M. Hasegawa, Hiroki Sato, Katsuhisa Hoshino, Yasuhisa Arao, J. Ishii
A cycloaliphatic tetracarboxylic dianhydride, octahydro-2,3,6,7-anthracenetetracarboxylic dianhydride (OHADA) was synthesized to obtain novel colorless polyimides (PIs). Herein, approaches for decolorizing an OHADA prototype and simplifying the entire process are described, and a plausible steric structure for OHADA is proposed. The polyaddition of OHADA and 2,2′-bis(trifluoromethyl)benzidine (TFMB) was unsuccessful; specifically, the reaction mixture remained inhomogeneous even after prolonged stirring. However, the modified one-pot process was applicable to the OHADA/TFMB system. The isolated PI powder form, as well as those for the other OHADA-based PIs, was highly soluble in numerous solvents and afforded a homogeneous and stable solution with a high solid content (20–30 wt%). Solution casting produced a colorless and ductile PI film with a very high glass transition temperature (Tg~300 °C). Furthermore, the OHADA/TFMB system exhibited remarkable thermal stability compared with those of the other related TFMB-derived semi-cycloaliphatic PIs. However, contrary to our expectations, this PI film did not exhibit a low linear coefficient of thermal expansion (CTE). This PI film also possessed excellent thermoplasticity, probably reflecting its peculiar steric structure. The use of an amide-containing diamine significantly enhanced the Tg (355 °C) and somewhat reduced the CTE (41.5 ppm K−1) while maintaining high optical transparency and excellent solubility.
{"title":"Colorless Polyimides Derived from Octahydro-2,3,6,7-anthracenetetracarboxylic Dianhydride","authors":"M. Hasegawa, Hiroki Sato, Katsuhisa Hoshino, Yasuhisa Arao, J. Ishii","doi":"10.3390/macromol3020011","DOIUrl":"https://doi.org/10.3390/macromol3020011","url":null,"abstract":"A cycloaliphatic tetracarboxylic dianhydride, octahydro-2,3,6,7-anthracenetetracarboxylic dianhydride (OHADA) was synthesized to obtain novel colorless polyimides (PIs). Herein, approaches for decolorizing an OHADA prototype and simplifying the entire process are described, and a plausible steric structure for OHADA is proposed. The polyaddition of OHADA and 2,2′-bis(trifluoromethyl)benzidine (TFMB) was unsuccessful; specifically, the reaction mixture remained inhomogeneous even after prolonged stirring. However, the modified one-pot process was applicable to the OHADA/TFMB system. The isolated PI powder form, as well as those for the other OHADA-based PIs, was highly soluble in numerous solvents and afforded a homogeneous and stable solution with a high solid content (20–30 wt%). Solution casting produced a colorless and ductile PI film with a very high glass transition temperature (Tg~300 °C). Furthermore, the OHADA/TFMB system exhibited remarkable thermal stability compared with those of the other related TFMB-derived semi-cycloaliphatic PIs. However, contrary to our expectations, this PI film did not exhibit a low linear coefficient of thermal expansion (CTE). This PI film also possessed excellent thermoplasticity, probably reflecting its peculiar steric structure. The use of an amide-containing diamine significantly enhanced the Tg (355 °C) and somewhat reduced the CTE (41.5 ppm K−1) while maintaining high optical transparency and excellent solubility.","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"5 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83892361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The design of photoinitiators activable under low-light intensity is an active research field, supported by the recent energetic sobriety plans imposed by numerous countries in Europe. With an aim to simplify the composition of the photocurable resins, Type I photoinitiators are actively researched as these structures can act as monocomponent systems. In this field, a family of structures has been under-investigated at present, namely, glyoxylates. Besides, the different works carried out in three years have evidenced that glyoxylates and related structures can be versatile for the design of Type I photoinitiators. In this review, an overview of the different glyoxylates and related structures reported to date is provided.
{"title":"Recent Advances on Glyoxylates and Related Structures as Photoinitiators of Polymerization","authors":"F. Dumur","doi":"10.3390/macromol3020010","DOIUrl":"https://doi.org/10.3390/macromol3020010","url":null,"abstract":"The design of photoinitiators activable under low-light intensity is an active research field, supported by the recent energetic sobriety plans imposed by numerous countries in Europe. With an aim to simplify the composition of the photocurable resins, Type I photoinitiators are actively researched as these structures can act as monocomponent systems. In this field, a family of structures has been under-investigated at present, namely, glyoxylates. Besides, the different works carried out in three years have evidenced that glyoxylates and related structures can be versatile for the design of Type I photoinitiators. In this review, an overview of the different glyoxylates and related structures reported to date is provided.","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"39 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77544900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
S. Bianchi, F. Bartoli, Cosimo Bruni, C. Fernandez-Avila, L. Rodriguez-Turienzo, Jorge Mellado-Carretero, Daniele Spinelli, M. Coltelli
The recovery and recycling of textile waste is becoming urgent since textiles are generating more and more waste. In one year, about 92 million tons of textile waste are produced and the fashion industry accounts for 58 million tons of plastic waste per year. Several different synthetic fibres are used in textiles, thanks to their excellent processability and mechanical properties, but on the other hand, the difficulties linked to their end of life and the release of microplastics from them during washing is currently a cause of great concern. In this context, policy actions have been aimed at promoting recycling of waste and replacing fossil-based fibres with biobased fibres. The current review, considering both scientific papers published on international journals and web sources, considers the sorting of textiles and the possible recycling of polyesters, polyamides and acrylics. Nevertheless, the contamination and presence of mixed fibres in fabrics is another issue to face for recycling. Methodologies to solve the issue linked to the presence of elastane, present in the stretch fabrics, as well as the possibility of recycling textiles in the non-woven and composite sector are investigated. Moreover, chemical recycling and enzymatic recycling of fossil polymers are also considered. Thanks to the comprehensive scheme of this review, it is possible to deduce that, while the use of biobased materials should rapidly increase in textile applications, the perspective of recycling materials obtained from waste textile into durable and/or high-performance products seems the most promising.
{"title":"Opportunities and Limitations in Recycling Fossil Polymers from Textiles","authors":"S. Bianchi, F. Bartoli, Cosimo Bruni, C. Fernandez-Avila, L. Rodriguez-Turienzo, Jorge Mellado-Carretero, Daniele Spinelli, M. Coltelli","doi":"10.3390/macromol3020009","DOIUrl":"https://doi.org/10.3390/macromol3020009","url":null,"abstract":"The recovery and recycling of textile waste is becoming urgent since textiles are generating more and more waste. In one year, about 92 million tons of textile waste are produced and the fashion industry accounts for 58 million tons of plastic waste per year. Several different synthetic fibres are used in textiles, thanks to their excellent processability and mechanical properties, but on the other hand, the difficulties linked to their end of life and the release of microplastics from them during washing is currently a cause of great concern. In this context, policy actions have been aimed at promoting recycling of waste and replacing fossil-based fibres with biobased fibres. The current review, considering both scientific papers published on international journals and web sources, considers the sorting of textiles and the possible recycling of polyesters, polyamides and acrylics. Nevertheless, the contamination and presence of mixed fibres in fabrics is another issue to face for recycling. Methodologies to solve the issue linked to the presence of elastane, present in the stretch fabrics, as well as the possibility of recycling textiles in the non-woven and composite sector are investigated. Moreover, chemical recycling and enzymatic recycling of fossil polymers are also considered. Thanks to the comprehensive scheme of this review, it is possible to deduce that, while the use of biobased materials should rapidly increase in textile applications, the perspective of recycling materials obtained from waste textile into durable and/or high-performance products seems the most promising.","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"140 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82611425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymeric materials have recently attracted a lot of attention due to their potential applications in many fields, ranging from biomedicine, the food industry and environmental monitoring to electronic, energy storage and sensing devices. Their versatility, functionalization capability, chemical/physical stability, reusability, long shelf-life, as well as good mechanical and thermal properties, also make them idoneous candidates for use in forensic sciences, which deal with the investigation of crimes, finding relations between evidence and criminals. In particular, molecularly imprinted polymers (MIPs), designed based on the principle of generating template-specific polymeric cavities fitted to the target molecules in the presence of selected chemicals via non-covalent or covalent interactions, are highly suitable for forensic analysis. In addition, their combination with other compounds such as carbon nanomaterials can provide composites with improved properties to be used in the analysis of illicit drugs, doping substances, biological agents, toxins and so forth. In this article, recent applications of polymeric materials in the field of forensic analysis are discussed. The goal is to summarize their current uses and put forth a projection of their potential as promising alternatives for standard competitors.
{"title":"Perspectives of Polymers in Forensic Analysis","authors":"A. Díez-Pascual","doi":"10.3390/macromol3020008","DOIUrl":"https://doi.org/10.3390/macromol3020008","url":null,"abstract":"Polymeric materials have recently attracted a lot of attention due to their potential applications in many fields, ranging from biomedicine, the food industry and environmental monitoring to electronic, energy storage and sensing devices. Their versatility, functionalization capability, chemical/physical stability, reusability, long shelf-life, as well as good mechanical and thermal properties, also make them idoneous candidates for use in forensic sciences, which deal with the investigation of crimes, finding relations between evidence and criminals. In particular, molecularly imprinted polymers (MIPs), designed based on the principle of generating template-specific polymeric cavities fitted to the target molecules in the presence of selected chemicals via non-covalent or covalent interactions, are highly suitable for forensic analysis. In addition, their combination with other compounds such as carbon nanomaterials can provide composites with improved properties to be used in the analysis of illicit drugs, doping substances, biological agents, toxins and so forth. In this article, recent applications of polymeric materials in the field of forensic analysis are discussed. The goal is to summarize their current uses and put forth a projection of their potential as promising alternatives for standard competitors.","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"489 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89338866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The study of the styrene–Ground Tire Rubber (GTR) graft radical polymerization is particularly challenging due to the complexity of the underlying kinetic mechanisms and nature of GTR. In this work, an experimental study on two scales (∼10 mL and ∼100 mL) and a machine learning (ML) modeling approach are combined to establish a quantitative relationship between operating conditions and styrene conversion. The two-scale experimental approach enables to verify the impact of upscaling on thermal and mixing effects that are particularly important in this heterogeneous system, as also evidenced in previous works. The adopted experimental setups are designed in view of multiple data production, while paying specific attention in data reliability by eliminating the uncertainty related to sampling for analyses. At the same time, all the potential sources of uncertainty, such as the mass loss along the different steps of the process and the precision of the experimental equipment, are also carefully identified and monitored. The experimental results on both scales validate previously observed effects of GTR, benzoyl peroxide initiator and temperature on styrene conversion but, at the same time, reveal the need of an efficient design of the experimental procedure in terms of mixing and of monitoring uncertainties. Subsequently, the most reliable experimental data (i.e., 69 data from the 10 mL system) are used for the screening of a series of diverse supervised-learning regression ML models and the optimization of the hyperparameters of the best-performing ones. These are gradient boosting, multilayer perceptrons and random forest with, respectively, a test R2 of 0.91 ± 0.04, 0.90 ± 0.04 and 0.89 ± 0.05. Finally, the effect of additional parameters, such as the scaling method, the number of folds and the random partitioning of data in the train/test splits, as well as the integration of the experimental uncertainties in the learning procedure, are exploited as means to improve the performance of the developed models.
{"title":"A Comprehensive Study on the Styrene–GTR Radical Graft Polymerization: Combination of an Experimental Approach, on Different Scales, with Machine Learning Modeling","authors":"Cindy Trinh, S. Hoppe, R. Laine, D. Meimaroglou","doi":"10.3390/macromol3010007","DOIUrl":"https://doi.org/10.3390/macromol3010007","url":null,"abstract":"The study of the styrene–Ground Tire Rubber (GTR) graft radical polymerization is particularly challenging due to the complexity of the underlying kinetic mechanisms and nature of GTR. In this work, an experimental study on two scales (∼10 mL and ∼100 mL) and a machine learning (ML) modeling approach are combined to establish a quantitative relationship between operating conditions and styrene conversion. The two-scale experimental approach enables to verify the impact of upscaling on thermal and mixing effects that are particularly important in this heterogeneous system, as also evidenced in previous works. The adopted experimental setups are designed in view of multiple data production, while paying specific attention in data reliability by eliminating the uncertainty related to sampling for analyses. At the same time, all the potential sources of uncertainty, such as the mass loss along the different steps of the process and the precision of the experimental equipment, are also carefully identified and monitored. The experimental results on both scales validate previously observed effects of GTR, benzoyl peroxide initiator and temperature on styrene conversion but, at the same time, reveal the need of an efficient design of the experimental procedure in terms of mixing and of monitoring uncertainties. Subsequently, the most reliable experimental data (i.e., 69 data from the 10 mL system) are used for the screening of a series of diverse supervised-learning regression ML models and the optimization of the hyperparameters of the best-performing ones. These are gradient boosting, multilayer perceptrons and random forest with, respectively, a test R2 of 0.91 ± 0.04, 0.90 ± 0.04 and 0.89 ± 0.05. Finally, the effect of additional parameters, such as the scaling method, the number of folds and the random partitioning of data in the train/test splits, as well as the integration of the experimental uncertainties in the learning procedure, are exploited as means to improve the performance of the developed models.","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"7 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88551677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cecilia Zárate-Pérez, R. Ramírez-Aguilar, E. Franco-Urquiza, Carlos Sánchez-Alvarado
This work is a collaborative effort between academia and industry to promote the development of new sustainable and profitable materials for manufacturing products. Incorporating wood flour particles (WF) in polypropylene (PP) grants environmental advantages in developing products that use renewable resources to manufacture PP/WF composites using the melt intercalation process. However, the interaction between a hydrophilic strengthening phase (wood flour) with a nonpolar polymer matrix (PP) is poor, resulting in deficient mechanical performance. This investigation details the use of graft and masterbatch coupling agents to evaluate their effects on mechanical parameters. The low compatibility between the constituents favors increasing the composites’ thermal properties because the reinforcing phase acts as a nucleating agent. PP showed typical mechanical behavior, with a marked necking and a wide deformation capacity of approximately 180%. The mechanical behavior of the PP/WF composites revealed an elastic region followed by a termination after their yield point, shortening the stress–strain curves and reducing their ductility at strain values of approximately 2–4%. Graft coupling agents have better intermolecular performance with PP than masterbatch coupling agents. The modulus of elasticity of the composites increased to around 82% relative to PP. Processing methods influenced the thermal properties of the composites. The melt-blending process promoted molecular orientation, while injection molding erased the thermomechanical history of the extruded pellets. The melting temperature was similar in the composites, so there was no evidence of thermal degradation. The results showed that the coupling agents favor the crystallinity of the PP over tensile strength. SEM observations showed insufficient adhesion between the WF and PP, which promotes a reduction in stress transfer during tensile testing. The WF particles act as fillers that increase the stiffness and reduce the ductility of composites.
{"title":"The Role of Coupling Agents in the Mechanical and Thermal Properties of Polypropylene/Wood Flour Composites","authors":"Cecilia Zárate-Pérez, R. Ramírez-Aguilar, E. Franco-Urquiza, Carlos Sánchez-Alvarado","doi":"10.3390/macromol3010006","DOIUrl":"https://doi.org/10.3390/macromol3010006","url":null,"abstract":"This work is a collaborative effort between academia and industry to promote the development of new sustainable and profitable materials for manufacturing products. Incorporating wood flour particles (WF) in polypropylene (PP) grants environmental advantages in developing products that use renewable resources to manufacture PP/WF composites using the melt intercalation process. However, the interaction between a hydrophilic strengthening phase (wood flour) with a nonpolar polymer matrix (PP) is poor, resulting in deficient mechanical performance. This investigation details the use of graft and masterbatch coupling agents to evaluate their effects on mechanical parameters. The low compatibility between the constituents favors increasing the composites’ thermal properties because the reinforcing phase acts as a nucleating agent. PP showed typical mechanical behavior, with a marked necking and a wide deformation capacity of approximately 180%. The mechanical behavior of the PP/WF composites revealed an elastic region followed by a termination after their yield point, shortening the stress–strain curves and reducing their ductility at strain values of approximately 2–4%. Graft coupling agents have better intermolecular performance with PP than masterbatch coupling agents. The modulus of elasticity of the composites increased to around 82% relative to PP. Processing methods influenced the thermal properties of the composites. The melt-blending process promoted molecular orientation, while injection molding erased the thermomechanical history of the extruded pellets. The melting temperature was similar in the composites, so there was no evidence of thermal degradation. The results showed that the coupling agents favor the crystallinity of the PP over tensile strength. SEM observations showed insufficient adhesion between the WF and PP, which promotes a reduction in stress transfer during tensile testing. The WF particles act as fillers that increase the stiffness and reduce the ductility of composites.","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86059154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoling Ma, Qingqing Ye, Shao-jie Zheng, Ji-jiang Hu, Zhen Yao
In this work, nylon 6 (PA6) and cationic dyeable polyester (CDP) modified with benzenesulfonate groups were reactively blended in a twin-screw extruder. The well-mixed CDP/PA6 blends were re-molten and statically kept for various amounts of time. The morphology evolution caused by phase separation was observed by a scanning electron microscope (SEM) and an atomic force microscopy-infrared (AFM-IR) technique. In the absence of shear force, the homogeneously mixed blends were found to separate rapidly into two phases because of the poor miscibility between polyester and polyamide. In the early stage, the dispersed phase was small in size and irregular in shape. With prolongation of the phase separation time, the dispersed phase turned into larger and spherical particles to minimize the interface between phases. The phase separation process typically lasted 2 to 7 min. This means that the effects of phase separation on the morphology of the blends cannot be ignored in injection molding, compression molding, or other processing processes short of shear force. The effects of the ratio between polyester and polyamide, the benzenesulfonate content, and the molecular weight of polymers on phase separation behavior were investigated.
{"title":"Experimental Studies on the Phase Separation Behavior of Molten Benzenesulfonate-Modified PET/PA6 Blends","authors":"Xiaoling Ma, Qingqing Ye, Shao-jie Zheng, Ji-jiang Hu, Zhen Yao","doi":"10.3390/macromol3010005","DOIUrl":"https://doi.org/10.3390/macromol3010005","url":null,"abstract":"In this work, nylon 6 (PA6) and cationic dyeable polyester (CDP) modified with benzenesulfonate groups were reactively blended in a twin-screw extruder. The well-mixed CDP/PA6 blends were re-molten and statically kept for various amounts of time. The morphology evolution caused by phase separation was observed by a scanning electron microscope (SEM) and an atomic force microscopy-infrared (AFM-IR) technique. In the absence of shear force, the homogeneously mixed blends were found to separate rapidly into two phases because of the poor miscibility between polyester and polyamide. In the early stage, the dispersed phase was small in size and irregular in shape. With prolongation of the phase separation time, the dispersed phase turned into larger and spherical particles to minimize the interface between phases. The phase separation process typically lasted 2 to 7 min. This means that the effects of phase separation on the morphology of the blends cannot be ignored in injection molding, compression molding, or other processing processes short of shear force. The effects of the ratio between polyester and polyamide, the benzenesulfonate content, and the molecular weight of polymers on phase separation behavior were investigated.","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72966723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A simple, efficient procedure has been employed to effect intra- and inter-chain crosslinking of two commercially available thiolated poly(dimethylsiloxane) copolymers (T-PDMS) with 4–6% or 13–17% of mercaptopropyl side-chains. The thiol functional groups were converted to disulfides (D-PDMS) in chloroform solutions of I2. Importantly, the conditions employed avoid over-oxidation to other types of sulfur-containing species, and the concentration of T-PDMS during the crosslinking reaction dictated the rheological properties and liquid or solid nature of the D-PDMS. The procedure for obtaining the crosslinked copolymers is simpler than other approaches in the literature used to crosslink polysiloxane backbones and to modulate their properties. By changing the concentration of T-PDMS during the treatment with I2, the degree of intra- and inter-chain crosslinking can be controlled (as assessed qualitatively by the solid or liquid nature of the products and their viscoelastic properties). For each of the T-PDMS materials, there is a concentration threshold, above which products are solids, and below which they are oils. Liquid and solid materials were characterized using 1H and 13C solution-state and 13C solid-state NMR spectroscopy, respectively. They indicate greater than 90% conversion of thiols to disulfides in the presence of excess I2. The rheological behavior of the liquid products, solvent swelling ability of solid products, and the thermal stability of the reactants and products are described. Furthermore, the solid products exhibit some of the highest swelling values reported in the literature for poly(dimethylsiloxane) (PDMS) materials. As assessed by thermal gravimetric analyses, the disulfide-crosslinked materials are more stable thermally than the corresponding thiols.
{"title":"Influence of Concentration of Thiol-Substituted Poly(dimethylsiloxane)s on the Properties, Phases, and Swelling Behaviors of Their Crosslinked Disulfides","authors":"Danielle M. Beaupre, A. Goroncy, R. Weiss","doi":"10.3390/macromol3010004","DOIUrl":"https://doi.org/10.3390/macromol3010004","url":null,"abstract":"A simple, efficient procedure has been employed to effect intra- and inter-chain crosslinking of two commercially available thiolated poly(dimethylsiloxane) copolymers (T-PDMS) with 4–6% or 13–17% of mercaptopropyl side-chains. The thiol functional groups were converted to disulfides (D-PDMS) in chloroform solutions of I2. Importantly, the conditions employed avoid over-oxidation to other types of sulfur-containing species, and the concentration of T-PDMS during the crosslinking reaction dictated the rheological properties and liquid or solid nature of the D-PDMS. The procedure for obtaining the crosslinked copolymers is simpler than other approaches in the literature used to crosslink polysiloxane backbones and to modulate their properties. By changing the concentration of T-PDMS during the treatment with I2, the degree of intra- and inter-chain crosslinking can be controlled (as assessed qualitatively by the solid or liquid nature of the products and their viscoelastic properties). For each of the T-PDMS materials, there is a concentration threshold, above which products are solids, and below which they are oils. Liquid and solid materials were characterized using 1H and 13C solution-state and 13C solid-state NMR spectroscopy, respectively. They indicate greater than 90% conversion of thiols to disulfides in the presence of excess I2. The rheological behavior of the liquid products, solvent swelling ability of solid products, and the thermal stability of the reactants and products are described. Furthermore, the solid products exhibit some of the highest swelling values reported in the literature for poly(dimethylsiloxane) (PDMS) materials. As assessed by thermal gravimetric analyses, the disulfide-crosslinked materials are more stable thermally than the corresponding thiols.","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"92 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83802180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
High-quality academic publishing is built on rigorous peer review [...]
高质量的学术出版建立在严格的同行评审的基础上[…]
{"title":"Acknowledgment to the Reviewers of Macromol in 2022","authors":"","doi":"10.3390/macromol3010003","DOIUrl":"https://doi.org/10.3390/macromol3010003","url":null,"abstract":"High-quality academic publishing is built on rigorous peer review [...]","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"28 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91314837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In 1920, Hermann Staudinger discovered that macromolecules consist of long chains of covalently linked building blocks and subsequently published the first paper on polymerization [...]
{"title":"Hot Topics in 2022 and Future Perspectives of Macromolecular Science","authors":"A. Díez-Pascual","doi":"10.3390/macromol3010002","DOIUrl":"https://doi.org/10.3390/macromol3010002","url":null,"abstract":"In 1920, Hermann Staudinger discovered that macromolecules consist of long chains of covalently linked building blocks and subsequently published the first paper on polymerization [...]","PeriodicalId":18139,"journal":{"name":"Macromol","volume":"2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78868536","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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