In this paper,crystallization kinetics of a series of ethylene-propylene copolymers prepared by living polymerization coordination catalyzed by a fluorinated bis(phenoxyimine)Ti catalyst(FI-EP copolymers)was studied,a...In this paper,crystallization kinetics of a series of ethylene-propylene copolymers prepared by living polymerization coordination catalyzed by a fluorinated bis(phenoxyimine)Ti catalyst(FI-EP copolymers)was studied,and was compared with that of ethylene-propylene copolymers prepared by a conventional Ziegler-Natta catalyst(ZN-EP copolymers).It is found that,the Avrami exponent and the crystallization rate constant of the FI-EP and ZN-EP copolymer show similar dependence on crystallization temperature,but t...展开更多
Transformation of living ring-opening metathesis polymerization into coordination polymerization by converting the titanacyclobutane group attached to a polynorbornene chain into titanocene alkoxide has been used for ...Transformation of living ring-opening metathesis polymerization into coordination polymerization by converting the titanacyclobutane group attached to a polynorbornene chain into titanocene alkoxide has been used for the synthesis of polynorbornene-poly(ethylene-co-propylene) block copolymer. Preliminary characterizations of the copolymerization products by solvent extraction and C-13 NMR spectrum are reported.展开更多
The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above a...The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.展开更多
Well - defined diblock copolymers Of styrene (St ) and ethylene oxide (EO )have been prepared by sequential living anionic polymerization of the twocomonomers in THF. Diphenyl methyl potassium has been used as initiat...Well - defined diblock copolymers Of styrene (St ) and ethylene oxide (EO )have been prepared by sequential living anionic polymerization of the twocomonomers in THF. Diphenyl methyl potassium has been used as initiator. Theblock copolymers were characterized in detail by methods Of size exclusion chromatography (SEC ) , 1H - Nab, FT - IR, dynamic mechanical analysis(Daal ) and WAXD.展开更多
Crystallization behavior and resultant crystalline structure of a series of temperature-rising elu-tion-fractionated specimen of a Ziegler-Natta catalyst-synthesized propylene-ethylene random co-polymer were studied b...Crystallization behavior and resultant crystalline structure of a series of temperature-rising elu-tion-fractionated specimen of a Ziegler-Natta catalyst-synthesized propylene-ethylene random co-polymer were studied by DSC, WAXD and AFM. The experimental results indicate that both crystalliza-tion temperature and propylene sequence length exhibit great influence on the crystallization behavior and crystalline structure of the copolymer. It was found that the ethylene co-monomers acting as point defects inserted into the polypropylene chains play an important role in the formation of γ-iPP. As the co-monomer content increases, the crystallizable sequence length of iPP decreases, which produces an appropriate condition for its γ crystallization. At the same time, the existence of chain defects leads to a lower crystallinity of the copolymer and imperfection of the resultant crystals. For each individual sample with certain propylene sequence length or ethylene content, the increment of γ-iPP crystal content with increasing crystallization temperature demonstrates that higher crystallization tempera-ture is in favor of the γ-iPP crystallization. Pure γ-iPP crystals have been got in samples with propylene sequence length lower than 21 under suitable crystallization conditions.展开更多
Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction tempe...Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction temperature, ethylene/propylene molar ratio, aluminium/vanadium （Al/V） molar ratio and titanium/vanadium molar ratio on the catalytic activity were investigated. The molecular weight, molecular weight distribution, sequence composition and crystallinity of the products were measured by gel permeation chromatography, ^13C-NMR and differential scanning calorimetry analysis, respectively. In comparison to the vanadium and titanium catalysts, the bimetallic catalyst showed higher catalytic activity and better copolymerization performance. The obtained ethylene/propylene copolymers have high molecular weight （105）, broad molecular weight distribution, high propylene content with random or short blocked sequence structures （rErp = 1.919）, low melting temperatures and low crystallinities （Xc 〈 20%）.展开更多
Two commercial ethylene-propylene random copolymers(A and B) for hot water piping of which A has better long term heat stability and slow crack growth resistance performance than B were fractionated with respect to th...Two commercial ethylene-propylene random copolymers(A and B) for hot water piping of which A has better long term heat stability and slow crack growth resistance performance than B were fractionated with respect to the isotactity distribution by preparative temperature-rising elution fractionation(TREF).The molecular weight and distribution of fractions and the original resins were investigated by gel permeation chromatography.The results indicated that both A and B had broad isotacticity distribution and A had fewer portions of high isotacticity than B.At the same time A had broader and more typical double-peak molecular weight distribution.The fractions of A had higher molecular weight and broader molecular weight distribution than those of B’s.All of these results implied the differences between the catalysts or the polymerization processes for the two copolymers.展开更多
基金the National Basic Research Program of China(No.2005CB623804).
文摘In this paper,crystallization kinetics of a series of ethylene-propylene copolymers prepared by living polymerization coordination catalyzed by a fluorinated bis(phenoxyimine)Ti catalyst(FI-EP copolymers)was studied,and was compared with that of ethylene-propylene copolymers prepared by a conventional Ziegler-Natta catalyst(ZN-EP copolymers).It is found that,the Avrami exponent and the crystallization rate constant of the FI-EP and ZN-EP copolymer show similar dependence on crystallization temperature,but t...
文摘Transformation of living ring-opening metathesis polymerization into coordination polymerization by converting the titanacyclobutane group attached to a polynorbornene chain into titanocene alkoxide has been used for the synthesis of polynorbornene-poly(ethylene-co-propylene) block copolymer. Preliminary characterizations of the copolymerization products by solvent extraction and C-13 NMR spectrum are reported.
基金Supported by the Foundation of Educational Ministry of China.
文摘The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.
文摘Well - defined diblock copolymers Of styrene (St ) and ethylene oxide (EO )have been prepared by sequential living anionic polymerization of the twocomonomers in THF. Diphenyl methyl potassium has been used as initiator. Theblock copolymers were characterized in detail by methods Of size exclusion chromatography (SEC ) , 1H - Nab, FT - IR, dynamic mechanical analysis(Daal ) and WAXD.
基金the Outstanding Youth Fund of the National Natural Science Founda-tion of China (Grant No 20425414)National Natural Science Foundations of China (Grant Nos. 50521302, 20423003, 20574079,and 20604031)State "973" Pro-grams from the Ministry of Science and Technology of China (Grant No.2003CB615602)
文摘Crystallization behavior and resultant crystalline structure of a series of temperature-rising elu-tion-fractionated specimen of a Ziegler-Natta catalyst-synthesized propylene-ethylene random co-polymer were studied by DSC, WAXD and AFM. The experimental results indicate that both crystalliza-tion temperature and propylene sequence length exhibit great influence on the crystallization behavior and crystalline structure of the copolymer. It was found that the ethylene co-monomers acting as point defects inserted into the polypropylene chains play an important role in the formation of γ-iPP. As the co-monomer content increases, the crystallizable sequence length of iPP decreases, which produces an appropriate condition for its γ crystallization. At the same time, the existence of chain defects leads to a lower crystallinity of the copolymer and imperfection of the resultant crystals. For each individual sample with certain propylene sequence length or ethylene content, the increment of γ-iPP crystal content with increasing crystallization temperature demonstrates that higher crystallization tempera-ture is in favor of the γ-iPP crystallization. Pure γ-iPP crystals have been got in samples with propylene sequence length lower than 21 under suitable crystallization conditions.
基金supported by the Program for New Century Excellent Talents in Universities(NCET-07-0142)the Program for New Century Excellent Talents in Heilongjiang Provincial Universities(NCET-06-010)+1 种基金the National Natural Science Foundation of China(No.20972025)the Science Foundation of Tianjin University of Science & Technology(No.20090420)
文摘Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction temperature, ethylene/propylene molar ratio, aluminium/vanadium （Al/V） molar ratio and titanium/vanadium molar ratio on the catalytic activity were investigated. The molecular weight, molecular weight distribution, sequence composition and crystallinity of the products were measured by gel permeation chromatography, ^13C-NMR and differential scanning calorimetry analysis, respectively. In comparison to the vanadium and titanium catalysts, the bimetallic catalyst showed higher catalytic activity and better copolymerization performance. The obtained ethylene/propylene copolymers have high molecular weight （105）, broad molecular weight distribution, high propylene content with random or short blocked sequence structures （rErp = 1.919）, low melting temperatures and low crystallinities （Xc 〈 20%）.
文摘Two commercial ethylene-propylene random copolymers(A and B) for hot water piping of which A has better long term heat stability and slow crack growth resistance performance than B were fractionated with respect to the isotactity distribution by preparative temperature-rising elution fractionation(TREF).The molecular weight and distribution of fractions and the original resins were investigated by gel permeation chromatography.The results indicated that both A and B had broad isotacticity distribution and A had fewer portions of high isotacticity than B.At the same time A had broader and more typical double-peak molecular weight distribution.The fractions of A had higher molecular weight and broader molecular weight distribution than those of B’s.All of these results implied the differences between the catalysts or the polymerization processes for the two copolymers.
