Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperat...Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperatures and faces issues like low selectivity for liquid aromatics,separation difficulties,and rapid catalyst deactivation due to coking.To address this,a multifunctional Ni/HZSM-5 catalyst was developed to efficiently upgrade various polyolefins—including polyvinyl chloride—into gaseous alkanes(C_(1)–C_(5))and easily separable liquid aromatics(C_(6)–C_(12))at 400°C,without added solvents or hydrogen.Aromatic products make up 57.1 wt%of total output,with more than 97.8%selectivity for the liquid phase and a BTX(benzene,toluene,and xylene)selectivity of 76.1%.The high activity and selectivity for aromatics stem from synergistic interactions between Ni nanoparticles(NPs)and acid sites in the zeolite,which promote selective C–C bond breaking and control hydrogenolysis and aromatization pathways.This synergy allows precise control over the distribution of products by carbon number and favors the formation of separable aromatics.Notably,the catalyst also prevents coking by hydrogenolyzing and hydrogenating reactive intermediates before they form stable graphite-like deposits.Consequently,Ni/ZSM-5 catalyst demonstrates excellent stability,maintaining consistent aromatics yield over 13 consecutive cycles and processing over 30 times its weight in plastics without regeneration.After regeneration,the activity of the catalyst was fully restored,highlighting its potential for industrial use.This work offers valuable insights for designing durable,high-activity catalysts,providing a practical route to improve plastic recycling technologies.展开更多
In this communication, by means of stress relaxation experiments, the viscous stress at various strains during tensile deformation of oriented polyolefin samples including high density polyethylene （HDPE）, linear lo...In this communication, by means of stress relaxation experiments, the viscous stress at various strains during tensile deformation of oriented polyolefin samples including high density polyethylene （HDPE）, linear low density polyethylene （LLDPE） and isotactic polypropylene （iPP）, has been determined. The viscous stress in the oriented samples takes up to 50%-70% of the total stress, which is unusually high compared with their isotropic counterparts. The unusual high viscous stress was discussed based on mainly the existence of shish structure in oriented polyolefins, which could enhance the inter-lamella coupling significantly.展开更多
Recent successful examples for synthesis of new polyolefins containing (polar) functionalities by adopting the approaches by controlled incorporation of reactive functionalities (and the subsequent introduction of pol...Recent successful examples for synthesis of new polyolefins containing (polar) functionalities by adopting the approaches by controlled incorporation of reactive functionalities (and the subsequent introduction of polar functionalities under mild conditions) by coordination polymerization in the presence of transition metal complex catalysts have been described. Related methods (such as direct copolymerization of olefin with polar monomer using living radical or coordination insertion methods) have also been demonstrated for comparison. Our recent efforts for precise synthesis of polyolefins containing polar functionalities by efficient incorporation of reactive functionality by copolymerization of ethylene with nonconjugateddiene (1,7-octadiene, vinylcyclohexene etc.) or divinyl-biphenyl using nonbridged half-titanocene [ex. Cp’TiCl2(O-2,6-iPr2C6H3), Cp’ = C5Me5, tBuC5H4 etc.] catalysts have been introduced.展开更多
The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC （Fluid Catalytic Cracking） catalyst which was dispersed in it. The activation energy of the...The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC （Fluid Catalytic Cracking） catalyst which was dispersed in it. The activation energy of the catalytic cracking of polyethylene was about 74 kJ/mol. The cracked product was naphtha and middle distillate as the major product and gaseous hydrocarbon （C1-C4） as the minor product while little heavy oil was produced. The chemical compositions of the product were： aromatic hydrocarbons, isoparaffins and branched olefins, whereas that of the non-catalyzed products were： n-olefins and n-paraffins with minor amount of dienes with increasing the process time. Additionally, the product pattern shifted from naphtha rich product to kerosene and gas-oil rich product. However, any catalytic product showed low fluid point （〈 -10 ℃）, while that of the non-catalyzed product was as high as 40 ℃. Catalyst could process, more than 100 times by weight of polyethylene with fairly small amount （- 30 wt%） of coke deposition. Spent catalyst gave higher hydrocarbons while fresh catalyst gave gaseous product as the major product. Other polyolefins such as polypropylene and polystyrene were tested on same catalyst to show that their reactivity is higher than that of polyethylene and gave the aliphatic products, alkyl benzenes and C6-C9 iso-paraffins as the major product. Product pattern of the cracked product suggested that the reaction proceeded via the primary reactions making paraffins and olefins which were followed by the isomerization, secondary cracking, aromatization and hydrogen transfer which based on the carbenium ion mechanism.展开更多
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金supported by the National Key R&D Program of China(2021YFA1501700)the National Natural Science Foundation of China(22272114)+2 种基金the Funding for Hundred Talent Program(20822041E4079)the Fundamental Research Funds from Sichuan University(2022SCUNL103)This work has also been supported by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.via collaborative project No.36800000-24-ZC0607-0175.
文摘Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperatures and faces issues like low selectivity for liquid aromatics,separation difficulties,and rapid catalyst deactivation due to coking.To address this,a multifunctional Ni/HZSM-5 catalyst was developed to efficiently upgrade various polyolefins—including polyvinyl chloride—into gaseous alkanes(C_(1)–C_(5))and easily separable liquid aromatics(C_(6)–C_(12))at 400°C,without added solvents or hydrogen.Aromatic products make up 57.1 wt%of total output,with more than 97.8%selectivity for the liquid phase and a BTX(benzene,toluene,and xylene)selectivity of 76.1%.The high activity and selectivity for aromatics stem from synergistic interactions between Ni nanoparticles(NPs)and acid sites in the zeolite,which promote selective C–C bond breaking and control hydrogenolysis and aromatization pathways.This synergy allows precise control over the distribution of products by carbon number and favors the formation of separable aromatics.Notably,the catalyst also prevents coking by hydrogenolyzing and hydrogenating reactive intermediates before they form stable graphite-like deposits.Consequently,Ni/ZSM-5 catalyst demonstrates excellent stability,maintaining consistent aromatics yield over 13 consecutive cycles and processing over 30 times its weight in plastics without regeneration.After regeneration,the activity of the catalyst was fully restored,highlighting its potential for industrial use.This work offers valuable insights for designing durable,high-activity catalysts,providing a practical route to improve plastic recycling technologies.
基金This work was financially supported by the National Natural Science Foundation of China (Nos. 20404008, 50533050 and 20490220)This work was subsidized by the Special Funds for Major State Basic Research Projects of China (No. 2003CB615600).
文摘In this communication, by means of stress relaxation experiments, the viscous stress at various strains during tensile deformation of oriented polyolefin samples including high density polyethylene （HDPE）, linear low density polyethylene （LLDPE） and isotactic polypropylene （iPP）, has been determined. The viscous stress in the oriented samples takes up to 50%-70% of the total stress, which is unusually high compared with their isotropic counterparts. The unusual high viscous stress was discussed based on mainly the existence of shish structure in oriented polyolefins, which could enhance the inter-lamella coupling significantly.
文摘Recent successful examples for synthesis of new polyolefins containing (polar) functionalities by adopting the approaches by controlled incorporation of reactive functionalities (and the subsequent introduction of polar functionalities under mild conditions) by coordination polymerization in the presence of transition metal complex catalysts have been described. Related methods (such as direct copolymerization of olefin with polar monomer using living radical or coordination insertion methods) have also been demonstrated for comparison. Our recent efforts for precise synthesis of polyolefins containing polar functionalities by efficient incorporation of reactive functionality by copolymerization of ethylene with nonconjugateddiene (1,7-octadiene, vinylcyclohexene etc.) or divinyl-biphenyl using nonbridged half-titanocene [ex. Cp’TiCl2(O-2,6-iPr2C6H3), Cp’ = C5Me5, tBuC5H4 etc.] catalysts have been introduced.
文摘The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC （Fluid Catalytic Cracking） catalyst which was dispersed in it. The activation energy of the catalytic cracking of polyethylene was about 74 kJ/mol. The cracked product was naphtha and middle distillate as the major product and gaseous hydrocarbon （C1-C4） as the minor product while little heavy oil was produced. The chemical compositions of the product were： aromatic hydrocarbons, isoparaffins and branched olefins, whereas that of the non-catalyzed products were： n-olefins and n-paraffins with minor amount of dienes with increasing the process time. Additionally, the product pattern shifted from naphtha rich product to kerosene and gas-oil rich product. However, any catalytic product showed low fluid point （〈 -10 ℃）, while that of the non-catalyzed product was as high as 40 ℃. Catalyst could process, more than 100 times by weight of polyethylene with fairly small amount （- 30 wt%） of coke deposition. Spent catalyst gave higher hydrocarbons while fresh catalyst gave gaseous product as the major product. Other polyolefins such as polypropylene and polystyrene were tested on same catalyst to show that their reactivity is higher than that of polyethylene and gave the aliphatic products, alkyl benzenes and C6-C9 iso-paraffins as the major product. Product pattern of the cracked product suggested that the reaction proceeded via the primary reactions making paraffins and olefins which were followed by the isomerization, secondary cracking, aromatization and hydrogen transfer which based on the carbenium ion mechanism.
