other groups. [24,[37][38][39][40] In contrast with the traditional polycarbonates produced by polycondensation of carbonylation reagents and diols, all the prepared CO 2 -derived polycarbonates display controlled molecular weight (M n ) with narrow polydispersity (Đ). For e-beam resists utilization, all these CO 2 -PC materials were processed by the conventional integrated circuit fabrication process of spin-coating, prebaking, e-beam exposure, and development.…”

Section: Synthetic Routes and The Processing Scheme Of The Co 2 -Pc Resistsmentioning

confidence: 99%

CO₂‐Based Dual‐Tone Resists for Electron Beam Lithography

Luo

Wang

et al. 2020

Adv Funct Materials

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The increasing global environmental and energy crisis has urgently motivated the advancement of sustainable materials. Significant effort has been focused on developing new materials to replace the fossil‐based resists in the semiconductor industry based on greener sources such as ice, dry ice, small organic molecules, and proteins. Such resist materials, however, have yet to meet the stringent requirements of high sensitivity, high resolution, reliable repeatability, and good compatibility with the current protocols. To this end, CO2‐based polycarbonates (CO2‐PCs) obtained from the copolymerization of CO2 and epoxides are demonstrated as sustainable dual‐tone (positive & negative tone) resists for electron beam lithography. By adjusting the chemical structure, developing agent, and molecular weight, the CO2‐PCs present high sensitivities to electron beam (1.3/120 µC cm−2), narrow critical dimensions (29/58 nm), and moderate line edge roughness (4.6/26.7 nm) for negative and positive resists, respectively. A deep understanding of the exposure mechanism of CO2‐PC resists is provided on the basis of the Fourier transform infrared, Raman, and electron ionization mass spectroscopy. 2D photonic crystal devices are fabricated using the negative and positive CO2‐PC resists, respectively, and both devices show distinct colors derived from their well‐defined nanostructures, indicating the great practical potential of CO2‐derived electron beam resists.

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Chemoselective Alternating Copolymerization of Limonene Dioxide and Carbon Dioxide: A New Highly Functional Aliphatic Epoxy Polycarbonate

Cited by 39 publications

References 60 publications

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides

CO₂‐Based Dual‐Tone Resists for Electron Beam Lithography

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Chemoselective Alternating Copolymerization of Limonene Dioxide and Carbon Dioxide: A New Highly Functional Aliphatic Epoxy Polycarbonate

Cited by 39 publications

References 60 publications

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides

CO2‐Based Dual‐Tone Resists for Electron Beam Lithography

Contact Info

Product

Resources

About

CO₂‐Based Dual‐Tone Resists for Electron Beam Lithography