Polymers

Research

18 pages, 7800 KiB

Open AccessArticle

Demonstrating the Efficacy of Core-Shell Silica Catalyst in Depolymerizing Polycarbonate

by Onofrio Losito, Pasquale Pisani, Alessia De Cataldo, Cosimo Annese, Marina Clausi, Roberto Comparelli, Daniela Pinto and Lucia D’Accolti

Polymers 2024, 16(22), 3209; https://doi.org/10.3390/polym16223209 - 19 Nov 2024

Cited by 1 | Viewed by 1219

Abstract

Polycarbonate (PC) is a highly versatile plastic material that is extensively utilized across various industries due to its superior properties, including high impact strength and heat resistance. However, its durability presents significant challenges for recycling and waste management. Polycarbonate is a thermoplastic polymer [...] Read more.

Polycarbonate (PC) is a highly versatile plastic material that is extensively utilized across various industries due to its superior properties, including high impact strength and heat resistance. However, its durability presents significant challenges for recycling and waste management. Polycarbonate is a thermoplastic polymer representative of the class of condensation reaction polymers obtained from the reaction of bisphenol A (BPA) and a carbonyl source, such as phosgene or alkyl and aryl carbonate. The recycling processes for PC waste include mechanical recycling, blending with other materials, pyrolysis, and chemical recycling. The latter is based on the cleavage of carbonate units to their corresponding monomers or derivatives through alcoholysis and/or hydrolysis and ammonolysis, normally under basic conditions and without catalysts. This study investigates the efficacy of the use of several heterogeneous catalysts based on silica gel as a robust support, including Sc(III)silicate (thortveitite), which has been previously reported for the preparation of polyesters, core-shell Si-ILs, and core-shell Si-ILs-ZnO, which has never been used before in the depolymerization of polycarbonate, proposing a sustainable and efficient method for recycling this valuable polymer. We chose to explore core-shell catalysts because these catalysts are robust and recyclable, and have been used in very harsh industrial processes. The core-shell silica catalysts used in this study were characterized by XRD; SEM_EDX, FT-IR, and ICP-OES analysis. In our experimental protocol, polycarbonate samples were exposed to the catalyst under controlled conditions (60–150 °C, for 12–24 h) using both oxygen and nitrogen nucleophiles. The depolymerization process was systematically monitored using advanced analytical techniques (GC/MS and GPC chromatography). The experimental results indicated that core-shell silica catalyst exhibits high efficacy, with up to 75% yield for the ammonolysis reaction, producing monomers of high purity. These monomers can be reused for the synthesis of new polycarbonate materials, contributing to a more sustainable approach to polycarbonate recycling. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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19 pages, 3604 KiB

Open AccessArticle

Factorial Analysis and Thermal Kinetics of Chemical Recycling of Poly(ethylene terephthalate) Aided by Neoteric Imidazolium-Based Ionic Liquids

by Oscar Gil-Castell, Ramón Jiménez-Robles, Alejandro Gálvez-Subiela, Gorka Marco-Velasco, M. Pilar Cumplido, Laia Martín-Pérez, Amparo Cháfer and Jose D. Badia

Polymers 2024, 16(17), 2451; https://doi.org/10.3390/polym16172451 - 29 Aug 2024

Viewed by 1141

Abstract

Poly(ethylene terephthalate) (PET) waste accumulation poses significant environmental challenges due to its persistent nature and current management limitations. This study explores the effectiveness of imidazolium-based neoteric solvents [Emim][OAc] and [Bmim][OAc] as catalytic co-solvents in the glycolysis of PET with ethylene glycol (EG). Reaction [...] Read more.

Poly(ethylene terephthalate) (PET) waste accumulation poses significant environmental challenges due to its persistent nature and current management limitations. This study explores the effectiveness of imidazolium-based neoteric solvents [Emim][OAc] and [Bmim][OAc] as catalytic co-solvents in the glycolysis of PET with ethylene glycol (EG). Reaction thermal kinetics showed that both ionic liquids (ILs) significantly enhanced the depolymerization rate of PET compared to traditional methods. The use of [Emim][OAc] offered a lower activation energy of 88.69 kJ·mol⁻¹, thus making the process more energy-efficient. The contribution of key process parameters, including temperature (T), plastic-to-ionic liquid (P/IL) mass ratio, and plastic-to-solvent (P/S) mass ratio, were evaluated by means of a factorial analysis and optimized to achieve the maximum PET conversion for both neoteric solvents. The relevance sequence for both ionic liquids involved the linear factors T and P/S, followed by the interaction factors T×P/S and T×P/IL, with P/IL being the less significant parameter. The optimal conditions, with a predicted conversion of 100%, involved a temperature of 190 °C, with a P/IL of 1:1 and a P/S of 1:2.5, regardless of the IL used as the catalytic co-solvent. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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16 pages, 2239 KiB

Open AccessArticle

Effects of Copper(II) Oxide on the Co-Pyrolysis of Waste Polyester Enameled Wires and Poly(vinyl chloride)

by Xiaolu Wang, Bingyi Li, Zhidong Xia, Wei Zhou, Yufeng Wu, Zhaoxi Zhu and Guangze Zhu

Polymers 2024, 16(1), 27; https://doi.org/10.3390/polym16010027 - 20 Dec 2023

Cited by 4 | Viewed by 1671

Abstract

The emission of chlorinated pollutants is one of the main problems when recovering copper (Cu) via pyrolysis from waste enameled wires. This is mainly attributed to other wastes which possess high poly(vinyl chloride) content, such as electrical wires and cables, which are often [...] Read more.

The emission of chlorinated pollutants is one of the main problems when recovering copper (Cu) via pyrolysis from waste enameled wires. This is mainly attributed to other wastes which possess high poly(vinyl chloride) content, such as electrical wires and cables, which are often recycled together with enameled copper wires. In this research, to control the chlorinated pollutants, copper(II) oxide (CuO) was chosen and demonstrated to be an efficient dechlorinating agent, and CuO did not introduce any impurities that influence the quality of the recovered Cu. The pyrolysis and co-pyrolysis of polyester enameled wires, PVC, and CuO were investigated, and special attention was paid to chlorinated compounds in released pyrolytic products. In particular, the co-pyrolysis of this ternary mixture was studied for the first time, and some new pyrolysis behaviors were discovered. For example, the results of Py-GC/MS analyses showed that the addition of CuO removed about 75% of the chloro-organic products, the main types of which were chloroaromatic compounds rather than the more toxic chloroesters. Moreover, pyrolysis gases were collected and characterized via ion chromatography, and the results showed that the chlorine content in the pyrolysis gases decreased by about 71%. TG analysis indicated that CuO only minimally affected the pyrolysis of polyester paint. However, through the chlorine fixation effect, CuO influenced the dechlorination and dehydrochlorination of PVC, as well as secondary reactions between HCl and pyrolysis products of polyester paint, therefore changing the products and behaviors of co-pyrolysis. Mechanism of reducing chlorine-containing pollutants and reaction mechanism of forming typical pyrolysis products closely correlated to the effects of CuO were also proposed, providing theoretical guidance for the recycling of waste enameled wires. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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14 pages, 2330 KiB

Open AccessArticle

Optimization and Kinetic Evaluation for Glycolytic Depolymerization of Post-Consumer PET Waste with Sodium Methoxide

by Saqib Javed, Jonas Fisse and Dieter Vogt

Polymers 2023, 15(3), 687; https://doi.org/10.3390/polym15030687 - 29 Jan 2023

Cited by 21 | Viewed by 5235

Abstract

Glycolysis of post-consumer polyethylene terephthalate (PET) waste is a promising chemical recycling technique, back to the monomer, bis(2-hydroxyethyl) terephthalate (BHET). This work presents sodium methoxide (MeONa) as a low-cost catalyst for this purpose. BHET product was confirmed by gas chromatography-mass spectrometry (GCMS), Nuclear [...] Read more.

Glycolysis of post-consumer polyethylene terephthalate (PET) waste is a promising chemical recycling technique, back to the monomer, bis(2-hydroxyethyl) terephthalate (BHET). This work presents sodium methoxide (MeONa) as a low-cost catalyst for this purpose. BHET product was confirmed by gas chromatography-mass spectrometry (GCMS), Nuclear Magnetic Resonance (NMR) Spectroscopy, melting point, and Differential Scanning Calorimetry (DSC). It was shown, not surprisingly, that PET conversion increases with the glycolysis temperature. At a fixed temperature of 190 °C, the response surface methodology (RSM) based on the Box-Behnken design was applied. Four independent factors, namely the molar ratio of PET: MeONa (50–150), the molar ratio of ethylene glycol to PET (EG: PET) (3–7), the reaction time (2–6 h), and the particle size (0.25–1 mm) were studied. Based on the experimental results, regression models as a function of significant process factors were obtained and evaluated by analysis of variance (ANOVA), to predict the depolymerization performance of MeONa in terms of PET conversion. Coefficient of determination, R² of 95% indicated the adequacy for predicted model. Afterward, the regression model was validated and optimized within the design space with a prediction of 87% PET conversion at the optimum conditions demonstrating a deviation of less than 5% from predicted response. A van ‘t Hoff plot confirmed the endothermic nature of the depolymerization reaction. The ceiling temperature (T_C = 160 °C) was calculated from Gibbs’ free energy. A kinetic study for the depolymerization reaction was performed and the activation energy for MeONa was estimated from the Arrhenius plot (E_A = 130 kJ/mol). The catalytic depolymerization efficiency of MeONa was compared under similar conditions with widely studied zinc acetate and cobalt acetate. This study shows that MeONa’s performance, as a glycolysis catalyst is promising; in addition, it is much cheaper and environmentally more benign than heavy metal salts. These findings make a valuable contribution towards the chemical recycling of post-consumer PET waste to meet future recycling demands of a circular economy. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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7 pages, 2484 KiB

Open AccessCommunication

Reusable Macroporous Oil Sorbent Films from Plastic Wastes

by Junaid Saleem, Moghal Zubair Khalid Baig, Adriaan Stephanus Luyt, Rana Abdul Shakoor, Said Mansour and Gordon McKay

Polymers 2022, 14(22), 4867; https://doi.org/10.3390/polym14224867 - 11 Nov 2022

Cited by 6 | Viewed by 2426

Abstract

Plastic waste comprises 15% of the total municipal solid waste and can be a rich source for producing value-added materials. Among them, polyethylene (PE) and polypropylene (PP) account for 60% of the total plastic waste, mainly due to their low-end and one-time-use applications. [...] Read more.

Plastic waste comprises 15% of the total municipal solid waste and can be a rich source for producing value-added materials. Among them, polyethylene (PE) and polypropylene (PP) account for 60% of the total plastic waste, mainly due to their low-end and one-time-use applications. Herein, we report reusable oil sorbent films made by upcycling waste PE and PP. The as-prepared oil sorbent had an uptake capacity of 55 g/g. SEM analysis revealed a macroporous structure with a pore size range of 1–10 µm, which facilitates oil sorption. Similarly, the contact angle values reflected the oleophilic nature of the sorbent. Moreover, thermal properties and crystallinity were examined using DSC, while mechanical properties were calculated using tensile testing. Lastly, 95% of the sorbed oil could be easily recovered by squeezing mechanically or manually. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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13 pages, 2093 KiB

Open AccessArticle

Methanolysis of Poly(lactic Acid) Using Catalyst Mixtures and the Kinetics of Methyl Lactate Production

by Fabio M. Lamberti, Luis A. Román-Ramírez, Andrew P. Dove and Joseph Wood

Polymers 2022, 14(9), 1763; https://doi.org/10.3390/polym14091763 - 26 Apr 2022

Cited by 5 | Viewed by 4083

Abstract

Polylactic acid (PLA) is a leading bioplastic of which the market share is predicted to increase in the future; its growing production capacity means its end-of-life treatment is becoming increasingly important. One beneficial disposal route for PLA is its chemical recycling via alcoholysis. [...] Read more.

Polylactic acid (PLA) is a leading bioplastic of which the market share is predicted to increase in the future; its growing production capacity means its end-of-life treatment is becoming increasingly important. One beneficial disposal route for PLA is its chemical recycling via alcoholysis. The alcoholysis of PLA leads to the generation of value-added products alkyl lactates; this route also has potential for a circular economy. In this work, PLA was chemically recycled via methanolysis to generate methyl lactate (MeLa). Four commercially available catalysts were investigated: zinc acetate dihydrate (Zn(OAc)₂), magnesium acetate tetrahydrate (Mg(OAc)₂), 4-(dimethylamino)pyridine (DMAP), and triazabicyclodecene (TBD). Dual catalyst experiments displayed an increase in reactivity when Zn(OAc)₂ was paired with TBD or DMAP, or when Mg(OAc)₂ was paired with TBD. Zn(OAc)₂ coupled with TBD displayed the greatest reactivity. Out of the single catalyst reactions, Zn(OAc)₂ exhibited the highest activity: a higher mol% was found to increase reaction rate but plateaued at 4 mol%, and a higher equivalent of methanol was found to increase the reaction rate, but plateaued at 17 equivalents. PLA methanolysis was modelled as a two-step reversible reaction; the activation energies were estimated at: Ea₁ = 25.23 kJ∙mol⁻¹, Ea₂ = 34.16 kJ∙mol⁻¹ and Ea_-2 = 47.93 kJ∙mol⁻¹. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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12 pages, 6415 KiB

Open AccessArticle

In-Situ Synthesis of TiO₂@GO Nanosheets for Polymers Degradation in a Natural Environment

by Yueqin Shi, Zhanyang Yu, Zhengjun Li, Xiaodong Zhao and Yongjun Yuan

Polymers 2021, 13(13), 2158; https://doi.org/10.3390/polym13132158 - 30 Jun 2021

Cited by 14 | Viewed by 2476

Abstract

Plastic photodegradation naturally takes 300–500 years, and their chemical degradation typically needs additional energy or causes secondary pollution. The main components of global plastic are polymers. Hence, new technologies are urgently required for the effective decomposition of the polymers in natural environments, which [...] Read more.

Plastic photodegradation naturally takes 300–500 years, and their chemical degradation typically needs additional energy or causes secondary pollution. The main components of global plastic are polymers. Hence, new technologies are urgently required for the effective decomposition of the polymers in natural environments, which lays the foundation for this study on future plastic degradation. This study synthesizes the in-situ growth of TiO₂ at graphene oxide (GO) matrix to form the TiO₂@GO photocatalyst, and studies its application in conjugated polymers’ photodegradation. The photodegradation process could be probed by UV-vis absorption originating from the conjugated backbone of polymers. We have found that the complete decomposition of various polymers in a natural environment by employing the photocatalyst TiO₂@GO within 12 days. It is obvious that the TiO₂@GO shows a higher photocatalyst activity than the TiO₂, due to the higher crystallinity morphology and smaller size of TiO₂, and the faster transmission of photogenerated electrons from TiO₂ to GO. The stronger fluorescence (FL) intensity of TiO₂@GO compared to TiO₂ at the terephthalic acid aqueous solution indicates that more hydroxyl radicals (•OH) are produced for TiO₂@GO. This further confirms that the GO could effectively decrease the generation of recombination centers, enhance the separation efficiency of photoinduced electrons and holes, and increase the photocatalytic activity of TiO₂@GO. This work establishes the underlying basic mechanism of polymers photodegradation, which might open new avenues for simultaneously addressing the white pollution crisis in a natural environment. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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15 pages, 3471 KiB

Open AccessArticle

Thermomechanical Devulcanisation of Ethylene Propylene Diene Monomer (EPDM) Rubber and Its Subsequent Reintegration into Virgin Rubber

by Dávid Zoltán Pirityi and Kornél Pölöskei

Polymers 2021, 13(7), 1116; https://doi.org/10.3390/polym13071116 - 1 Apr 2021

Cited by 21 | Viewed by 5431

Abstract

Rubber waste remains a challenge for material science because its covalently cross-linked structure hinders the establishment of the circular economy of rubber. Devulcanisation may provide a solution, as it converts rubber vulcanisates back into their original, uncured state. Devulcanised rubber may be revulcanised [...] Read more.

Rubber waste remains a challenge for material science because its covalently cross-linked structure hinders the establishment of the circular economy of rubber. Devulcanisation may provide a solution, as it converts rubber vulcanisates back into their original, uncured state. Devulcanised rubber may be revulcanised or incorporated into virgin rubber, thus waste is utilized and the use of primary resources is reduced at the same time. In this paper, we treated sulphur-cured EPDM (ethylene propylene diene monomer) rubber on a two-roll mill at various temperatures and frictions. We determined the effectiveness of devulcanisation via Horikx’s analysis, which suggested that low devulcanisation temperatures would result in a 50% decrease in cross-link density with minimal polymer degradation. The devulcanisate was recycled via two methods: (a) revulcanisation with extra curing agents, and (b) mixing it with various amounts of the original rubber mixture, preparing rubber samples with 25, 50, 75, and 100 wt% recycled content. Tensile tests revealed that the samples’ elastic properties were severely compromised at 75 and 100 wt% devulcanisate contents. However, tensile strength decreased only by 15% and 20% for revulcanisates containing 25% and 50% recycled rubber, respectively. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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18 pages, 6593 KiB

Open AccessArticle

Recyclable High-Performance Epoxy-Anhydride Resins with DMP-30 as the Catalyst of Transesterification Reactions

by Wenzhe Zhao, Le An and Shujuan Wang

Polymers 2021, 13(2), 296; https://doi.org/10.3390/polym13020296 - 18 Jan 2021

Cited by 55 | Viewed by 8622

Abstract

Epoxy-anhydride resins are widely used in engineering fields due to their excellent performance. However, the insolubility and infusibility make the recycling of epoxy resins challenging. The development of degradable epoxy resins with stable covalent networks provides an efficient solution to the recycling of [...] Read more.

Epoxy-anhydride resins are widely used in engineering fields due to their excellent performance. However, the insolubility and infusibility make the recycling of epoxy resins challenging. The development of degradable epoxy resins with stable covalent networks provides an efficient solution to the recycling of thermosets. In this paper, 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) is incorporated into the epoxy-glutaric anhydride (GA) system to prepare high-performance epoxy resins that can be recycled below 200 °C at ordinary pressure via ethylene glycol (EG) participated transesterification. The tertiary amine groups in DMP-30 can catalyze the curing reaction of epoxy and anhydride, as well as the transesterification between ester bonds and alcoholic hydroxyl groups. Compared with early recyclable anhydride-cured epoxy resins, the preparation and recycling of diglycidyl ether of bisphenol A (DGEBA)/GA/DMP-30 systems do not need any special catalysts such as TBD, Zn(Ac)₂, etc., which are usually expensive, toxic, and have poor compatibility with other compounds. The resulting resins have glass transition temperatures and strengths similar to those of conventional epoxy resins. The influences of GA content, DMP-30 content, and temperature on the dissolution rate were studied. The decomposed epoxy oligomer (DEO) is further used as a reaction ingredient to prepare new resins. It is found that the DEO can improve the toughness of epoxy resins significantly. This work provides a simple method to prepare readily recyclable epoxy resins, which is of low-cost and easy to implement. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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13 pages, 3239 KiB

Open AccessArticle

Reprocessable, Reworkable, and Mechanochromic Polyhexahydrotriazine Thermoset with Multiple Stimulus Responsiveness

by Li Chen, Siyao Zhu, Innocent Toendepi, Qiuran Jiang, Yi Wei, Yiping Qiu and Wanshuang Liu

Polymers 2020, 12(10), 2375; https://doi.org/10.3390/polym12102375 - 15 Oct 2020

Cited by 16 | Viewed by 4371

Abstract

Developing recyclable, reworkable, and intelligent thermosetting polymers, as a long-standing challenge, is highly desirable for modern manufacturing industries. Herein, we report a polyhexahydrotriazine thermoset (PHT) prepared by a one-pot polycondensation between 4-aminophenyl disulfide and paraformaldehyde. The PHT has a glass transition temperature of [...] Read more.

Developing recyclable, reworkable, and intelligent thermosetting polymers, as a long-standing challenge, is highly desirable for modern manufacturing industries. Herein, we report a polyhexahydrotriazine thermoset (PHT) prepared by a one-pot polycondensation between 4-aminophenyl disulfide and paraformaldehyde. The PHT has a glass transition temperature of 135 °C and good solvent resistance. The incorporation of dual stimuli-responsive groups (disulfide bond and hexahydrotriazine ring) endows the PHT with re-processability, re-workability, and damage monitoring function. The PHT can be repeatedly reprocessed by hot pressing, and a near 100% recovery of flexural strength is achieved. The PHT can also degrade in inorganic acid or organic thiol solutions at room temperature. The thermally reworkable test demonstrates that, after heating the PHT at 200 °C for 1 h, the residuals can be easily wiped off. Finally, the PHT exhibits a reversible mechanochromic behavior when damaged. Full article

(This article belongs to the Special Issue Chemical Recycling of Polymers)

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