The melt memory effect is a widely observed phenomenon in semi-crystalline polymers. In practical applications, various additives are usually introduced into polymers, which may affect their melt memory behavior. In t...The melt memory effect is a widely observed phenomenon in semi-crystalline polymers. In practical applications, various additives are usually introduced into polymers, which may affect their melt memory behavior. In this work, the effect of talc on the melt memory effect of metallocene-made isotactic polypropylene(M-PP) was investigated in detail by using the differential scanning calorimetry. The results indicated that the introduction of talc significantly strengthened the melt memory effect of M-PP. Specifically, the upper limit temperature of Domain II increased from 161 ℃ to 174 ℃, resulting in a substantial widening of the temperature range of Domain IIa from 1 ℃ to 14 ℃. Analysis of the crystal orientation of the M-PP containing talc cooled from various Ts suggested that the remarkably enhanced melt memory effect could be ascribed to the stabilization of oriented nuclei facilitated by talc. This stabilizing effect was likely attributable to the prefreezing effect or the sorption interaction between talc and the M-PP chains.展开更多
The effects of weight-average molecular （Mw）, molecular weight distribution （MWD）, and isotacticity on the linear viscoelastic behavior of polybutene-1 melts are studied. It is observed that the linear viscoelasti...The effects of weight-average molecular （Mw）, molecular weight distribution （MWD）, and isotacticity on the linear viscoelastic behavior of polybutene-1 melts are studied. It is observed that the linear viscoelastic region becomes slightly narrower with increasing frequency. In frequency sweeps, the transition of the polymer melts flow from Newtonian flow to power-law flow can be observed. The melts with higher Mw and：or broader MWD, as well as higher isotacficity exhibit higher complex viscosity, zero shear viscosity, viscoelasticity moduli, relaxation modulus, broader transition zone, while lower critical shear rate, non-Newtonian index, and the frequency at which elasticity begins to play an important role. The relationship of zero shear viscosity on Mw has been established, which agrees with the classical power law. Furthermore, it is found that the cross-over frequency decreases with increasing Mw and the cross-over modulus increases with narrowing MWD.展开更多
For the solid-solid transformation from form Ⅱ to form Ⅰ of isotactic polybutene-1(iPB),the temperature dependence of form Ⅰ nucleation and growth was deemed to control the transformation process.However,the relati...For the solid-solid transformation from form Ⅱ to form Ⅰ of isotactic polybutene-1(iPB),the temperature dependence of form Ⅰ nucleation and growth was deemed to control the transformation process.However,the relationship between formⅠ formation and form Ⅱ disappearance in the transformation process is not clear.In this work,the spontaneous crystal transformation from form Ⅱ to Ⅰ of iPB with 81 mol%mmmm sequence concentration is studied firstly by tracking the two processes,the decay of form Ⅱ and the yielding of form Ⅰ in a wide range of temperature spanning from 0℃ to 50℃ and in a long transformation time ranging from 5 min to 65 days with in situ FTIR and WAXD.Unlike the literature reports,the decay rate of form Ⅱ is firstly found to be lower than the yielding rate of form Ⅰ at all studied temperatures,especially at low transition temperature.This is attributed to the amorphous chains which locate near crystal lamella participating into the nucleation of form Ⅱ.The regular chain folding and growth of i PB form Ⅰ from amorphous chains containing short isotactic sequences also lead to an increase in crystallinity of form Ⅰ compared with that of initial form Ⅱ crystallized at 60℃.An increase in the annealing temperature results in decrease in crystallinity and increase in lamellae thickness of i PB formⅠ.展开更多
A poly（ tert -butyl methacrylate）（PBMA） macromonomer was synthesized by anionic polymerization with bis（2,6-di- t -butyl phenoxy） methyl aluminum [MeAl（ODBP）2] as the initiator and trimethylsilylmethacrylate（...A poly（ tert -butyl methacrylate）（PBMA） macromonomer was synthesized by anionic polymerization with bis（2,6-di- t -butyl phenoxy） methyl aluminum [MeAl（ODBP）2] as the initiator and trimethylsilylmethacrylate（TMSMA） as the end capping agent in dry THF. Then, a poly（methacrylic acid）（PMAA） macromonomer was obtained by means of hydrolysis reaction from the PBMA macromonomer in the presence of hydrochloric acid. The structures of the PBMA macromonomer were characterized by using 1H NMR. It was found that the resulted PBMA macromonomer has highly isotactic properties and the PMAA macromonomer has an end vinyl group on per polymer chain. The monodisperse polymeric microspheres, which consisted of polystyrene cores and PMAA branches on their surfaces, were prepared by the dispersion copolymerization of styrene with the PMAA macromonomer in an ethanol/water mixed solvent. It was found that the concentration of the PMAA macromonomer would affect the microsphere formation, the morphology and its size in the copolymerization system.展开更多
Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent...Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent were used as diluents. The effect of α （DOP mass fraction in diluent） on the morphology and performance of the hollow fiber was investigated. With increasing α, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.展开更多
An aryl dicarboxylic acid amide compound TMB-5 is an efficient β-form nucleating agent for isotactic polypropylene （iPP）. Because of the solubility of TMB-5, superstructure and morphology of iPP crystals changed wi...An aryl dicarboxylic acid amide compound TMB-5 is an efficient β-form nucleating agent for isotactic polypropylene （iPP）. Because of the solubility of TMB-5, superstructure and morphology of iPP crystals changed with melting conditions. Effects of final heating temperature （Tf） on heterogeneous nucleation of iPP/TMB-5 were investigated. It was discovered that the crystallization temperature increased with decreasing Tf value. The optical microscopic images indicated that when TMB-5 partially dissolved in iPP melt, the remaining （non-dissolved） TMB-5 facilitated the recrystallization of dissolved nucleating agent from the melt, which promoted crystallization. Complete solubility of nucleating agent caused the decreasing efficiency. TMB-5 recrystallized in the form of tiny needles, whose aggregates induced dendritic iPP crystals.展开更多
Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic poly...Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.展开更多
In this study, recovery processes of isotactic polypropylene （iPP） melted spherulites at 135 ℃ after melting at higher temperatures （170 ℃-176 ℃） were investigated with polarized optical microscopy and Fourier ...In this study, recovery processes of isotactic polypropylene （iPP） melted spherulites at 135 ℃ after melting at higher temperatures （170 ℃-176 ℃） were investigated with polarized optical microscopy and Fourier transform infrared spectroscopy. The recovery temperature was fixed to exclude the interference from heterogeneous nuclei. After melting at temperatures between 170 ℃ and 174 ℃, the melted spherulite could recover back to the origin spberulite at low temperatures. Interestingly, a distinct infrared spectrum from iPP melt and crystal was observed in the early stage of recovery process after melting at low temperatures, where only IR bands resulting from short helices with 12 monomers or less can be seen, which indicates that the presence of crystal residues is not the necessary condition for the polymer memory effect. Avrami analysis further indicated that crystallization mainly took place in melted lamellae. After melting at higher temperatures, melted spherulite cannot recover. Based on above findings, it is proposed that the memory effect can be mainly ascribed to melted lamellae, during which crystalline order is lost but conformational order still exists. These conformational ordered segments formed aggregates, which can play as nucleation precursors at low temperatures.展开更多
One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of C...One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of CMRB were systematically investigated. Scanning electronic microscopy （SEM） observations showed blurry interface of compatibilized common blend （CCB）. The crystallization behavior of neat iPP, CCB, microfibrillar reinforced iPP/PET blend （MRB） and CMRB was investigated by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The increase of crystallization temperature and crystallization rate during nonisothermal crystallization process indicated both PET particles and mierofibrils could serve as nucleating agents and PET microfibrils exhibited higher heterogeneous nucleation ability, which were also vividly revealed by results of POM. Compared with MRB sample, CMRB sample has lower crystallization temperature due to existence of PET microfibrils with smaller aspect ratio and wider distribution. In addition, since in situ compatibilizer tends to stay in the interphase, it could also hinder the diffusion ofiPP molecules to the surface of PET phase, leading to decrease of crystallization rate. Two-dimensional wide-angle X-ray diffi：action （2D-WAXD） was preformed to characterize the crystalline structure of the samples by injection molding, and it was found that well-developed PET microfibrils contained in MRB sample promoted formation of t-phase of/PP.展开更多
A relatively high predetermined crystallization temperature （135℃） was chosen to grow well developed iPP spherulites, then the partial melting was carried out at a temperature of 165℃, where the preformed spheruli...A relatively high predetermined crystallization temperature （135℃） was chosen to grow well developed iPP spherulites, then the partial melting was carried out at a temperature of 165℃, where the preformed spherulites were seen to only decrease their size but not completely melted. The crystallization behavior of partially melted isotactic polypropylene （iPP） has been carefully examined by different scanning calorimetry （DSC） and polarized light microscopy （PLM）. The experimental results show that at a special annealing temperature （165℃） the melting behavior of iPP includes two parts with different mechanism, one part is the melting of iPP spherulite outside, another is the partial lamellae perfection during longer annealing time in the unmelted spherulite. The conformational orders of the iPP melt decrease with the increase of the annealing temperature.展开更多
The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5 （iPP/TMB-5） were investigated by synchrotron radiation wide angel X-ray diffraction （SR-WAXD）, differential scan...The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5 （iPP/TMB-5） were investigated by synchrotron radiation wide angel X-ray diffraction （SR-WAXD）, differential scanning calorimeter （DSC） and polarized light microscope （PLM）. It was found that α-crystallization lagged behind β-crystallization at normal temperatures, but the discrepancy reduced with increasing temperature. TMB-5 could not induce β-iPP when the nucleation agent is wrapped up with α-crystal that crystallized at high temperatures. The polymorphic composition of iPP/TMB-5 was susceptible to the introductory moment of shear. New crystallization process of β-nucleated iPP was proposed to understand the experimental phenomena which could not be explained by those reported in the literature. It was supposed that polymer crystallization initiated from mesophase, and the formations of iPP crystals involved the organization of helical conformation ordering within rnesophase. It was proposed that the iPP melt contained mesophases with stereocomplex-type ordering of right-handed and left-handed helical chains which could be disturbed by shear or TMB-5, leading to different polymorphic structures.展开更多
The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isota...The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isotactic polypropylene sheets were also measured in this work. The texture component method was used to analyze the rolling texture. The rolling texture consists mainly of （010）[001], （130）[001] and [001]//RD fiber components in the sample with a rolling true strain of 1.5. The results reveal that crystallinity drastically decreases during rolling. It is suggested that amorphization is a deformation mechanism which takes place as an alternative to crystallographic intralamellar slip depending on the orientation of the lamellae. Both the orientation and crystallinity affect the tensile mechanical properties of rolled polypropylene. Crystallinity influences the elastic modulus on both directions and yield strength on transverse direction at the first stage of deformation. Orientation is the main reason for the changes of mechanical properties, especially at the latter part of deformation. The changes of both tensile strength and elongation percentage on rolling direction are larger than those on transverse direction, which results from the orientation. At last, the anisotropic mechanical properties occur on the rolling and transverse direction： high tensile strength with low elongation percentage on rolling direction and low tensile strength with high elongation percentage on transverse direction.展开更多
Herein,isotactic polypropylene films with smallβ-nucleating agent content were fabricated via a melt-extrusion-stretched technology with intended"shear-free"in barrel and die.Compared with neat films,the te...Herein,isotactic polypropylene films with smallβ-nucleating agent content were fabricated via a melt-extrusion-stretched technology with intended"shear-free"in barrel and die.Compared with neat films,the tensile strength,elongation at break and strain energy density at break of i PP film with 0.05 wt%β-nucleating agent are significantly improved by 13.8%,39.6%and 90.6%,respectively,indicating the simultaneously enhanced toughness and strength.Additionally,theβ-crystal content gradually increases with increasingβ-NA content,while the relative total daughter content ofα-andβ-crystal exhibits opposite tendency.Moreover,nucleation and crystal growth induced by variousβ-NA contents are different.This work proves an efficient strategy to enhance mechanical properties of isotactic polypropylene film via controlling elongation flow and addition of appropriateβ-NA content.展开更多
Aggregation process of isotactic poly（methyl methacrylate） （i-PMMA） has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, howe...Aggregation process of isotactic poly（methyl methacrylate） （i-PMMA） has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95 ± 0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements.展开更多
A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibr...A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibration treatment were investigated by means of differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The results reveal that the crystallinity of the vibrated samples decreases at a high cooling rate, but it remains constant at a low cooling rate because of the chain relaxation of iPP. It has been found that vibration obviously increases the content of β-form of crystal phase and the amount of β-crystal mainly depends on the vibration amplitude.展开更多
In the present work, the TIPS behavior of isotactic polypropylene(iP P)/di-n-butyl phthalate(DBP)/dioctyl phthalate(DOP)/nano-SiO_2 system and the competition relation between liquid–liquid phase separation and polym...In the present work, the TIPS behavior of isotactic polypropylene(iP P)/di-n-butyl phthalate(DBP)/dioctyl phthalate(DOP)/nano-SiO_2 system and the competition relation between liquid–liquid phase separation and polymer crystallization are successfully adjusted by adding nano-SiO_2. The liquid–liquid phase separation temperature of the system increases with increasing nano-SiO_2 content. Besides, iP P crystallization temperature is also changed after adding nano-SiO_2. IPP/nano-SiO_2 blend hollow fiber microporous membrane is prepared via TIPS method. SEM photos show that the membrane exhibits mixed morphology combining cellular structure relating to liquid–liquid phase separation and branch structure originating from polymer crystallization. The relative weight of cellular structure first decreases and then increases with the increase of nano-SiO_2 content. Furthermore, porosity, connectivity among pores and pure water flux of the membrane first increase and then decrease with increasing nano-SiO_2 content. However, mechanical performance of the membrane is improved at all times with increasing nano-SiO_2 content.展开更多
In our current work, the effect of the shear temperature on the growth of β-crystal in isotactic polypropylene（iPP） with β-nucleating agent is investigated by means of in situ two-dimensional wide-angle X-ray diff...In our current work, the effect of the shear temperature on the growth of β-crystal in isotactic polypropylene（iPP） with β-nucleating agent is investigated by means of in situ two-dimensional wide-angle X-ray diffraction（2 D-WAXD）. At low shear temperatures, the formed shear-induced oriented precursors are hard to relax back to random coiled state due to the weak mobility of molecular chains. Therefore, plenty of oriented α-crystals are induced by shear-induced oriented precursors, while β-crystal is greatly depressed. As the shear temperature increases, oriented β-crystal gradually increases along with the decrease of α-crystal. It is deduced that the shear temperature at which the content of β-crystal increases to the（maximum） value found in quiescent crystallization is almost the same as that at which the accelerating effect of flow on crystallization kinetics is completely erased. Our work manifests its significance in regulating β-crystal and thus in the structure and property manipulation of i PP.展开更多
Microcellular injection molding of neat isotactic polypropylene(iPP) and isotactic polypropylene/nano-calcium carbonate composites(i PP/nano-CaCO_3) was performed using supercritical carbon dioxide as the physical blo...Microcellular injection molding of neat isotactic polypropylene(iPP) and isotactic polypropylene/nano-calcium carbonate composites(i PP/nano-CaCO_3) was performed using supercritical carbon dioxide as the physical blowing agent. The influences of filler content and operating conditions on microstructure morphology of i PP and i PP/nano-CaCO_3 microcellular samples were studied systematically. The results showed the bubble size of the microcellular samples could be effectively decreased while the cell density increased for i PP/nano-CaCO_3 composites, especially at high CO_2 concentration and back pressure, low mold temperature and injection speed, and high filler content. Then Moldex 3D was applied to simulate the microcellular injection molding process, with the application of the measured ScCO_2 solubility and diffusion data for i PP and i PP/nano-Ca CO_3 composites respectively. For neat i PP, the simulated bubble size and density distribution in the center section of tensile bars showed a good agreement with the experimental values. However, for i PP/nano-CaCO_3 composites, the correction factor for nucleation activation energy F and the pre-exponential factor of nucleation rate f_0 were obtained by nonlinear regression on the experimental bubble size and density distribution. The parameters F and f_0 can be used to predict the microcellular injection molding process for i PP/nano-CaCO_3 composites by Moldex 3D.展开更多
The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means ...The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G″) plots at 180 and 200 ℃ versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0.01-100 rad/s for Ziegler-Natta catalyzing ethylene-propylene random copolymerization(PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G″(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus(G 0_N) of UHPPH from a certain experimental temperature G″(ω) curve directly. For UHPPH, the G 0_N determined to be 4.28×10 5 and 3.62×10 5 Pa at 180 and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G 0_N has no relation to the molecular weight.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 51973037 and 52173056)PetroChina Company Limited,China。
文摘The melt memory effect is a widely observed phenomenon in semi-crystalline polymers. In practical applications, various additives are usually introduced into polymers, which may affect their melt memory behavior. In this work, the effect of talc on the melt memory effect of metallocene-made isotactic polypropylene(M-PP) was investigated in detail by using the differential scanning calorimetry. The results indicated that the introduction of talc significantly strengthened the melt memory effect of M-PP. Specifically, the upper limit temperature of Domain II increased from 161 ℃ to 174 ℃, resulting in a substantial widening of the temperature range of Domain IIa from 1 ℃ to 14 ℃. Analysis of the crystal orientation of the M-PP containing talc cooled from various Ts suggested that the remarkably enhanced melt memory effect could be ascribed to the stabilization of oriented nuclei facilitated by talc. This stabilizing effect was likely attributable to the prefreezing effect or the sorption interaction between talc and the M-PP chains.
基金financially supported by the National Basic Research Program of China(No.2015CB654700(2015CB654706))Special Foundation of Taishan Mountain Scholar Constructive Program+5 种基金National Key Technology R&D Program of China(No.2011BAE26B05)Shandong Provincial Natural Science Fund for Distinguished Young Scholars(No.JQ201213)the National Natural Science Foundation of China(No.21174074)the Nature Science Foundation of Shandong Province(No.ZR2013BM004)Shandong province science and technology development plan(2012GGA05042)support from the Yellow River Delta Scholar program(Office of National University Science&Technology Park Administrative Committee(China University of Petroleum)
文摘The effects of weight-average molecular （Mw）, molecular weight distribution （MWD）, and isotacticity on the linear viscoelastic behavior of polybutene-1 melts are studied. It is observed that the linear viscoelastic region becomes slightly narrower with increasing frequency. In frequency sweeps, the transition of the polymer melts flow from Newtonian flow to power-law flow can be observed. The melts with higher Mw and：or broader MWD, as well as higher isotacficity exhibit higher complex viscosity, zero shear viscosity, viscoelasticity moduli, relaxation modulus, broader transition zone, while lower critical shear rate, non-Newtonian index, and the frequency at which elasticity begins to play an important role. The relationship of zero shear viscosity on Mw has been established, which agrees with the classical power law. Furthermore, it is found that the cross-over frequency decreases with increasing Mw and the cross-over modulus increases with narrowing MWD.
基金financially supported by the Major Science and Technology Innovation Project of Shandong Province (No. 2019JZZY010352)Natural Science Foundation of Shandong Province (ZR2019MB072)Taishan Scholar Program
文摘For the solid-solid transformation from form Ⅱ to form Ⅰ of isotactic polybutene-1(iPB),the temperature dependence of form Ⅰ nucleation and growth was deemed to control the transformation process.However,the relationship between formⅠ formation and form Ⅱ disappearance in the transformation process is not clear.In this work,the spontaneous crystal transformation from form Ⅱ to Ⅰ of iPB with 81 mol%mmmm sequence concentration is studied firstly by tracking the two processes,the decay of form Ⅱ and the yielding of form Ⅰ in a wide range of temperature spanning from 0℃ to 50℃ and in a long transformation time ranging from 5 min to 65 days with in situ FTIR and WAXD.Unlike the literature reports,the decay rate of form Ⅱ is firstly found to be lower than the yielding rate of form Ⅰ at all studied temperatures,especially at low transition temperature.This is attributed to the amorphous chains which locate near crystal lamella participating into the nucleation of form Ⅱ.The regular chain folding and growth of i PB form Ⅰ from amorphous chains containing short isotactic sequences also lead to an increase in crystallinity of form Ⅰ compared with that of initial form Ⅱ crystallized at 60℃.An increase in the annealing temperature results in decrease in crystallinity and increase in lamellae thickness of i PB formⅠ.
基金Supported by the Foundation for U niversity Key Teacher by The Ministry of Education,P. R. China and was supported in part by the Grant- in- Aid for Scientific Research on Priority Areas,"New Polym ers and Their Nano- Organized System s"(No.2 77/ 10 5
文摘A poly（ tert -butyl methacrylate）（PBMA） macromonomer was synthesized by anionic polymerization with bis（2,6-di- t -butyl phenoxy） methyl aluminum [MeAl（ODBP）2] as the initiator and trimethylsilylmethacrylate（TMSMA） as the end capping agent in dry THF. Then, a poly（methacrylic acid）（PMAA） macromonomer was obtained by means of hydrolysis reaction from the PBMA macromonomer in the presence of hydrochloric acid. The structures of the PBMA macromonomer were characterized by using 1H NMR. It was found that the resulted PBMA macromonomer has highly isotactic properties and the PMAA macromonomer has an end vinyl group on per polymer chain. The monodisperse polymeric microspheres, which consisted of polystyrene cores and PMAA branches on their surfaces, were prepared by the dispersion copolymerization of styrene with the PMAA macromonomer in an ethanol/water mixed solvent. It was found that the concentration of the PMAA macromonomer would affect the microsphere formation, the morphology and its size in the copolymerization system.
基金Supported by the National Natural Science Foundation of China （No.20236030）.
文摘Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent were used as diluents. The effect of α （DOP mass fraction in diluent） on the morphology and performance of the hollow fiber was investigated. With increasing α, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.
文摘An aryl dicarboxylic acid amide compound TMB-5 is an efficient β-form nucleating agent for isotactic polypropylene （iPP）. Because of the solubility of TMB-5, superstructure and morphology of iPP crystals changed with melting conditions. Effects of final heating temperature （Tf） on heterogeneous nucleation of iPP/TMB-5 were investigated. It was discovered that the crystallization temperature increased with decreasing Tf value. The optical microscopic images indicated that when TMB-5 partially dissolved in iPP melt, the remaining （non-dissolved） TMB-5 facilitated the recrystallization of dissolved nucleating agent from the melt, which promoted crystallization. Complete solubility of nucleating agent caused the decreasing efficiency. TMB-5 recrystallized in the form of tiny needles, whose aggregates induced dendritic iPP crystals.
基金the National Natural Science Foundation of China(20374043)SINOPEC(X501025)
文摘Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.
基金financially supported by the China Postdoctoral Science Foundation(No.2012M521233)the Fundamental Research Funds for the Central Universities(WK2310000031)+3 种基金the National Natural Science Foundation of China(Nos.51033004,51227801,51303166)National Natural Science Funds for Distinguished Young Scholars(No.51325301)the 973 program of MOST(2010CB934504)supported by the Opening Project of Soochow University Biomedical Polymers Laboratory and the Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application(Soochow University)
文摘In this study, recovery processes of isotactic polypropylene （iPP） melted spherulites at 135 ℃ after melting at higher temperatures （170 ℃-176 ℃） were investigated with polarized optical microscopy and Fourier transform infrared spectroscopy. The recovery temperature was fixed to exclude the interference from heterogeneous nuclei. After melting at temperatures between 170 ℃ and 174 ℃, the melted spherulite could recover back to the origin spberulite at low temperatures. Interestingly, a distinct infrared spectrum from iPP melt and crystal was observed in the early stage of recovery process after melting at low temperatures, where only IR bands resulting from short helices with 12 monomers or less can be seen, which indicates that the presence of crystal residues is not the necessary condition for the polymer memory effect. Avrami analysis further indicated that crystallization mainly took place in melted lamellae. After melting at higher temperatures, melted spherulite cannot recover. Based on above findings, it is proposed that the memory effect can be mainly ascribed to melted lamellae, during which crystalline order is lost but conformational order still exists. These conformational ordered segments formed aggregates, which can play as nucleation precursors at low temperatures.
基金financially supported by National Natural Science Foundation of China(No.20776087)National Programs for High Technology Research and Development of China(No.2008AA03Z510)
文摘One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of CMRB were systematically investigated. Scanning electronic microscopy （SEM） observations showed blurry interface of compatibilized common blend （CCB）. The crystallization behavior of neat iPP, CCB, microfibrillar reinforced iPP/PET blend （MRB） and CMRB was investigated by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The increase of crystallization temperature and crystallization rate during nonisothermal crystallization process indicated both PET particles and mierofibrils could serve as nucleating agents and PET microfibrils exhibited higher heterogeneous nucleation ability, which were also vividly revealed by results of POM. Compared with MRB sample, CMRB sample has lower crystallization temperature due to existence of PET microfibrils with smaller aspect ratio and wider distribution. In addition, since in situ compatibilizer tends to stay in the interphase, it could also hinder the diffusion ofiPP molecules to the surface of PET phase, leading to decrease of crystallization rate. Two-dimensional wide-angle X-ray diffi：action （2D-WAXD） was preformed to characterize the crystalline structure of the samples by injection molding, and it was found that well-developed PET microfibrils contained in MRB sample promoted formation of t-phase of/PP.
基金supported by the National Natural Science Foundation of China(Nos.50533050 and 20634050)
文摘A relatively high predetermined crystallization temperature （135℃） was chosen to grow well developed iPP spherulites, then the partial melting was carried out at a temperature of 165℃, where the preformed spherulites were seen to only decrease their size but not completely melted. The crystallization behavior of partially melted isotactic polypropylene （iPP） has been carefully examined by different scanning calorimetry （DSC） and polarized light microscopy （PLM）. The experimental results show that at a special annealing temperature （165℃） the melting behavior of iPP includes two parts with different mechanism, one part is the melting of iPP spherulite outside, another is the partial lamellae perfection during longer annealing time in the unmelted spherulite. The conformational orders of the iPP melt decrease with the increase of the annealing temperature.
基金supported by the National Natural Science Foundation of China(Nos.51573131,51173130,21274149 and 21374077)
文摘The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5 （iPP/TMB-5） were investigated by synchrotron radiation wide angel X-ray diffraction （SR-WAXD）, differential scanning calorimeter （DSC） and polarized light microscope （PLM）. It was found that α-crystallization lagged behind β-crystallization at normal temperatures, but the discrepancy reduced with increasing temperature. TMB-5 could not induce β-iPP when the nucleation agent is wrapped up with α-crystal that crystallized at high temperatures. The polymorphic composition of iPP/TMB-5 was susceptible to the introductory moment of shear. New crystallization process of β-nucleated iPP was proposed to understand the experimental phenomena which could not be explained by those reported in the literature. It was supposed that polymer crystallization initiated from mesophase, and the formations of iPP crystals involved the organization of helical conformation ordering within rnesophase. It was proposed that the iPP melt contained mesophases with stereocomplex-type ordering of right-handed and left-handed helical chains which could be disturbed by shear or TMB-5, leading to different polymorphic structures.
文摘The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isotactic polypropylene sheets were also measured in this work. The texture component method was used to analyze the rolling texture. The rolling texture consists mainly of （010）[001], （130）[001] and [001]//RD fiber components in the sample with a rolling true strain of 1.5. The results reveal that crystallinity drastically decreases during rolling. It is suggested that amorphization is a deformation mechanism which takes place as an alternative to crystallographic intralamellar slip depending on the orientation of the lamellae. Both the orientation and crystallinity affect the tensile mechanical properties of rolled polypropylene. Crystallinity influences the elastic modulus on both directions and yield strength on transverse direction at the first stage of deformation. Orientation is the main reason for the changes of mechanical properties, especially at the latter part of deformation. The changes of both tensile strength and elongation percentage on rolling direction are larger than those on transverse direction, which results from the orientation. At last, the anisotropic mechanical properties occur on the rolling and transverse direction： high tensile strength with low elongation percentage on rolling direction and low tensile strength with high elongation percentage on transverse direction.
基金financially supported by the National Natural Science Foundation of China(Nos.11432003 and 11572290)Young Teacher Project of Zhongyuan University of Technology(No.2019XQG05)。
文摘Herein,isotactic polypropylene films with smallβ-nucleating agent content were fabricated via a melt-extrusion-stretched technology with intended"shear-free"in barrel and die.Compared with neat films,the tensile strength,elongation at break and strain energy density at break of i PP film with 0.05 wt%β-nucleating agent are significantly improved by 13.8%,39.6%and 90.6%,respectively,indicating the simultaneously enhanced toughness and strength.Additionally,theβ-crystal content gradually increases with increasingβ-NA content,while the relative total daughter content ofα-andβ-crystal exhibits opposite tendency.Moreover,nucleation and crystal growth induced by variousβ-NA contents are different.This work proves an efficient strategy to enhance mechanical properties of isotactic polypropylene film via controlling elongation flow and addition of appropriateβ-NA content.
基金This work was supported by the National Natural Science Foundations of China.
文摘Aggregation process of isotactic poly（methyl methacrylate） （i-PMMA） has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95 ± 0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements.
基金Supported by the National Science Funds for Distinguished Young Scholars(No.5 0 12 5 312 ) Special Funds for MajorState Basic Research Project of China(No.G19990 6 4 80 0 ) and Key Program of the National Natural Science Foundation ofChina(No.5 0 1
文摘A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibration treatment were investigated by means of differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The results reveal that the crystallinity of the vibrated samples decreases at a high cooling rate, but it remains constant at a low cooling rate because of the chain relaxation of iPP. It has been found that vibration obviously increases the content of β-form of crystal phase and the amount of β-crystal mainly depends on the vibration amplitude.
基金Supported by the Key Project of Scientific and Technological Research of Hebei Provincial University(ZD2015107)
文摘In the present work, the TIPS behavior of isotactic polypropylene(iP P)/di-n-butyl phthalate(DBP)/dioctyl phthalate(DOP)/nano-SiO_2 system and the competition relation between liquid–liquid phase separation and polymer crystallization are successfully adjusted by adding nano-SiO_2. The liquid–liquid phase separation temperature of the system increases with increasing nano-SiO_2 content. Besides, iP P crystallization temperature is also changed after adding nano-SiO_2. IPP/nano-SiO_2 blend hollow fiber microporous membrane is prepared via TIPS method. SEM photos show that the membrane exhibits mixed morphology combining cellular structure relating to liquid–liquid phase separation and branch structure originating from polymer crystallization. The relative weight of cellular structure first decreases and then increases with the increase of nano-SiO_2 content. Furthermore, porosity, connectivity among pores and pure water flux of the membrane first increase and then decrease with increasing nano-SiO_2 content. However, mechanical performance of the membrane is improved at all times with increasing nano-SiO_2 content.
基金financially supported by the National Natural Science Foundation of China(Nos.51473135,51503170 and 21676217)the Opening State Key Laboratory of Polymer Materials Engineering(Sichuan University)(No.sklpme 2015-4-22)the Fundamental Research Funds for the Central Universities(No.3102016BJY01)
文摘In our current work, the effect of the shear temperature on the growth of β-crystal in isotactic polypropylene（iPP） with β-nucleating agent is investigated by means of in situ two-dimensional wide-angle X-ray diffraction（2 D-WAXD）. At low shear temperatures, the formed shear-induced oriented precursors are hard to relax back to random coiled state due to the weak mobility of molecular chains. Therefore, plenty of oriented α-crystals are induced by shear-induced oriented precursors, while β-crystal is greatly depressed. As the shear temperature increases, oriented β-crystal gradually increases along with the decrease of α-crystal. It is deduced that the shear temperature at which the content of β-crystal increases to the（maximum） value found in quiescent crystallization is almost the same as that at which the accelerating effect of flow on crystallization kinetics is completely erased. Our work manifests its significance in regulating β-crystal and thus in the structure and property manipulation of i PP.
基金Supported by the National High Technology Research and Development Program of China(2012AA040211)the National Natural Science Foundation of China(21306043)+2 种基金the Research Fund for the Doctoral Program of Higher Education of China(2012007412001920130074110013)the Fundamental Research Funds for the Central Universities
文摘Microcellular injection molding of neat isotactic polypropylene(iPP) and isotactic polypropylene/nano-calcium carbonate composites(i PP/nano-CaCO_3) was performed using supercritical carbon dioxide as the physical blowing agent. The influences of filler content and operating conditions on microstructure morphology of i PP and i PP/nano-CaCO_3 microcellular samples were studied systematically. The results showed the bubble size of the microcellular samples could be effectively decreased while the cell density increased for i PP/nano-CaCO_3 composites, especially at high CO_2 concentration and back pressure, low mold temperature and injection speed, and high filler content. Then Moldex 3D was applied to simulate the microcellular injection molding process, with the application of the measured ScCO_2 solubility and diffusion data for i PP and i PP/nano-Ca CO_3 composites respectively. For neat i PP, the simulated bubble size and density distribution in the center section of tensile bars showed a good agreement with the experimental values. However, for i PP/nano-CaCO_3 composites, the correction factor for nucleation activation energy F and the pre-exponential factor of nucleation rate f_0 were obtained by nonlinear regression on the experimental bubble size and density distribution. The parameters F and f_0 can be used to predict the microcellular injection molding process for i PP/nano-CaCO_3 composites by Moldex 3D.
文摘The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G″) plots at 180 and 200 ℃ versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0.01-100 rad/s for Ziegler-Natta catalyzing ethylene-propylene random copolymerization(PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G″(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus(G 0_N) of UHPPH from a certain experimental temperature G″(ω) curve directly. For UHPPH, the G 0_N determined to be 4.28×10 5 and 3.62×10 5 Pa at 180 and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G 0_N has no relation to the molecular weight.
