In this study,a novel iron-based catalyst system,Fe(acac)3/(isocyanoimino)triptenylphosphorane(IITP)/AlR3,was employed for the synthesis of syndiotactic 1,2-polybutadiene in hexane.This catalyst system exhibits remark...In this study,a novel iron-based catalyst system,Fe(acac)3/(isocyanoimino)triptenylphosphorane(IITP)/AlR3,was employed for the synthesis of syndiotactic 1,2-polybutadiene in hexane.This catalyst system exhibits remarkably high catalytic activity,achieving a polymerization activity of 762 kgpolymer·molcatalyst^(-1)·h^(-1)at 50℃with a[BD]/[Fe]molar ratio of 20000.Furthermore,living polymerization characteristic were observed during the investigation of the polymerization kinetics of 1,3-butadiene polymerization.These characteristics were well demonstrated by a narrow molecular weight distribution(PDI≈2.0)of the resulting polybutadiene and a linear relationship between-ln(1-c)and polymerization time as well as number average molecular weight and polymer yield.The resultant polymer showed a 1,2-selectivity of approximately 76%and stereoregularity ranging from 62%to 73%(rrrr).Additionally,through kinetic studies on polymerization reaction,an apparent activation energy Ea value of this catalytic system was calculated to be 84.98 kJ·mol^(-1),which suggests that high polymerization temperature favors efficient polymerization.展开更多
Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl_3 followed by the addition of two equivalents of LiCH_2SiMe_3 afforded a series of constrained-geometry-configuration rare-ear...Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl_3 followed by the addition of two equivalents of LiCH_2SiMe_3 afforded a series of constrained-geometry-configuration rare-earth metal bis(alkyl) complexes(Cp′CH_2-Py)Ln(CH_2SiMe_3)_2(THF)_n(Py = C_5H_4N, Cp′ = C_5H_4(Cp), Ln = Sc, n = 0(1); Cp′ = C_9H_6(Ind), Ln = Sc, n = 0(2); Cp′ = 3-Me_3Si-C_9H_5(3-Me_3Si-Ind), Ln = Sc, n = 0(3a), Ln = Lu(3b), Y(3c), n = 1; Cp′ = 2,7-(~tBu)_2C_(13)H_8(2,7-(~tBu)_2-Flu), Ln = Sc(4 a), n = 0, Ln = Lu(4b),Y(4c), n = 1) in moderate to good yields, which were characterized by NMR spectroscopy and single-crystal X-ray diffraction(for complex 3a). In the presence of [Ph_3C][B(C_6F_5)_4] and Al^iBu_3, these complexes displayed different performances towards styrene polymerization. Rare-earth metal bis(alkyl) precursors bearing Cp, Ind, and 3-Me_3Si-Ind segments exhibited very low catalytic activity to afford syndiotactic polystyrene. All electron-donating t Bu substituted complexes 4 a, 4 b, and 4 c showed very high activity and perfect syndiotactivity(rrrr > 99%), producing high molecular weight polystyrene(up to 54.1 × 10~4) with relatively narrow molecular distribution(PDI = 1.28-2.49).展开更多
Sulfonated syndiotactic polystyrene ionomers (SsPS) with 1.8 mol% degree of sulfonation have been studied. WAXD shows that the crystallinity of SsPS ionomers was decreased with increasing diameter size of the counter ...Sulfonated syndiotactic polystyrene ionomers (SsPS) with 1.8 mol% degree of sulfonation have been studied. WAXD shows that the crystallinity of SsPS ionomers was decreased with increasing diameter size of the counter ions and sPS > SsPS-H > SsPS-K > SsPS-Zn. Moreover, SsPS ionomers only have alpha crystal form, while original sPS has two crystal forms: alpha and beta crystal form. TGA shows that the thermal stability of SsPS ionomers is higher than that of the original sPS and SsPS-Zn > SsPS-K > SsPS-H. DSC shows that all the glass transition temperatures (T-g) of SsPS ionomers are higher than that of the neat sPS and SsPS-Zn > SsPS-Na > SsPS-K > SsPS-H. However, the melting temperature (T-m) and crystallization peak temperature (T-p) of SsPS ionomers are lower and SsPS-H > SsPS-Zn > SsPS-K > SsPS-Na, while the crystallinity (X-c) of SsPS-Zn is the lowest. Nonisothermal crystallization kinetics shows that the Avrami index of sPS and SsPS-H are both about 4, suggesting the nucleation growth of SsPS-H with lower degree of sulfonation still keeps its three-dimension form. FTIR spectra of SsPS ionomers show a splitting absorption band for asymmetric stretching vibration of sulfonation group. The CH in-plane bending vibration of benzene ring shifted to higher wavenumber and the symmetric stretching vibration of sulfonation group changed slightly with different counter ion neutralized SsPS ionomers.展开更多
Phase transition from form Ⅰ to form Ⅲ in syndiotactic polypropylene crystallized at different conditions during tensile deformation at different temperatures was investigated by using in situ synchrotron wide angle...Phase transition from form Ⅰ to form Ⅲ in syndiotactic polypropylene crystallized at different conditions during tensile deformation at different temperatures was investigated by using in situ synchrotron wide angle X-ray diffraction technique. In all cases, the occurrence of this phase transition was observed. The onset strain of this transition was found to be crystalline thickness decided by crystallization temperature and drawing temperature dependent. The effect of drawing temperature on this phase transition is understood by the changes in mechanical properties with temperature. Moreover, crystalline thickness dependency of the phase transition reveals that this form Ⅰ to from Ⅲ phase transition occurs first in those lamellae with their normal along the stretching direction which have not experienced stress induced melting and recrystallization.展开更多
A series of syndiotactic polystyrene (SPS) samples in β crystalline form were prepared by cooling from the melt at various cooling rates. The effects of cooling rate from the melt, and DSC heating rate on the multipl...A series of syndiotactic polystyrene (SPS) samples in β crystalline form were prepared by cooling from the melt at various cooling rates. The effects of cooling rate from the melt, and DSC heating rate on the multiple melting behaviors of β crystals were investigated by differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC), from which the nature.of the multiple melting behavior was ascribed to the occurring of a recrystallization process.展开更多
Novel highly active eta(5)-pentamethylcyclopentadienyltribenzyloxy titanium catalyst activated by modified methylaluminoxane (m-MAO) was prepared for styrene syndiospecific polymerization. The influences of the conten...Novel highly active eta(5)-pentamethylcyclopentadienyltribenzyloxy titanium catalyst activated by modified methylaluminoxane (m-MAO) was prepared for styrene syndiospecific polymerization. The influences of the contents of trimethylaluminum (TMA) in m-MAO and external addition of tri-isobutylaluminum (TIBA) on the distribution of the oxidation states of titanium were investigated in detail. The Ti (III) is in favour of styrene syndiospecific polymerization in higher catalytic activity.展开更多
Two types of salicylaldiminato-based nickel complexes,mono-ligated Ni(II)complexes([O-C_(6)H_(4)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(5),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(6),[O-(3-t-Bu)C_(6)H_(3)-o-C(H)=N-A...Two types of salicylaldiminato-based nickel complexes,mono-ligated Ni(II)complexes([O-C_(6)H_(4)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(5),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(6),[O-(3-t-Bu)C_(6)H_(3)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(7))and bis-ligated Ni(II)complexes([O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]_(2)Ni(8),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-2-C_(6)H_(4)(PhO)]_(2)Ni(9),Ar=2,6-C_(6)H_(3)(i-Pr)_(2))were synthesized and characterized by Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance(NMR),mass spectrography(MS)and elemental analysis(EA).In the presence of methylaluminoxane(MAO)as cocatalyst,all the nickel complexes exhibited high activities for the polymerization of methyl methacrylate(MMA)and syndiotactic-rich poly(methyl methacrylate)(PMMA)was obtained.The complexes with less bulky substituents on salicylaldiminato framework possessed higher activities,while with the same salicylaldiminato,the mono-ligated nickel complexes showed higher catalytic activity than bis-ligated ones.展开更多
Solid phase transition of the a form crystals to the 3 form crystals in syndiotactic polystyrene (sPS) samples has occurred in supercritical CO2. This transformation is different from those detected under other condit...Solid phase transition of the a form crystals to the 3 form crystals in syndiotactic polystyrene (sPS) samples has occurred in supercritical CO2. This transformation is different from those detected under other conditions. The effects of some factors (e.g. time, temperature, and pressure) on the solid phase transformation of sPS in supercritical CO2 were analyzed in detail. Experimental results show that longer time, higher temperature or higher pressure favors the transformation of the a form crystals to the beta form crystals.展开更多
Syndiotactic polypropylene （sPP） as-spun fiber （sPP1） and drawn fiber （sPP2） were prepared by melt-spinning and melt-spinning/hot-drawing, respectively. The structure transition of the two fibers induced by anne...Syndiotactic polypropylene （sPP） as-spun fiber （sPP1） and drawn fiber （sPP2） were prepared by melt-spinning and melt-spinning/hot-drawing, respectively. The structure transition of the two fibers induced by annealing at different temperatures and the corresponding mechanical properties were subsequently investigated by the combination of Fourier transform infrared spectroscopy （FTIR）, wide-angle X-ray diffraction （WAXD） and tensile testing. The results indicate that the chain conformation and crystal forms of the two sPP fibers are not obviously changed at low annealing temperature （40℃）. With increasing the annealing temperature, the trans-planar conformation and mesophase in sPP1 and sPP2 fibers can be completely transformed to helical conformation and crystal form I under tension. Upon removing the tension, a small amount of mesophase and trans-planar conformation will be regained. The mechanical properties of the annealed fibers are manifestly dependent on their initial structure and the annealing temperature.展开更多
The crystallization of uniaxial hot drawn syndiotactic polystyrene/multi-walled carbon nanotube （sPS/MWCNT） nanocomposite films was studied by FTIR spectroscopy. The effects of MWCNT content, draw ratio and drawing ...The crystallization of uniaxial hot drawn syndiotactic polystyrene/multi-walled carbon nanotube （sPS/MWCNT） nanocomposite films was studied by FTIR spectroscopy. The effects of MWCNT content, draw ratio and drawing temperature on the sPS crystallinity were investigated. The sPS/MWCMT nanocomposite films show reduced crystallinities with the increase of MWCNT content. In addition, with the increase of draw ratio, both the pure sPS and the sPS/MWCNT nanocomposite drawn films exhibit increased crystallinity. The effect of drawing temperature on the sPS crystallization is complex. In a temperature range of 100―135 °C, the crystallinity decreases with drawing temperature, whereas it increases at 140 °C for both pure sPS and its nanocomposite films.展开更多
A series of titanium complexes Ar[O,E]Cp~*TiCl(Cp~*=C_5Me_5,Ar=1,2-phenylene,E=NH(1a);Ar=1,2- phenylene,E=O(1b);Ar=2.2'-diphenylene,E=O(1c);Ar=2,2'-dinaphthalene,E=O(1d)) has been prepared by the reaction of c...A series of titanium complexes Ar[O,E]Cp~*TiCl(Cp~*=C_5Me_5,Ar=1,2-phenylene,E=NH(1a);Ar=1,2- phenylene,E=O(1b);Ar=2.2'-diphenylene,E=O(1c);Ar=2,2'-dinaphthalene,E=O(1d)) has been prepared by the reaction of corresponding phenol derivatives with Cp~*TiCl_3 in the presence of excessive triethylamine.Under the conditions of low Al/Ti molar ratio(e.g.500) and high reaction temperatures(>70℃),all the titanium complexes display higher catalytic activities towards the syndiospecific polymerization of styrene,in t...展开更多
The morphology and structure of the syndiotactic polystyrene (sPS)/atactic polystyrene (aPS) blends with various compositions have been studied by means of DSC, optical microscopy, SAXS, and WAXD. The results show tha...The morphology and structure of the syndiotactic polystyrene (sPS)/atactic polystyrene (aPS) blends with various compositions have been studied by means of DSC, optical microscopy, SAXS, and WAXD. The results show that aPS is miscible with amorphous region of sPS. There is no macroscopic evidence that aPS forms separated domains in the blends. The decrease in crystallinity of sPS in the blends implies segregation of the aPS to the interfibrillar regions of the spherulites of sPS. The constancy of interlamellar distance and melting points indicates that the fibrillar structural units of sPS is unchanged on addition of aPS to sPS, and the unchanging parameters of the sPS unit cells mean that aPS does not enter the unit cells of sPS.展开更多
Some highly active η~5-pentamethylcyclopentadienyltribenzyloxy titanium complexes [Cp Ti(OBz)_3] activated by modified methylaluminoxane (mMAO) were prepared and used as the catalyst for styrene syndiospecific polyme...Some highly active η~5-pentamethylcyclopentadienyltribenzyloxy titanium complexes [Cp Ti(OBz)_3] activated by modified methylaluminoxane (mMAO) were prepared and used as the catalyst for styrene syndiospecific polymerization and propene atactic polymerization. Styrene could be copolymerized with propene when the propene was prepolymerized for a period, to which styrene and tri-isobutylaluminum (TIBA) were then added. The titled block copolymer together with the related homopolymers was obtained. The copolymerization porducts can be divided into the homopolymers and the copolymer by successive solvent extraction with boiling butanone, heptane and tetrahydrofuran (THF), and each fraction was characterized by ~13C NMR, DSC and WAXD. It was found that aPS and aPP were soluble in boiling butanone and heptane respectively. The block copolymer (sPS-b-aPP) composed of syndiottactic polystyrene segment was soluble in boiling THF and the residue was chiefly sPS.展开更多
The crystallization behavior of syndiotactic polystyrene（s PS） γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl＇s crystallization theory. O...The crystallization behavior of syndiotactic polystyrene（s PS） γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl＇s crystallization theory. On the basis of the differential scanning calorimetric results, it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness, which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization. Further temperature dependent small-angle X-ray scattering（SAXS） measurement revealed the evolution of the γ form lamellae upon heating until phase transition, involving three different regimes： lamellae stable region（25-90 °C）, melt-recrystallization region（90-185 °C） and pre-phase transition region（185-195 °C）. As a result, recrystallization line, equilibrium recrystallization line and melting line were developed for the s PS γ form crystallization process. Since the melt of γ form involved a γ-to-α/β form phase transition, the melting line was also denoted as the phase transition line in this special case. Therefore, the equilibrium crystallization temperature and melting（phase transition） temperatures were determined at around 390 and 220 °C on the basis of the thermodynamic phase diagram of the s PS γ form.展开更多
The polymorphic behavior of syndiotactic polypropylene (s-PP) crystallized from the melt under different conditions was investigated by means of WAXD and DSC. The isothermal melt crystallization of s-PP proceeded in f...The polymorphic behavior of syndiotactic polypropylene (s-PP) crystallized from the melt under different conditions was investigated by means of WAXD and DSC. The isothermal melt crystallization of s-PP proceeded in form I at tc≥ 110℃ and in form Ⅱ at tc≤110 ℃ s-PP crystallized nonisothermally from the melt was the mixture of forms and . With increasing the cooling rate (a), the content of form increased, and the content of form decreased. On heating, at 10 K/min, of quenched s-PP, it crystallized in form at t≤70 , continuing heating resulted in form form transition, which was an endothermal process.展开更多
The crystal structure and morphology of syndiotactic polystyrene (sPS) melt crystallized in various electrostatic fields have been investigated by using wide angle X ray diffraction (WAXD), differential scanning cal...The crystal structure and morphology of syndiotactic polystyrene (sPS) melt crystallized in various electrostatic fields have been investigated by using wide angle X ray diffraction (WAXD), differential scanning calorimeter (DSC) and scanning electron microscope (SEM). WAXD and DSC analyses show that sPS is gradually transformed from α phase to β phase with increase of electrostatic intensity. The SEM observations indicate that the morphology of sPS micro crystals is strongly dependent on electrostatic intensity applied to the sample during solidification. The variation of the micro crystals orientation from disordered lamellae to ordered lamellare have been observed with increase of electrostatic intensity.展开更多
Morphologies,crystallization behavior and mechanical properties of polypropylene（PP）/syndiotactic 1,2-polybutadiene（s-1,2 PB）blends were investigated.Morphology observation shows the well dispersed domains of s-1,...Morphologies,crystallization behavior and mechanical properties of polypropylene（PP）/syndiotactic 1,2-polybutadiene（s-1,2 PB）blends were investigated.Morphology observation shows the well dispersed domains of s-1,2 PB in PP matrix with the rather small domain sizes from 0.1 to 0.5μm when the s-1,2 PB content increases from 5%to 20%（mass fraction）in the blends,and the phase structure tends to become co-continuous as s-1,2 PB content further increases.Crystallization temperature（Tc）of PP component in the blends is fluctuated with the variation of s-1,2 PB content in the blends.Compatibilization,to some extent,between the two components is inferred from the examination of both morphology and crystallization behavior.Improvement of impact strength of PP toughened by s-1,2 PB becomes significant only in the case of s-1,2 PB content above 20%（mass fraction）.展开更多
基金This work was financially supported by the National Key R&D Program of China(No.2022YFB3704700).
文摘In this study,a novel iron-based catalyst system,Fe(acac)3/(isocyanoimino)triptenylphosphorane(IITP)/AlR3,was employed for the synthesis of syndiotactic 1,2-polybutadiene in hexane.This catalyst system exhibits remarkably high catalytic activity,achieving a polymerization activity of 762 kgpolymer·molcatalyst^(-1)·h^(-1)at 50℃with a[BD]/[Fe]molar ratio of 20000.Furthermore,living polymerization characteristic were observed during the investigation of the polymerization kinetics of 1,3-butadiene polymerization.These characteristics were well demonstrated by a narrow molecular weight distribution(PDI≈2.0)of the resulting polybutadiene and a linear relationship between-ln(1-c)and polymerization time as well as number average molecular weight and polymer yield.The resultant polymer showed a 1,2-selectivity of approximately 76%and stereoregularity ranging from 62%to 73%(rrrr).Additionally,through kinetic studies on polymerization reaction,an apparent activation energy Ea value of this catalytic system was calculated to be 84.98 kJ·mol^(-1),which suggests that high polymerization temperature favors efficient polymerization.
基金financially supported by the National Natural Science Foundation of China (Nos. 51773193 and 21634007)department of science and technology of Jilin province (No.20180101171JC)the "973" project (No. 2015CB654702)
文摘Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl_3 followed by the addition of two equivalents of LiCH_2SiMe_3 afforded a series of constrained-geometry-configuration rare-earth metal bis(alkyl) complexes(Cp′CH_2-Py)Ln(CH_2SiMe_3)_2(THF)_n(Py = C_5H_4N, Cp′ = C_5H_4(Cp), Ln = Sc, n = 0(1); Cp′ = C_9H_6(Ind), Ln = Sc, n = 0(2); Cp′ = 3-Me_3Si-C_9H_5(3-Me_3Si-Ind), Ln = Sc, n = 0(3a), Ln = Lu(3b), Y(3c), n = 1; Cp′ = 2,7-(~tBu)_2C_(13)H_8(2,7-(~tBu)_2-Flu), Ln = Sc(4 a), n = 0, Ln = Lu(4b),Y(4c), n = 1) in moderate to good yields, which were characterized by NMR spectroscopy and single-crystal X-ray diffraction(for complex 3a). In the presence of [Ph_3C][B(C_6F_5)_4] and Al^iBu_3, these complexes displayed different performances towards styrene polymerization. Rare-earth metal bis(alkyl) precursors bearing Cp, Ind, and 3-Me_3Si-Ind segments exhibited very low catalytic activity to afford syndiotactic polystyrene. All electron-donating t Bu substituted complexes 4 a, 4 b, and 4 c showed very high activity and perfect syndiotactivity(rrrr > 99%), producing high molecular weight polystyrene(up to 54.1 × 10~4) with relatively narrow molecular distribution(PDI = 1.28-2.49).
文摘Sulfonated syndiotactic polystyrene ionomers (SsPS) with 1.8 mol% degree of sulfonation have been studied. WAXD shows that the crystallinity of SsPS ionomers was decreased with increasing diameter size of the counter ions and sPS > SsPS-H > SsPS-K > SsPS-Zn. Moreover, SsPS ionomers only have alpha crystal form, while original sPS has two crystal forms: alpha and beta crystal form. TGA shows that the thermal stability of SsPS ionomers is higher than that of the original sPS and SsPS-Zn > SsPS-K > SsPS-H. DSC shows that all the glass transition temperatures (T-g) of SsPS ionomers are higher than that of the neat sPS and SsPS-Zn > SsPS-Na > SsPS-K > SsPS-H. However, the melting temperature (T-m) and crystallization peak temperature (T-p) of SsPS ionomers are lower and SsPS-H > SsPS-Zn > SsPS-K > SsPS-Na, while the crystallinity (X-c) of SsPS-Zn is the lowest. Nonisothermal crystallization kinetics shows that the Avrami index of sPS and SsPS-H are both about 4, suggesting the nucleation growth of SsPS-H with lower degree of sulfonation still keeps its three-dimension form. FTIR spectra of SsPS ionomers show a splitting absorption band for asymmetric stretching vibration of sulfonation group. The CH in-plane bending vibration of benzene ring shifted to higher wavenumber and the symmetric stretching vibration of sulfonation group changed slightly with different counter ion neutralized SsPS ionomers.
基金financially supported by the National Natural Science Foundation of China(No.21134006)
文摘Phase transition from form Ⅰ to form Ⅲ in syndiotactic polypropylene crystallized at different conditions during tensile deformation at different temperatures was investigated by using in situ synchrotron wide angle X-ray diffraction technique. In all cases, the occurrence of this phase transition was observed. The onset strain of this transition was found to be crystalline thickness decided by crystallization temperature and drawing temperature dependent. The effect of drawing temperature on this phase transition is understood by the changes in mechanical properties with temperature. Moreover, crystalline thickness dependency of the phase transition reveals that this form Ⅰ to from Ⅲ phase transition occurs first in those lamellae with their normal along the stretching direction which have not experienced stress induced melting and recrystallization.
文摘A series of syndiotactic polystyrene (SPS) samples in β crystalline form were prepared by cooling from the melt at various cooling rates. The effects of cooling rate from the melt, and DSC heating rate on the multiple melting behaviors of β crystals were investigated by differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC), from which the nature.of the multiple melting behavior was ascribed to the occurring of a recrystallization process.
文摘Novel highly active eta(5)-pentamethylcyclopentadienyltribenzyloxy titanium catalyst activated by modified methylaluminoxane (m-MAO) was prepared for styrene syndiospecific polymerization. The influences of the contents of trimethylaluminum (TMA) in m-MAO and external addition of tri-isobutylaluminum (TIBA) on the distribution of the oxidation states of titanium were investigated in detail. The Ti (III) is in favour of styrene syndiospecific polymerization in higher catalytic activity.
基金sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry of China,the Science and Technology Innovation Program of the China National Petroleum Corporation,and the Key Laboratory of Advanced Polymer Materials of Shanghai(Grant No.08DZ2230500)the Science and Technology Innovation Program of China National Petroleum Corporation.
文摘Two types of salicylaldiminato-based nickel complexes,mono-ligated Ni(II)complexes([O-C_(6)H_(4)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(5),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(6),[O-(3-t-Bu)C_(6)H_(3)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(7))and bis-ligated Ni(II)complexes([O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]_(2)Ni(8),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-2-C_(6)H_(4)(PhO)]_(2)Ni(9),Ar=2,6-C_(6)H_(3)(i-Pr)_(2))were synthesized and characterized by Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance(NMR),mass spectrography(MS)and elemental analysis(EA).In the presence of methylaluminoxane(MAO)as cocatalyst,all the nickel complexes exhibited high activities for the polymerization of methyl methacrylate(MMA)and syndiotactic-rich poly(methyl methacrylate)(PMMA)was obtained.The complexes with less bulky substituents on salicylaldiminato framework possessed higher activities,while with the same salicylaldiminato,the mono-ligated nickel complexes showed higher catalytic activity than bis-ligated ones.
文摘Solid phase transition of the a form crystals to the 3 form crystals in syndiotactic polystyrene (sPS) samples has occurred in supercritical CO2. This transformation is different from those detected under other conditions. The effects of some factors (e.g. time, temperature, and pressure) on the solid phase transformation of sPS in supercritical CO2 were analyzed in detail. Experimental results show that longer time, higher temperature or higher pressure favors the transformation of the a form crystals to the beta form crystals.
基金supported by the National Natural Science Foundation of China(No.50603029)the Innovation Foundation of Center for Molecular Science,Chinese Academy of Sciences(CMS-Y200724)
文摘Syndiotactic polypropylene （sPP） as-spun fiber （sPP1） and drawn fiber （sPP2） were prepared by melt-spinning and melt-spinning/hot-drawing, respectively. The structure transition of the two fibers induced by annealing at different temperatures and the corresponding mechanical properties were subsequently investigated by the combination of Fourier transform infrared spectroscopy （FTIR）, wide-angle X-ray diffraction （WAXD） and tensile testing. The results indicate that the chain conformation and crystal forms of the two sPP fibers are not obviously changed at low annealing temperature （40℃）. With increasing the annealing temperature, the trans-planar conformation and mesophase in sPP1 and sPP2 fibers can be completely transformed to helical conformation and crystal form I under tension. Upon removing the tension, a small amount of mesophase and trans-planar conformation will be regained. The mechanical properties of the annealed fibers are manifestly dependent on their initial structure and the annealing temperature.
基金Supported by the National Natural Science Foundation of China(No.50873103)the K. C. Wong Education Foundation of Hong Kong, China
文摘The crystallization of uniaxial hot drawn syndiotactic polystyrene/multi-walled carbon nanotube （sPS/MWCNT） nanocomposite films was studied by FTIR spectroscopy. The effects of MWCNT content, draw ratio and drawing temperature on the sPS crystallinity were investigated. The sPS/MWCMT nanocomposite films show reduced crystallinities with the increase of MWCNT content. In addition, with the increase of draw ratio, both the pure sPS and the sPS/MWCNT nanocomposite drawn films exhibit increased crystallinity. The effect of drawing temperature on the sPS crystallization is complex. In a temperature range of 100―135 °C, the crystallinity decreases with drawing temperature, whereas it increases at 140 °C for both pure sPS and its nanocomposite films.
文摘A series of titanium complexes Ar[O,E]Cp~*TiCl(Cp~*=C_5Me_5,Ar=1,2-phenylene,E=NH(1a);Ar=1,2- phenylene,E=O(1b);Ar=2.2'-diphenylene,E=O(1c);Ar=2,2'-dinaphthalene,E=O(1d)) has been prepared by the reaction of corresponding phenol derivatives with Cp~*TiCl_3 in the presence of excessive triethylamine.Under the conditions of low Al/Ti molar ratio(e.g.500) and high reaction temperatures(>70℃),all the titanium complexes display higher catalytic activities towards the syndiospecific polymerization of styrene,in t...
文摘The morphology and structure of the syndiotactic polystyrene (sPS)/atactic polystyrene (aPS) blends with various compositions have been studied by means of DSC, optical microscopy, SAXS, and WAXD. The results show that aPS is miscible with amorphous region of sPS. There is no macroscopic evidence that aPS forms separated domains in the blends. The decrease in crystallinity of sPS in the blends implies segregation of the aPS to the interfibrillar regions of the spherulites of sPS. The constancy of interlamellar distance and melting points indicates that the fibrillar structural units of sPS is unchanged on addition of aPS to sPS, and the unchanging parameters of the sPS unit cells mean that aPS does not enter the unit cells of sPS.
文摘Some highly active η~5-pentamethylcyclopentadienyltribenzyloxy titanium complexes [Cp Ti(OBz)_3] activated by modified methylaluminoxane (mMAO) were prepared and used as the catalyst for styrene syndiospecific polymerization and propene atactic polymerization. Styrene could be copolymerized with propene when the propene was prepolymerized for a period, to which styrene and tri-isobutylaluminum (TIBA) were then added. The titled block copolymer together with the related homopolymers was obtained. The copolymerization porducts can be divided into the homopolymers and the copolymer by successive solvent extraction with boiling butanone, heptane and tetrahydrofuran (THF), and each fraction was characterized by ~13C NMR, DSC and WAXD. It was found that aPS and aPP were soluble in boiling butanone and heptane respectively. The block copolymer (sPS-b-aPP) composed of syndiottactic polystyrene segment was soluble in boiling THF and the residue was chiefly sPS.
基金financially supported by the National Natural Science Foundation of China (Nos. 51525305, 21134006 and 21704101)
文摘The crystallization behavior of syndiotactic polystyrene（s PS） γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl＇s crystallization theory. On the basis of the differential scanning calorimetric results, it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness, which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization. Further temperature dependent small-angle X-ray scattering（SAXS） measurement revealed the evolution of the γ form lamellae upon heating until phase transition, involving three different regimes： lamellae stable region（25-90 °C）, melt-recrystallization region（90-185 °C） and pre-phase transition region（185-195 °C）. As a result, recrystallization line, equilibrium recrystallization line and melting line were developed for the s PS γ form crystallization process. Since the melt of γ form involved a γ-to-α/β form phase transition, the melting line was also denoted as the phase transition line in this special case. Therefore, the equilibrium crystallization temperature and melting（phase transition） temperatures were determined at around 390 and 220 °C on the basis of the thermodynamic phase diagram of the s PS γ form.
基金Talent Bringing New Ideas Science Foundation of Henan University and the Key Teacher SubsidyPlan of Chinese Universities.
文摘The polymorphic behavior of syndiotactic polypropylene (s-PP) crystallized from the melt under different conditions was investigated by means of WAXD and DSC. The isothermal melt crystallization of s-PP proceeded in form I at tc≥ 110℃ and in form Ⅱ at tc≤110 ℃ s-PP crystallized nonisothermally from the melt was the mixture of forms and . With increasing the cooling rate (a), the content of form increased, and the content of form decreased. On heating, at 10 K/min, of quenched s-PP, it crystallized in form at t≤70 , continuing heating resulted in form form transition, which was an endothermal process.
文摘The crystal structure and morphology of syndiotactic polystyrene (sPS) melt crystallized in various electrostatic fields have been investigated by using wide angle X ray diffraction (WAXD), differential scanning calorimeter (DSC) and scanning electron microscope (SEM). WAXD and DSC analyses show that sPS is gradually transformed from α phase to β phase with increase of electrostatic intensity. The SEM observations indicate that the morphology of sPS micro crystals is strongly dependent on electrostatic intensity applied to the sample during solidification. The variation of the micro crystals orientation from disordered lamellae to ordered lamellare have been observed with increase of electrostatic intensity.
基金the Natural Science Foundation of Heilongjiang Province,China(No.B2005-09).
文摘Morphologies,crystallization behavior and mechanical properties of polypropylene（PP）/syndiotactic 1,2-polybutadiene（s-1,2 PB）blends were investigated.Morphology observation shows the well dispersed domains of s-1,2 PB in PP matrix with the rather small domain sizes from 0.1 to 0.5μm when the s-1,2 PB content increases from 5%to 20%（mass fraction）in the blends,and the phase structure tends to become co-continuous as s-1,2 PB content further increases.Crystallization temperature（Tc）of PP component in the blends is fluctuated with the variation of s-1,2 PB content in the blends.Compatibilization,to some extent,between the two components is inferred from the examination of both morphology and crystallization behavior.Improvement of impact strength of PP toughened by s-1,2 PB becomes significant only in the case of s-1,2 PB content above 20%（mass fraction）.
