In this work fibers derived from coffee</span><span style="font-family:Verdana;">,</span><span style="font-family:Verdana;"> hulls ha</span><span style="font-f...In this work fibers derived from coffee</span><span style="font-family:Verdana;">,</span><span style="font-family:Verdana;"> hulls ha</span><span style="font-family:Verdana;">ve</span><span style="font-family:Verdana;"> been incorporated into Linear Low Density Polyethylene (LLDPE). The influence of the filler content on </span><span style="font-family:Verdana;">the </span><span style="font-family:Verdana;">thermal and physicomechanical properties of the composites obtained was assessed. The results showed that the incorporation of fibers was able to improve the thermostability of LLDPE/Coffee hulls fibers;comparing the treated fiber composite with untreated fiber composites, the chemical treatment reduces by 58.3% the water absorption, while increasing the elongation and tensile strength by about 48% and 17% respectively. Moreover, due to better interfacial interaction induced by MAPE, the corresponding composite exhibited better properties compared to the untreated fiber composite. Results are indicative of the fact that both mercerization and MAPE (coupling agent) have significant positive effects on the fib</span><span style="font-family:Verdana;">er</span><span style="font-family:Verdana;">-matrix interaction in terms of adhesion, wetting and dispersion, this treatment produced a better fiber distribution and consequently a more uniform composite morphology without voids and gaps between the fibers and the matrix, allowing the possibility to use higher fiber contents (up to 30% wt.) with acceptable mechanical properties.展开更多
Background: Although abduction of the acetabular component is considered to predict factors for polyethylene wear attributable to osteolysis, other radiographic factors have yet to be elucidated. The purpose of the pr...Background: Although abduction of the acetabular component is considered to predict factors for polyethylene wear attributable to osteolysis, other radiographic factors have yet to be elucidated. The purpose of the present study was to evaluate whether anteversion or change in implantation angle of the acetabular component influences polyethylene linear wear by using standing and supine radiographs of the hip joint. Methods: Standing and supine plain anteroposterior radiographs of 62 hip joints in which cementless total hip arthroplasty was performed were examined for polyethylene linear wear rate (mm/year), pelvic inclination, and radiological inclination and anatomic anteversion of the acetabular component. Results: All correlation coefficients of measurements of polyethylene linear wear, pelvic inclination angle, anatomical anteversion angle and radiological inclination angle were calculated highly. And by the three-dimensional numerical analysis, anatomic anteversion of the acetabular component had at least some effect on the degree of polyethylene wear. Conclusion: This study suggests that increased anteversion of the acetabular component reduces polyethylene linear wear in metal-on-polyethylene total hiparthroplasty.展开更多
Straw utilization is a key issue related to agricultural production and air pollution control.In this study,a novel extrusion process was proposed to improve the physical and mechanical properties of the straw-reinfor...Straw utilization is a key issue related to agricultural production and air pollution control.In this study,a novel extrusion process was proposed to improve the physical and mechanical properties of the straw-reinforced linear low-density polyethylene(LLDPE)composite.Instead of crushing the straw and mixing it with plastic matrix,the new method mixes straw with plastic matrix in its original form.The intact long rice straws were parallelly spread on the LLDPE film and then rolled up together into a prefabricated roll.The rolls experienced three extrusion processes as follows:(1)twin-screw melting,cooling and crushing,single-screw extruding;(2)twin-screw melting and single-screw extruding;(3)directly single-screw extruding.The testing results showed that the straw/LLDPE composite(with a ratio of 6:4)prepared by Method(2)exhibited optimized properties.Characterization by scanning electron microscopy indicated that the damage to rice straw fibers was relatively minor,the orientation of long fibers was good,and the binding of fibers with the LLDPE matrix was excellent in this case.The results of dynamic mechanical testing(DMA),differential scanning calorimetry(DSC)and thermogravimetric(TG)analysis demonstrated that composites prepared by the new process exhibited significantly improved thermal stability and energy storage modulus,compared with those prepared by conventional processes(e.g.,extruded straw particles/LLDPE composite).The new proposed method yielded significantly enhanced mechanical properties while reducing dust pollution.展开更多
The open-cell structure foams of linear low-density polyethylene(LLDPE) and linear low-density polyethylene(LLDPE)/multi-wall carbon nanotubes(MWCNTs) composites are prepared by using supercritical carbon dioxid...The open-cell structure foams of linear low-density polyethylene(LLDPE) and linear low-density polyethylene(LLDPE)/multi-wall carbon nanotubes(MWCNTs) composites are prepared by using supercritical carbon dioxide(sc-CO2)as a foaming agent. The effects of processing parameters(foaming temperature, saturation pressure, and depressurization rate) and the addition of MWCNTs on the evolution of cell opening are studied systematically. For LLDPE foaming, the foaming temperature and saturation pressure are two key factors for preparing open-cell foams. An increase in temperature and pressure promotes both the cell wall thinning and cell rupture, because a high temperature results in a decrease in the viscosity of the polymer, and a high pressure leads to a larger amount of cell nucleation. Moreover, for the given temperature and pressure, the high pressurization rate results in a high pressure gradient, favoring cell rupture. For LLDPE/MWCNTs foaming, the addition of MWCNTs not only promotes the cell heterogeneous nucleation, but also prevents the cell collapse during cell opening, which is critical to achieve the open-cell structures with small cell size and high cell density.展开更多
In this study, effects of oscillatory shear with different frequencies (0-2.5 Hz) and amplitudes (0-20 mm) on the mechanical properties and crystalline morphology of linear low density polyethylene (LLDPE) were ...In this study, effects of oscillatory shear with different frequencies (0-2.5 Hz) and amplitudes (0-20 mm) on the mechanical properties and crystalline morphology of linear low density polyethylene (LLDPE) were investigated. It was found that the mechanical properties of LLDPE are improved because of the more perfect crystalline structure when LLDPE crystallizes under low-frequency and small-amplitude (0.2 Hz/4 mm) oscillatory shear. The mechanical properties can be further improved by increasing either the frequency or the amplitude of oscillatory shear. The Young's modulus and tensile strength of LLDPE are improved by 27% and 20%, respectively, when the frequency is increased to 2.5 Hz and the amplitude is maintained at 4 mm; while the Young's modulus and tensile strength are improved by 49% and 47%, respectively, when the amplitude is increased to 20 mm and the frequency is remained as 0.2 Hz. The crystallinity and microstructure of LLDPE under different oscillatory shear conditions were investigated by using differential scanning calorimetry, wide angle X-ray diffraction and scanning electron microscopy to shed light on the mechanism for the improvement of mechanical properties.展开更多
Based on successive multiple-step isothermal crystallization and self-nucleation annealing methods, a novel semi-quantitative method for the characterization of segment distribution in linear low density polyethylene ...Based on successive multiple-step isothermal crystallization and self-nucleation annealing methods, a novel semi-quantitative method for the characterization of segment distribution in linear low density polyethylene (LLDPE) was established by treating the thermal analysis data using the Gibbs-Thomson equation. The method was used to describe the segment distribution of Ziegler-Natta catalyzed LLDPE (Z-N LLDPE), metallocene catalyzed LLDPE (m-LLDPE) and two commercial LLDPEs with wide molecular weight distribution. The differences of the results obtained from the two thermally treated samples were compared. The results of segment distribution of the polymers were discussed according to their microstructure data and were compared with their characteristics. It can be deduced from the results that this characterization method is effective to characterize the sequence structure of the branched ethylene copolymers.展开更多
In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phe...In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phenyl substituents on para-Naryl structures.The activity of a-dimine nickl(Ⅱ)catalyst was 3.02x10^(6)g-mol_(ni)^(-1)·h^(-1) at 70℃,and resultant polyethylene possessed 135/1000C branches.The linear/branched block polyethylenes were synthesized from ethylene polymerization catalyzed by the a-dimine nicke(Ⅱ)complex/bis(phenoxy-imine)zirconium in the presence of diethyI zinc.With the addition of ZnEtz(from 0 to 400),the melting peak of resultant polyethylene changed from a single melting peak to bimodal melting peaks.The molecular weights of resultant polyethylene ranging from 26.8 kg/mol to 17.1 kg/mol and PDI values varying gradually from 24.4 to 15.2 were obtained vla adjusting ZnEt;equiv.and molar ratio of two catalysts.In addition,the branching degree of the polyethylene increased from 13/1000C to 56/1000 with the increase of the proportion of a dimine nickel(Ⅱ)catalyst.Using this binary catalyst system,the reaction temperature of chain shutting polymerization can be carried out at 70℃,which is more conducive to industrial application.展开更多
A case of household water tanks, 1000 L capacity, made of RCC, LLDPE and mild steel (stainless steel) was evaluated for life cycle analysis. The scope of the research comprised of the raw materials, energy inputs and ...A case of household water tanks, 1000 L capacity, made of RCC, LLDPE and mild steel (stainless steel) was evaluated for life cycle analysis. The scope of the research comprised of the raw materials, energy inputs and corresponding emissions during all phases of product making such as extraction of raw material, it’s processing, followed by manufacturing and transport, as well as use and reuse of the product. Simapro 8 (System for Integrated environMental Assessment of PROducts), a modelling software, from Dutch PRé Consultants was used to conduct the life cycle analysis. Simapro 8 enables systematic and transparent modelling and analysis of complex life cycles based on the recommendations of the ISO 14040 series of standards. In the present study the most common method which is acceptable worldwide “Recipe Endpoint method” (ReCiPe) was employed. ReCiPe computes the impact categories and classifies them into two classes based on relevant arrays of characterization factors. Simapro addresses impact categories viz. ozone depletion, human toxicity, ionizing radiation, photochemical oxidant formation, particulate matter formation, terrestrial acidification, climate change, terrestrial ecotoxicity, agricultural land occupation, urban land occupation, natural land transformation, marine ecotoxicity, marine eutrophication, fresh water eutrophication, fresh water ecotoxicity, fossil fuel depletion, minerals depletion, fresh water depletion at the midpoint level. While at the Endpoint level, the impact categories are multiplied by corresponding damage factors and integrated to be represented as three Endpoint level categories, viz. human health, ecosystems and resource depletion. The three endpoint categories are normalized, weighted, and aggregated into a single score. LCA studies indicate that household water tanks of LLDPE have least environmental implications considering impacts on human health, ecosystems and resource depletion as compared to its counterparts viz. Household water tanks made up of mild steel and RCC. The sequence of the material with decreasing impacts is concrete tanks > mild steel tank > LLDPE tanks. The overall assessment is centred on the elements such as material inputs, energy inputs and environmental emissions.展开更多
The N,N,N'-ferrous chloride complexes,[2-{CMeN(2,4-(CHPh)_(2)-6-FC_(6)H_(2))}-6-(CMeNAr)C_(5)H_(3)N]FeCl_(2)(Ar=2,6-Me_(2)C_(6)H_(3) Fe1,2,6-Et_(2)C_(6)H_(3)Fe2,2,6-^(i)Pr_(2)C_(6)H_(3) Fe3,2,4,6-Me_(3)C_(6)H_(2) ...The N,N,N'-ferrous chloride complexes,[2-{CMeN(2,4-(CHPh)_(2)-6-FC_(6)H_(2))}-6-(CMeNAr)C_(5)H_(3)N]FeCl_(2)(Ar=2,6-Me_(2)C_(6)H_(3) Fe1,2,6-Et_(2)C_(6)H_(3)Fe2,2,6-^(i)Pr_(2)C_(6)H_(3) Fe3,2,4,6-Me_(3)C_(6)H_(2) Fe4 and 2,6-Et_(2)-4-MeC_(6)H_(2) Fe5),each possessing one N-2,4-dibenzhydryl-6-fluorophenyl group,were readily synthesized from their respective unsymmetrical bis(imino)pyridines,L1-L5.Structural identification of Fe2 highlighted the variation in the steric properties provided by the dissimilar N-aryl groups.Following pre-treatment with either MAO or MMAO,complexes Fe1-Fe5 all displayed,at an operating temperature of 80℃,high activities for ethylene polymerization with levels falling in the order:Fe4> Fe1> Fe5> Fe2> Fe3.Notably,Fe4/MAO displayed the highest activity of 1.94×10^(7) g_(PE)·mol_(Fe)^(-1)·h^(-1) of the study with only a modest loss in performance at 90℃.Generally,the resulting polyethylenes were highly linear(T_(m) range:122-132℃),narrowly disperse and of low molecular weight(M_(w) range:6.73-46.04kg·mol^(-1)),with the most sterically hindered Fe3 forming the highest molecular weight polymer of the series.End-group analysis by ^(1)H-and ^(13)CNMR spectroscopy revealed saturated alkyl(n-propyl and i-propyl) and unsaturated vinyl chain ends indicative of the role of both β-H elimination and chain transfer to aluminum as termination pathways.By comparison with previou sly reported iron precatalysts with similar tridentate ligand skeletons,it is evident that the introduction of a large benzhydryl group in combination with a fluorine as the ortho-substituents of one N-aryl group has the effect of enhancing thermal stability of the iron polymerization catalyst whilst maintaining appreciable polymer molecular weight.展开更多
Herein, we demonstrate the synthesis of a well-defined diblock copolymer consisting of isotactic polystyrene (iPS) and linear polyethylene, isotactic polystyrene-block-polyethylene (iPS-b-PE), by the combination o...Herein, we demonstrate the synthesis of a well-defined diblock copolymer consisting of isotactic polystyrene (iPS) and linear polyethylene, isotactic polystyrene-block-polyethylene (iPS-b-PE), by the combination of sequential monomer addition and hydrogenation. Isospecific living polymerization of styrene and living trans-1,4-polymerization of 1,3-butadiene were catalyzed by 1,4-dithiabutandiyl-2,2'-bis(6-cumenyl-4-methylphenoxy) titanium dichloride (complex 1) activated by triisobutyl aluminum modified methylaluminoxane (MMAO) at room tempera^xre to provide highly isotactic polystyrene (iPS) and 1,4-trans-polybutadiene (1,4-trans-PBD) with narrow molecular weight distribution. Furthermore, the iPS-b-I,4- trans-PBD was synthesized via sequential monomer addition in the presence of complex 1 and MMAO. The hydrogenation of the 1,4-trans-PBD block was promoted by RuC12(PPh3)3 used as a catalyst to produce iPS-b-PE.展开更多
文摘In this work fibers derived from coffee</span><span style="font-family:Verdana;">,</span><span style="font-family:Verdana;"> hulls ha</span><span style="font-family:Verdana;">ve</span><span style="font-family:Verdana;"> been incorporated into Linear Low Density Polyethylene (LLDPE). The influence of the filler content on </span><span style="font-family:Verdana;">the </span><span style="font-family:Verdana;">thermal and physicomechanical properties of the composites obtained was assessed. The results showed that the incorporation of fibers was able to improve the thermostability of LLDPE/Coffee hulls fibers;comparing the treated fiber composite with untreated fiber composites, the chemical treatment reduces by 58.3% the water absorption, while increasing the elongation and tensile strength by about 48% and 17% respectively. Moreover, due to better interfacial interaction induced by MAPE, the corresponding composite exhibited better properties compared to the untreated fiber composite. Results are indicative of the fact that both mercerization and MAPE (coupling agent) have significant positive effects on the fib</span><span style="font-family:Verdana;">er</span><span style="font-family:Verdana;">-matrix interaction in terms of adhesion, wetting and dispersion, this treatment produced a better fiber distribution and consequently a more uniform composite morphology without voids and gaps between the fibers and the matrix, allowing the possibility to use higher fiber contents (up to 30% wt.) with acceptable mechanical properties.
文摘Background: Although abduction of the acetabular component is considered to predict factors for polyethylene wear attributable to osteolysis, other radiographic factors have yet to be elucidated. The purpose of the present study was to evaluate whether anteversion or change in implantation angle of the acetabular component influences polyethylene linear wear by using standing and supine radiographs of the hip joint. Methods: Standing and supine plain anteroposterior radiographs of 62 hip joints in which cementless total hip arthroplasty was performed were examined for polyethylene linear wear rate (mm/year), pelvic inclination, and radiological inclination and anatomic anteversion of the acetabular component. Results: All correlation coefficients of measurements of polyethylene linear wear, pelvic inclination angle, anatomical anteversion angle and radiological inclination angle were calculated highly. And by the three-dimensional numerical analysis, anatomic anteversion of the acetabular component had at least some effect on the degree of polyethylene wear. Conclusion: This study suggests that increased anteversion of the acetabular component reduces polyethylene linear wear in metal-on-polyethylene total hiparthroplasty.
基金supported by the Natural Science Foundation of China(No.32071704).
文摘Straw utilization is a key issue related to agricultural production and air pollution control.In this study,a novel extrusion process was proposed to improve the physical and mechanical properties of the straw-reinforced linear low-density polyethylene(LLDPE)composite.Instead of crushing the straw and mixing it with plastic matrix,the new method mixes straw with plastic matrix in its original form.The intact long rice straws were parallelly spread on the LLDPE film and then rolled up together into a prefabricated roll.The rolls experienced three extrusion processes as follows:(1)twin-screw melting,cooling and crushing,single-screw extruding;(2)twin-screw melting and single-screw extruding;(3)directly single-screw extruding.The testing results showed that the straw/LLDPE composite(with a ratio of 6:4)prepared by Method(2)exhibited optimized properties.Characterization by scanning electron microscopy indicated that the damage to rice straw fibers was relatively minor,the orientation of long fibers was good,and the binding of fibers with the LLDPE matrix was excellent in this case.The results of dynamic mechanical testing(DMA),differential scanning calorimetry(DSC)and thermogravimetric(TG)analysis demonstrated that composites prepared by the new process exhibited significantly improved thermal stability and energy storage modulus,compared with those prepared by conventional processes(e.g.,extruded straw particles/LLDPE composite).The new proposed method yielded significantly enhanced mechanical properties while reducing dust pollution.
基金financially supported by the National Natural Science Foundation of China(Nos.21306090 and 51403110)Scientific Research Fund of Zhejiang Provincial Education Department(Nos.Y201430774 and Y201327472)K.C.Wong Magna Fund in Ningbo University
文摘The open-cell structure foams of linear low-density polyethylene(LLDPE) and linear low-density polyethylene(LLDPE)/multi-wall carbon nanotubes(MWCNTs) composites are prepared by using supercritical carbon dioxide(sc-CO2)as a foaming agent. The effects of processing parameters(foaming temperature, saturation pressure, and depressurization rate) and the addition of MWCNTs on the evolution of cell opening are studied systematically. For LLDPE foaming, the foaming temperature and saturation pressure are two key factors for preparing open-cell foams. An increase in temperature and pressure promotes both the cell wall thinning and cell rupture, because a high temperature results in a decrease in the viscosity of the polymer, and a high pressure leads to a larger amount of cell nucleation. Moreover, for the given temperature and pressure, the high pressurization rate results in a high pressure gradient, favoring cell rupture. For LLDPE/MWCNTs foaming, the addition of MWCNTs not only promotes the cell heterogeneous nucleation, but also prevents the cell collapse during cell opening, which is critical to achieve the open-cell structures with small cell size and high cell density.
基金financially supported by the National Natural Science Foundation of China(Nos.51373153 and 51073139)the Zhejiang Provincial Natural Science Foundation of China(No.LY13E030002)the Zhejiang Leading Team of S&T Innovation(No.2011R50005)
文摘In this study, effects of oscillatory shear with different frequencies (0-2.5 Hz) and amplitudes (0-20 mm) on the mechanical properties and crystalline morphology of linear low density polyethylene (LLDPE) were investigated. It was found that the mechanical properties of LLDPE are improved because of the more perfect crystalline structure when LLDPE crystallizes under low-frequency and small-amplitude (0.2 Hz/4 mm) oscillatory shear. The mechanical properties can be further improved by increasing either the frequency or the amplitude of oscillatory shear. The Young's modulus and tensile strength of LLDPE are improved by 27% and 20%, respectively, when the frequency is increased to 2.5 Hz and the amplitude is maintained at 4 mm; while the Young's modulus and tensile strength are improved by 49% and 47%, respectively, when the amplitude is increased to 20 mm and the frequency is remained as 0.2 Hz. The crystallinity and microstructure of LLDPE under different oscillatory shear conditions were investigated by using differential scanning calorimetry, wide angle X-ray diffraction and scanning electron microscopy to shed light on the mechanism for the improvement of mechanical properties.
基金This work was supported by the Science Foundations of State Key Laboratory of Polymer Physics and Chemisny, Chinese Academy of Sciences (00-B-15) and National Natural Science Foundation of China (No. B040504).
文摘Based on successive multiple-step isothermal crystallization and self-nucleation annealing methods, a novel semi-quantitative method for the characterization of segment distribution in linear low density polyethylene (LLDPE) was established by treating the thermal analysis data using the Gibbs-Thomson equation. The method was used to describe the segment distribution of Ziegler-Natta catalyzed LLDPE (Z-N LLDPE), metallocene catalyzed LLDPE (m-LLDPE) and two commercial LLDPEs with wide molecular weight distribution. The differences of the results obtained from the two thermally treated samples were compared. The results of segment distribution of the polymers were discussed according to their microstructure data and were compared with their characteristics. It can be deduced from the results that this characterization method is effective to characterize the sequence structure of the branched ethylene copolymers.
基金by the National Natural Science Foundation of China(Nos.21004017 and 21004043)the Natural Science Foundation of Hebei Provinee(No.B2015202049).
文摘In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phenyl substituents on para-Naryl structures.The activity of a-dimine nickl(Ⅱ)catalyst was 3.02x10^(6)g-mol_(ni)^(-1)·h^(-1) at 70℃,and resultant polyethylene possessed 135/1000C branches.The linear/branched block polyethylenes were synthesized from ethylene polymerization catalyzed by the a-dimine nicke(Ⅱ)complex/bis(phenoxy-imine)zirconium in the presence of diethyI zinc.With the addition of ZnEtz(from 0 to 400),the melting peak of resultant polyethylene changed from a single melting peak to bimodal melting peaks.The molecular weights of resultant polyethylene ranging from 26.8 kg/mol to 17.1 kg/mol and PDI values varying gradually from 24.4 to 15.2 were obtained vla adjusting ZnEt;equiv.and molar ratio of two catalysts.In addition,the branching degree of the polyethylene increased from 13/1000C to 56/1000 with the increase of the proportion of a dimine nickel(Ⅱ)catalyst.Using this binary catalyst system,the reaction temperature of chain shutting polymerization can be carried out at 70℃,which is more conducive to industrial application.
文摘A case of household water tanks, 1000 L capacity, made of RCC, LLDPE and mild steel (stainless steel) was evaluated for life cycle analysis. The scope of the research comprised of the raw materials, energy inputs and corresponding emissions during all phases of product making such as extraction of raw material, it’s processing, followed by manufacturing and transport, as well as use and reuse of the product. Simapro 8 (System for Integrated environMental Assessment of PROducts), a modelling software, from Dutch PRé Consultants was used to conduct the life cycle analysis. Simapro 8 enables systematic and transparent modelling and analysis of complex life cycles based on the recommendations of the ISO 14040 series of standards. In the present study the most common method which is acceptable worldwide “Recipe Endpoint method” (ReCiPe) was employed. ReCiPe computes the impact categories and classifies them into two classes based on relevant arrays of characterization factors. Simapro addresses impact categories viz. ozone depletion, human toxicity, ionizing radiation, photochemical oxidant formation, particulate matter formation, terrestrial acidification, climate change, terrestrial ecotoxicity, agricultural land occupation, urban land occupation, natural land transformation, marine ecotoxicity, marine eutrophication, fresh water eutrophication, fresh water ecotoxicity, fossil fuel depletion, minerals depletion, fresh water depletion at the midpoint level. While at the Endpoint level, the impact categories are multiplied by corresponding damage factors and integrated to be represented as three Endpoint level categories, viz. human health, ecosystems and resource depletion. The three endpoint categories are normalized, weighted, and aggregated into a single score. LCA studies indicate that household water tanks of LLDPE have least environmental implications considering impacts on human health, ecosystems and resource depletion as compared to its counterparts viz. Household water tanks made up of mild steel and RCC. The sequence of the material with decreasing impacts is concrete tanks > mild steel tank > LLDPE tanks. The overall assessment is centred on the elements such as material inputs, energy inputs and environmental emissions.
基金Chinese Academy of Sciences for a President's International Fellowship for Visiting Scientists。
文摘The N,N,N'-ferrous chloride complexes,[2-{CMeN(2,4-(CHPh)_(2)-6-FC_(6)H_(2))}-6-(CMeNAr)C_(5)H_(3)N]FeCl_(2)(Ar=2,6-Me_(2)C_(6)H_(3) Fe1,2,6-Et_(2)C_(6)H_(3)Fe2,2,6-^(i)Pr_(2)C_(6)H_(3) Fe3,2,4,6-Me_(3)C_(6)H_(2) Fe4 and 2,6-Et_(2)-4-MeC_(6)H_(2) Fe5),each possessing one N-2,4-dibenzhydryl-6-fluorophenyl group,were readily synthesized from their respective unsymmetrical bis(imino)pyridines,L1-L5.Structural identification of Fe2 highlighted the variation in the steric properties provided by the dissimilar N-aryl groups.Following pre-treatment with either MAO or MMAO,complexes Fe1-Fe5 all displayed,at an operating temperature of 80℃,high activities for ethylene polymerization with levels falling in the order:Fe4> Fe1> Fe5> Fe2> Fe3.Notably,Fe4/MAO displayed the highest activity of 1.94×10^(7) g_(PE)·mol_(Fe)^(-1)·h^(-1) of the study with only a modest loss in performance at 90℃.Generally,the resulting polyethylenes were highly linear(T_(m) range:122-132℃),narrowly disperse and of low molecular weight(M_(w) range:6.73-46.04kg·mol^(-1)),with the most sterically hindered Fe3 forming the highest molecular weight polymer of the series.End-group analysis by ^(1)H-and ^(13)CNMR spectroscopy revealed saturated alkyl(n-propyl and i-propyl) and unsaturated vinyl chain ends indicative of the role of both β-H elimination and chain transfer to aluminum as termination pathways.By comparison with previou sly reported iron precatalysts with similar tridentate ligand skeletons,it is evident that the introduction of a large benzhydryl group in combination with a fluorine as the ortho-substituents of one N-aryl group has the effect of enhancing thermal stability of the iron polymerization catalyst whilst maintaining appreciable polymer molecular weight.
基金supported by the National Natural Science Foundation of China(Nos.21174167 and51573212)the Natural Science Foundation of Guangdong Province(Nos.S2013030013474 and 2014A030313178)
文摘Herein, we demonstrate the synthesis of a well-defined diblock copolymer consisting of isotactic polystyrene (iPS) and linear polyethylene, isotactic polystyrene-block-polyethylene (iPS-b-PE), by the combination of sequential monomer addition and hydrogenation. Isospecific living polymerization of styrene and living trans-1,4-polymerization of 1,3-butadiene were catalyzed by 1,4-dithiabutandiyl-2,2'-bis(6-cumenyl-4-methylphenoxy) titanium dichloride (complex 1) activated by triisobutyl aluminum modified methylaluminoxane (MMAO) at room tempera^xre to provide highly isotactic polystyrene (iPS) and 1,4-trans-polybutadiene (1,4-trans-PBD) with narrow molecular weight distribution. Furthermore, the iPS-b-I,4- trans-PBD was synthesized via sequential monomer addition in the presence of complex 1 and MMAO. The hydrogenation of the 1,4-trans-PBD block was promoted by RuC12(PPh3)3 used as a catalyst to produce iPS-b-PE.