Synthesis of Terephthalic Acid by p‐Cymene Oxidation using Oxygen: Toward a More Sustainable Production of Bio‐Polyethylene Terephthalate

Neaţu, Florentina; Culică, Geanina; Florea, Mihaela; Pârvulescu, Vasile I.; Cavani, Fabrizio

doi:10.1002/cssc.201600718

Cited by 45 publications

(31 citation statements)

References 76 publications

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“…Increased awareness of environmental impact from plastics has intensied the research into bio-based and recyclable polymeric materials. [1][2][3][4] A class of plastics showing strong potential is polyesters. Polyesters are challenged in high-temperature environments due to their vulnerability to thermally induced mechanical changes which limits service life.…”

Section: Introductionmentioning

confidence: 99%

Accelerated physical ageing of poly(1,4-cyclohexylenedimethylene-co-2,2,4,4-tetramethyl-1,3-cyclobutanediol terephthalate)

et al. 2019

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Successfully evaluating plastic lifetime requires understanding of the relationships between polymer dynamics and mechanical performance as a function of thermal ageing. The relatively high T g (T g ¼ 110 C) of poly(1,4-cyclohexylenedimethylene-co-2,2,4,4-tetramethyl-1,3-cyclobutanediol terephthalate) (PCTT) renders it useful as a substituent for PET in higher temperature applications. This work links thermal ageing and mechanical performance of a commercial PCTT plastic after exposure to 40-80 C for up to 2950 h. No chemical or conformational changes were found while pronounced physical ageing, measured as enthalpic relaxation, caused yield hardening (28% increase in yield strength) and embrittlement (80% decrease in toughness). Enthalpic relaxation increased with temperature and time to 3.8 J g À1 and correlated to the determined toughness and yield strength. Finally, a 9% increase in Young's modulus was observed independent of temperature and with no correlation to enthalpic relaxation. Enthalpic relaxation followed Vogel-Fulcher-Tammann behaviour, while yield strength and charpy v-notch toughness followed Arrhenius behaviour enabling prediction of the different properties with time and temperature. View Article Onlinewhere M C and M T are the molecular weights of the CHDM and TMCD repeating units (both 274 g mol À1 ), respectively. TMCD/CHDM ratio (f T/C ) was calculated from the carbonyl 13 C-NMR CHDM (1, 167.8 ppm) and TMCD (7, 168.4 ppm) peaks as given in eqn (4):This journal is

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Section: Introductionmentioning

confidence: 99%

Accelerated physical ageing of poly(1,4-cyclohexylenedimethylene-co-2,2,4,4-tetramethyl-1,3-cyclobutanediol terephthalate)

et al. 2019

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“…Polyester materials such as polyethylene and polybutylene terephthalate (PET and PBT, respectively) rank among the most relevant commercial plastics due to their excellent thermoplastic, crystalline and mechanical properties. They find applications in a wide range of markets from automotive to packaging to textile to medical, with market volumes over 60 Mt a -1 for PET and 1 Mt a -1 for PBT [1][2][3]. Along the shift towards more sustainability and growing corporate interest in "green" materials that can be made from 100% renewable resources, also their furan-based counterparts, such as polyethylene and polybutylene furanoate (PEF and PBF, respectively), as well as bio-PET and bio-PBT, are receiving significant attention recently [4][5][6][7][8].…”

Section: Introductionmentioning

confidence: 99%

Reaction kinetics and simulations of ring-opening polymerization for the synthesis of polybutylene terephthalate

Rosenboom

Lorenzi

Storti

et al. 2018

Polymer

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Cyclic polybutylene terephthalate (PBT) was polymerized with 2-ethylhexanoic acid tin(II) salt activated by 1-dodecanol in order to study the reaction mechanisms dominant in ring-opening polymerization (ROP) for polyester synthesis. Initiator-to-monomer content and temperatures were varied from 0.05% to 0.5% and 190 o C to 250 o C, respectively. The living-like character of ROP was confirmed by the characteristic effect of initiator content on cyclic oligomer conversion, along with the linear dependence of the number-average molecular weight upon conversion. The molecular weight distribution is mainly a function of the interplay between chain transfer and transesterification reactions. Since the PBT macrocycles appear in different sizes from 2 to 7 repeat units, each carbonyl group theoretically contributes to ring reactivity, where in this system both size-dependent and size-independent approaches to simulate propagation deliver appreciable results. The corresponding rate constants have been determined and, in contrast to other polymer systems, the proximity of these values to those of chain transfer and transesterification is significant.

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“…The reaction pathway for the p-cymene oxidation is very complex, consisting of parallel and consecutive reactions, as elsewhere described. [49] Therefore, considering the reaction products obtained in the presence of MnÀ Co mixed oxides catalysts during this study, a reaction pathway was proposed in Scheme 2. The reaction products were classified into three main groups: i) low oxidation products (LOP) shown in Scheme 2 by the green line and includes tertiary cymene hydroperoxide (TCHP), p-cymenol (COL), p-tolualdehyde (TALD), p,α-dimethylstyrene (DMS), p-methylacetophenone (MAP), primary cymene hydroperoxide (PCHP) and cuminaldehyde (CA), ii) advanced oxidation products (AOP) that includes p-toluic acid (TOA) and p-isopropylbenzoic acid (IBA) -shown by the blue line in Scheme 2 and iii) the most valuable product, terephthalic acid (TA), shown with the red line in Scheme 2.…”

Section: Catalytic Testsmentioning

confidence: 99%

The Role of Acidity in Terephthalic Acid Synthesis from Renewable Carbon Source

et al. 2020

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In this study, manganese‐cobalt (MnCo) mixed oxide catalysts were prepared by two different routes: co‐precipitation and citrate method. The structures and properties of the mixed oxide catalysts were investigated by several techniques: nitrogen adsorption‐desorption isotherms, X‐ray diffraction, X‐ray photoelectron spectroscopy, SEM, FTIR and UV‐Vis spectroscopies, temperature‐programmed reduction with H2 (H2‐TPR) and temperature‐programmed desorption of NH3 (NH3‐TPD). Their catalytic performance was investigated in the liquid‐phase selective oxidation of naturally occurred p‐cymene to terephthalic acid, as an alternative to p‐xylene, a fossil derivative fuel component. Within this study, we demonstrate that the materials prepared by the co‐precipitation method present strong acid sites that boost the oxidation rate and allow oxidation of p‐cymene up to terephthalic acid. The co‐existence of a significant number of strong acid and centers in higher oxidation state (Co3+) are required for these materials to be selective.

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Synthesis of Terephthalic Acid by p‐Cymene Oxidation using Oxygen: Toward a More Sustainable Production of Bio‐Polyethylene Terephthalate

Cited by 45 publications

References 76 publications

Accelerated physical ageing of poly(1,4-cyclohexylenedimethylene-co-2,2,4,4-tetramethyl-1,3-cyclobutanediol terephthalate)

Accelerated physical ageing of poly(1,4-cyclohexylenedimethylene-co-2,2,4,4-tetramethyl-1,3-cyclobutanediol terephthalate)

Reaction kinetics and simulations of ring-opening polymerization for the synthesis of polybutylene terephthalate

The Role of Acidity in Terephthalic Acid Synthesis from Renewable Carbon Source

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