An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecul...An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecular weight polyethylene with high melting transition temperature, as well as atactic oligopropylene with average molecular weight of ~1150 g mol-1.展开更多
The NdCl_3/MgCl_2 bisupported catalyst was prepared by using NdCl_3 ,MgCl_2, (CH_3)_2(CH_2)_2 OH and TiCl_4. It is shown that the structure of bisupported catalyst was different from those of either NdCl_3 or MgCl_2 s...The NdCl_3/MgCl_2 bisupported catalyst was prepared by using NdCl_3 ,MgCl_2, (CH_3)_2(CH_2)_2 OH and TiCl_4. It is shown that the structure of bisupported catalyst was different from those of either NdCl_3 or MgCl_2 single supported catalyst. A peculiar type of kinetic curve for ethylene polymerization was found.展开更多
In this paper, highly active Ziegler-Natta catalysts of MgCl_2 supported TiCl_4 for synthesis ofpolyolefins, using di-n-butyl phthalate (DNBP) as internal donor and diphenyl dimethoxyl silane(DPDMS) as external donor,...In this paper, highly active Ziegler-Natta catalysts of MgCl_2 supported TiCl_4 for synthesis ofpolyolefins, using di-n-butyl phthalate (DNBP) as internal donor and diphenyl dimethoxyl silane(DPDMS) as external donor, have been prepared. The conditions controlling the treatment ofsupport were studied. The interactions of various components present in the catalysts and theirinfluences on catalytic performance were investigated. It is found that by using DNBP and DPDMSas internal and external donors together the polymer products with higher isotactic index can beobtained. Plausible structure model and mechanism were proposed.展开更多
As one of the most important products in petrochemical industry, polyolefin, including mainly polyethylene, polypropylene and α\|olefin polymers, is also a major raw material for plastics industry. The market demand ...As one of the most important products in petrochemical industry, polyolefin, including mainly polyethylene, polypropylene and α\|olefin polymers, is also a major raw material for plastics industry. The market demand for polyolefin in 2002 reached 88 Mt, making two thirds of the demand for thermoplastics. The growth rate of demand will be 5%-7 % in the next five years\+\{\\}. Because of its close relation to nations economy and its peoples daily life, the output of polyolefin becomes an important index of the nations industria lization and modernization level.展开更多
The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction a...The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes: (i) Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl.(ii) The transition states were formed. The energy di?erence between transition states and the coordination compounds was 40.687 kJ/mol. (iii) Double bond opened and Ti-C(4) bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.展开更多
Novel Ni(II)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethyl...Novel Ni(II)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethylene oligomerization and polymerization reactions, activated by methylaluminoxane (MAO). The MAO-treated 1-3b presents an active catalytic center, which may oligomerize and polymerize ethylene to produce linear α-olefins and polyethylene, respectively. The molecular weight distributions of oligomers that are obtained are in good agreement with the Schulz-Flory rules for oligomers〉C4. The activity of 3b-MAO complex is 6.3×10^7 g/(molNi.h) at 50 ℃. The activities and molecular weight distributions of oligomers show significant reliance on the structures of catalyst precursors.展开更多
In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as het...In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as heterogeneous catalysts due to their excellent processability. In this study, nine types of heterogeneous procatalyst Ln/Ni2+-micas were synthesized via a one-pot preparation method, which includes both the condensation reaction of the ligand derivatives and the intercalation of the ligands into the Ni2+ ion-exchanged fluorotetrasilicic mica interlayer. The ligand structures of the prepared procatalysts were [Ln: R-N = C(Nap)-C(Nap) = N-R] [(Nap = 1,8-naphthdiyl) (L1, R = 2-MePh;L2, R = 2-FPh;L3, R = 2-BrPh;L4, R = 4-MePh;L5, R = 4-FPh;L6, R = 4-BrPh;L7, R = 2,4-F2Ph;L8, R = 2,4-Br2Ph;L9, R = 2,6-F2Ph). At 50℃ and 0.7 MPaethylene pressure, the triisobutylaluminum-activated L1-L6/Ni2+-mica showed a catalytic activity for the ethylene oligo-/polymerization in the range of 334 - 549 g-ethylene•g-cat–1•h–1. A high catalyst activity was obtained when the substituent having a larger steric bulk than that of a methyl substituent was introduced at the ortho-position of the aryl rings. The introduction of the fluorine substituent as a strong electron-withdrawing group to the para-position also increased the catalytic activity. The L2, L4, L5, and L6/Ni2+-micas showed moderate selectivities to oligomers consisting of C4-C20 in the range of 19.9 - 41.6 wt% at 50℃. The calculated Schulz-Flory constants α based on the mole fraction of C12 and C14 were within 0.61 - 0.78.展开更多
Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After dec...Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After decades of research,recent developments in a variety of high-performance catalytic systems have shown that this field is on the brink of industrialization.This review summarizes representative olefin-polar monomer coordination copolymerization catalyst systems that may be suitable for industrial polyolefin production via homogeneous solution-phase processes or heterogeneous gas-phase/slurry-phase processes.展开更多
Three ansa-metallocenes(Me_2C)(Me_2Si)Cp_2TiCl_2(1),[(CH_2)_5C](Me_2Si)Cp_2TiCl_2 (2)and (Me_2C)(Me_2Si)Cp_2ZrCl_2 (3)with larger dihedral angles and longer distance from metal to the center of Cp planes were synthesi...Three ansa-metallocenes(Me_2C)(Me_2Si)Cp_2TiCl_2(1),[(CH_2)_5C](Me_2Si)Cp_2TiCl_2 (2)and (Me_2C)(Me_2Si)Cp_2ZrCl_2 (3)with larger dihedral angles and longer distance from metal to the center of Cp planes were synthesized and used as catalysts for ethylene polymerization in the presence of methylaluminoxane (MAO).In the case of ethylene polymerization,compared the feature structures of unbridged metallocenes, singly bridged metallocenes and doubly bridged metallocenes 1,2,3,there exhibit the relationship bet...展开更多
(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe3)(NR)(OR?)(PMe3)2 [R = Ad, C6H5, 2,6-Me2C6H3, 2,6-Cl2C6H3;R?= 2,6-Me2C6H3, 2,6-i Pr2C6H3, 2,6-F2C6H3, C6F5, C6Cl5] exhibited from moderate to remarkable catalyt...(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe3)(NR)(OR?)(PMe3)2 [R = Ad, C6H5, 2,6-Me2C6H3, 2,6-Cl2C6H3;R?= 2,6-Me2C6H3, 2,6-i Pr2C6H3, 2,6-F2C6H3, C6F5, C6Cl5] exhibited from moderate to remarkable catalytic activities for ringopening metathesis polymerization(ROMP) of norbornene(NBE). The catalytic activities were affected by the ligand substituents, and V(CHSiMe3)(N-2,6-Cl2C6H3)(OC6X5)(PMe3)2(X = F, Cl) demonstrated the exceptionally high catalytic activities for ROMP of NBE.The complexes polymerized cycloheptene(CHPE) and cis-cyclooctene(COE), and ROMP of COE by the OC6 Cl5 analogue proceeded in a living manner even at 80℃, and the activity increased with increasing the temperature up to 120 ℃. Highly active catalysts for ROMP of cyclic olefins(NBE, cyclopentene, and CHPE) can be generated in situ by premixing isolated V(CHSiMe3)(NC6F5)(O-2,6-iPr2C6H3)(PMe3)2 with 1.0 equiv. of C6F5OH or C6Cl5OH via immediate phenoxy exchange;the activity was affected by the kind of phenol added [TOF in the ROMPs of NBE: 4.62 × 10^4 min^–1(upon addition of C6F5OH) versus 37.3 min^–1(none)].展开更多
Polymerizations of linear α-olefins(CnH2n, CH2=CH―R, R = Cn-2) catalyzed by early transition metals typically afford amorphous polymers with alkyl chains(Cn-2), while chain-straightening polymerizations of α-olefin...Polymerizations of linear α-olefins(CnH2n, CH2=CH―R, R = Cn-2) catalyzed by early transition metals typically afford amorphous polymers with alkyl chains(Cn-2), while chain-straightening polymerizations of α-olefins with nickel-based catalysts produce semicrystalline polyolefins. Polymerizations of various α-olefins were carried out using an α-diamine nickel catalyst with a significantly distorted chelating ring. The influences of temperature, monomer concentration, and chain length of α-olefins on polyolefin microstructure were examined in detail. The α-diamine nickel catalyst realized highly regioselective 2,1-insertion of α-olefins regardless of reaction temperature and monomer concentration. Increased chain length of α-olefins led to the formation of more linear polyolefin.Semicrystalline polyolefins with high melting temperatures(Tm) were made from α-olefins through highly regioselective 2,1-insertion and precise chain-straightening.展开更多
Polyolefins are an indispensable class of materials that have become the most widely produced and utilized polymers today.They are readily synthesized from cheap and abundant monomer feedstocks,such as ethylene and pr...Polyolefins are an indispensable class of materials that have become the most widely produced and utilized polymers today.They are readily synthesized from cheap and abundant monomer feedstocks,such as ethylene and propylene,and are capable of achieving a vast array of thermal and mechanical properties based upon their composition and topology.However,despite their numerous advantages, polyolefins are typically devoid of functional groups which can limit their applicability to many product families,such as coatings,adhesives,and cross-linked polyolefins.展开更多
Brookhart-typeα-diimine nickel and palladium catalysts have been extensively studied over the past several decades;however,the heterogenization of these metal complexes has received much less attention.In this contri...Brookhart-typeα-diimine nickel and palladium catalysts have been extensively studied over the past several decades;however,the heterogenization of these metal complexes has received much less attention.In this contribution,we installed a trifluoroborate potassium substituent on anα-diimine framework.The ionic nature of trifluoroborate potassium endowed theα-diimine nickel complex with a strong affinity for the SiO_(2)support,while its electron-donating nature enhanced the catalyst stability and polyethylene molecular weight.In the presence of only 100 equiv.of Et2AlCl cocatalyst,the SiO_(2)-supported catalyst demonstrated significantly better performance than its homogeneous analog during ethylene polymerization,with extremely high activity(1.42–6.53×10^(7)g mol^(−1)h^(−1))and high thermal stability.The heterogeneous system led to the formation of high-molecular-weight polyethylenes(Mn 142,500–732,800 g/mol),narrow polydispersities(2.18–3.00),tunable branching densities(21–64 per 1000 carbon atoms),and great mechanical properties.Moreover,the efficient copolymerization of ethylene with comonomers such as methyl 10-undecenoate,6-chloro-1-hexene or 5-hexenylacetate was achieved.These superior properties enabled by the trifluoroborate potassium moiety may inspire its applications in other polymerization catalyst systems.展开更多
文摘An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecular weight polyethylene with high melting transition temperature, as well as atactic oligopropylene with average molecular weight of ~1150 g mol-1.
文摘The NdCl_3/MgCl_2 bisupported catalyst was prepared by using NdCl_3 ,MgCl_2, (CH_3)_2(CH_2)_2 OH and TiCl_4. It is shown that the structure of bisupported catalyst was different from those of either NdCl_3 or MgCl_2 single supported catalyst. A peculiar type of kinetic curve for ethylene polymerization was found.
基金This work was supported by the National Natural Science Foundation of China
文摘In this paper, highly active Ziegler-Natta catalysts of MgCl_2 supported TiCl_4 for synthesis ofpolyolefins, using di-n-butyl phthalate (DNBP) as internal donor and diphenyl dimethoxyl silane(DPDMS) as external donor, have been prepared. The conditions controlling the treatment ofsupport were studied. The interactions of various components present in the catalysts and theirinfluences on catalytic performance were investigated. It is found that by using DNBP and DPDMSas internal and external donors together the polymer products with higher isotactic index can beobtained. Plausible structure model and mechanism were proposed.
文摘As one of the most important products in petrochemical industry, polyolefin, including mainly polyethylene, polypropylene and α\|olefin polymers, is also a major raw material for plastics industry. The market demand for polyolefin in 2002 reached 88 Mt, making two thirds of the demand for thermoplastics. The growth rate of demand will be 5%-7 % in the next five years\+\{\\}. Because of its close relation to nations economy and its peoples daily life, the output of polyolefin becomes an important index of the nations industria lization and modernization level.
文摘The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes: (i) Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl.(ii) The transition states were formed. The energy di?erence between transition states and the coordination compounds was 40.687 kJ/mol. (iii) Double bond opened and Ti-C(4) bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.
基金This work is supported by PetroChina Company Limited (No.030414-01)
文摘Novel Ni(II)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethylene oligomerization and polymerization reactions, activated by methylaluminoxane (MAO). The MAO-treated 1-3b presents an active catalytic center, which may oligomerize and polymerize ethylene to produce linear α-olefins and polyethylene, respectively. The molecular weight distributions of oligomers that are obtained are in good agreement with the Schulz-Flory rules for oligomers〉C4. The activity of 3b-MAO complex is 6.3×10^7 g/(molNi.h) at 50 ℃. The activities and molecular weight distributions of oligomers show significant reliance on the structures of catalyst precursors.
文摘In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as heterogeneous catalysts due to their excellent processability. In this study, nine types of heterogeneous procatalyst Ln/Ni2+-micas were synthesized via a one-pot preparation method, which includes both the condensation reaction of the ligand derivatives and the intercalation of the ligands into the Ni2+ ion-exchanged fluorotetrasilicic mica interlayer. The ligand structures of the prepared procatalysts were [Ln: R-N = C(Nap)-C(Nap) = N-R] [(Nap = 1,8-naphthdiyl) (L1, R = 2-MePh;L2, R = 2-FPh;L3, R = 2-BrPh;L4, R = 4-MePh;L5, R = 4-FPh;L6, R = 4-BrPh;L7, R = 2,4-F2Ph;L8, R = 2,4-Br2Ph;L9, R = 2,6-F2Ph). At 50℃ and 0.7 MPaethylene pressure, the triisobutylaluminum-activated L1-L6/Ni2+-mica showed a catalytic activity for the ethylene oligo-/polymerization in the range of 334 - 549 g-ethylene•g-cat–1•h–1. A high catalyst activity was obtained when the substituent having a larger steric bulk than that of a methyl substituent was introduced at the ortho-position of the aryl rings. The introduction of the fluorine substituent as a strong electron-withdrawing group to the para-position also increased the catalytic activity. The L2, L4, L5, and L6/Ni2+-micas showed moderate selectivities to oligomers consisting of C4-C20 in the range of 19.9 - 41.6 wt% at 50℃. The calculated Schulz-Flory constants α based on the mole fraction of C12 and C14 were within 0.61 - 0.78.
基金supported by the National Key R&D Program of China(grant no.2021YFA1501700)the National Natural Science Foundation of China(grant nos.52025031,22001004,52373002,U1904212,and 52203016).
文摘Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After decades of research,recent developments in a variety of high-performance catalytic systems have shown that this field is on the brink of industrialization.This review summarizes representative olefin-polar monomer coordination copolymerization catalyst systems that may be suitable for industrial polyolefin production via homogeneous solution-phase processes or heterogeneous gas-phase/slurry-phase processes.
基金the National Natural Science Foundation of China(No.50573018)
文摘Three ansa-metallocenes(Me_2C)(Me_2Si)Cp_2TiCl_2(1),[(CH_2)_5C](Me_2Si)Cp_2TiCl_2 (2)and (Me_2C)(Me_2Si)Cp_2ZrCl_2 (3)with larger dihedral angles and longer distance from metal to the center of Cp planes were synthesized and used as catalysts for ethylene polymerization in the presence of methylaluminoxane (MAO).In the case of ethylene polymerization,compared the feature structures of unbridged metallocenes, singly bridged metallocenes and doubly bridged metallocenes 1,2,3,there exhibit the relationship bet...
基金partly supported by Grant-in-Aid for Scientific Research on Innovative Areas ("3D Active-Site Science", No. 26105003) from The Ministry of Education, Culture, Sports, Science and Technology (MEXT), JapanGrant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (JSPS, Nos. 15H03812, 18H01982)the Tokyo Metropolitan government (Tokyo Human Resources Fund for City Diplomacy) for pre-doctoral fellowship
文摘(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe3)(NR)(OR?)(PMe3)2 [R = Ad, C6H5, 2,6-Me2C6H3, 2,6-Cl2C6H3;R?= 2,6-Me2C6H3, 2,6-i Pr2C6H3, 2,6-F2C6H3, C6F5, C6Cl5] exhibited from moderate to remarkable catalytic activities for ringopening metathesis polymerization(ROMP) of norbornene(NBE). The catalytic activities were affected by the ligand substituents, and V(CHSiMe3)(N-2,6-Cl2C6H3)(OC6X5)(PMe3)2(X = F, Cl) demonstrated the exceptionally high catalytic activities for ROMP of NBE.The complexes polymerized cycloheptene(CHPE) and cis-cyclooctene(COE), and ROMP of COE by the OC6 Cl5 analogue proceeded in a living manner even at 80℃, and the activity increased with increasing the temperature up to 120 ℃. Highly active catalysts for ROMP of cyclic olefins(NBE, cyclopentene, and CHPE) can be generated in situ by premixing isolated V(CHSiMe3)(NC6F5)(O-2,6-iPr2C6H3)(PMe3)2 with 1.0 equiv. of C6F5OH or C6Cl5OH via immediate phenoxy exchange;the activity was affected by the kind of phenol added [TOF in the ROMPs of NBE: 4.62 × 10^4 min^–1(upon addition of C6F5OH) versus 37.3 min^–1(none)].
基金financially supported by the National Natural Science Foundation of China (Nos. 21674130, 51873234)Natural Science Foundation of Guangdong Province (No. 2017A030310 349)+1 种基金Fundamental Research Funds for the Central Universities (No. 17lgjc02)PetroChina Innovation Foundation (No. 2017D-5007-0505)
文摘Polymerizations of linear α-olefins(CnH2n, CH2=CH―R, R = Cn-2) catalyzed by early transition metals typically afford amorphous polymers with alkyl chains(Cn-2), while chain-straightening polymerizations of α-olefins with nickel-based catalysts produce semicrystalline polyolefins. Polymerizations of various α-olefins were carried out using an α-diamine nickel catalyst with a significantly distorted chelating ring. The influences of temperature, monomer concentration, and chain length of α-olefins on polyolefin microstructure were examined in detail. The α-diamine nickel catalyst realized highly regioselective 2,1-insertion of α-olefins regardless of reaction temperature and monomer concentration. Increased chain length of α-olefins led to the formation of more linear polyolefin.Semicrystalline polyolefins with high melting temperatures(Tm) were made from α-olefins through highly regioselective 2,1-insertion and precise chain-straightening.
文摘Polyolefins are an indispensable class of materials that have become the most widely produced and utilized polymers today.They are readily synthesized from cheap and abundant monomer feedstocks,such as ethylene and propylene,and are capable of achieving a vast array of thermal and mechanical properties based upon their composition and topology.However,despite their numerous advantages, polyolefins are typically devoid of functional groups which can limit their applicability to many product families,such as coatings,adhesives,and cross-linked polyolefins.
基金supported by National Key R&D Program of China(No.2021YFA1501700)National Natural Science Foundation of China(Nos.52025031,U19B6001 and U1904212)K.C.Wong Education Foundation.
文摘Brookhart-typeα-diimine nickel and palladium catalysts have been extensively studied over the past several decades;however,the heterogenization of these metal complexes has received much less attention.In this contribution,we installed a trifluoroborate potassium substituent on anα-diimine framework.The ionic nature of trifluoroborate potassium endowed theα-diimine nickel complex with a strong affinity for the SiO_(2)support,while its electron-donating nature enhanced the catalyst stability and polyethylene molecular weight.In the presence of only 100 equiv.of Et2AlCl cocatalyst,the SiO_(2)-supported catalyst demonstrated significantly better performance than its homogeneous analog during ethylene polymerization,with extremely high activity(1.42–6.53×10^(7)g mol^(−1)h^(−1))and high thermal stability.The heterogeneous system led to the formation of high-molecular-weight polyethylenes(Mn 142,500–732,800 g/mol),narrow polydispersities(2.18–3.00),tunable branching densities(21–64 per 1000 carbon atoms),and great mechanical properties.Moreover,the efficient copolymerization of ethylene with comonomers such as methyl 10-undecenoate,6-chloro-1-hexene or 5-hexenylacetate was achieved.These superior properties enabled by the trifluoroborate potassium moiety may inspire its applications in other polymerization catalyst systems.