The phase transition from tetragonal form II to hexagonal form I was studied for the butene-1/ethylene and butene-1/1,5- hexadiene random copolymers, which have comparable molecular weight but distinct linear ethylene...The phase transition from tetragonal form II to hexagonal form I was studied for the butene-1/ethylene and butene-1/1,5- hexadiene random copolymers, which have comparable molecular weight but distinct linear ethylene and ringlike methylene-1,3- cyclopentane （MCP） structural co-units, respectively. It is known that this solid phase transition follows the nucleation-growth mechanism, so the stepwise annealing protocol was utilized to investigate the influences of co-units on the optimal nucleation and growth temperatures. Compared with optimal nucleation and growth temperatures of-10 and 3 5 ℃, respectively, in polybutene-1 homopolymer, two butene-1/ethylene copolymers with 1.5 mol% and 4.3 mol% co-units have the slightly lower optimal nucleation temperature of-15 ℃ but much higher optimal growth temperature of 50 ℃. Clearly, the effect of ethylene co-unit is more significant on varying optimal temperature for growth than for nucleation. Furthermore, when the incorporated co-unit is ringlike MCP, the optimal nucleation temperature is -15 ℃ for 2.15 mol% co-units, the same with above BE copolymers, but -13 ℃ for a very low concentration of 0.65 mol%. Interestingly, the optimal growth temperature of butene-1/1,5-hexadiene copolymers with 0.65 mo1%-2.15 mol% MCP co- units increases to 55 ℃, which is also independent on co-unit concentration. These obtained values of optimal temperatures provide crucial parameters for rapid II-I phase transition.展开更多
In the present work,a series of poly(ethylene glycol) grafted polybutene-1 copolymers(PB-g-PEG) were designed and successfully synthesized with reaction intermediate method,of which the branch densities and length cou...In the present work,a series of poly(ethylene glycol) grafted polybutene-1 copolymers(PB-g-PEG) were designed and successfully synthesized with reaction intermediate method,of which the branch densities and length could be tuned independently.The branch density varied from 0.39 mol% to 1.23 mol% and the branch length was tuned by employing PEG number-averaged molecular weight(Mn) from 350 Da to 750 Da and 1000 Da.The non-isothermal crystallization and phase transition behaviors of these butene-1 copolymers with varying branches were systematically explored by differential scanning calorimeter.The results first showed that compared with the linear polybutene-1 homopolymer,presence of steric 4-[4-(trimethylsilylalkynyl)-phenyl]-1-butene(TMS) groups suppressed crystallization and phase transition of copolymers.Interestingly,the introduction of long poly(ethylene glycol)(PEG) branches with M_(n)=350-1000 Da not only elevated the peak temperature of the non-isothermal crystallization but also enhanced the Ⅱ-Ⅰ phase transition,with respect to copolymers with TMS groups.Furthermore,the quantitative correlations between phase transition kinetics with the branch parameters(density and length) were explored.It was found that the phase transition presents a non-monotonic trend with increasing branch density and branch length.In this case,the optimal branch density and length obtained were 0.77 mol% and 750 Da,respectively.Employing the small angle X-ray scattering and transmission electron microscopy,a direct correlation between the phase transition kinetics and the long periodicity of separated phase was obtained,which may be due to the increased internal stress and facilitated stress transport.展开更多
Propene/1-decene copolymers （P-co-D） were synthesized by means of slurry polymerization process under atmospheric pressure using Ziegler-Natta catalyst （MgCl2/TiCl4/AlEt3）. The random P-co-Ds were elastic, low-cry...Propene/1-decene copolymers （P-co-D） were synthesized by means of slurry polymerization process under atmospheric pressure using Ziegler-Natta catalyst （MgCl2/TiCl4/AlEt3）. The random P-co-Ds were elastic, low-crystalline, thermally stable and therefore suitable to be used as membrane materials in organophilic pervaporation with chloroform/water mixture. Its mechanical strength is better than polydimethylsiloxane （PDMS）. The correlation between structural parameters （glass transition temperature and crystallinity） and properties of organophilic pervaporation were investigated.展开更多
A ^(13)C-NMR method is presented for a quantitative determination of the respective monomercomposition and sequence distributions in ethylene-1-octene copolymers prepared with supportedtitanium/magnesium catalyst. On ...A ^(13)C-NMR method is presented for a quantitative determination of the respective monomercomposition and sequence distributions in ethylene-1-octene copolymers prepared with supportedtitanium/magnesium catalyst. On the basis of the sequence distributions, the ethylene-1-octenecopolymerization mechanism was studied. It was found that the observed sequence distributions inethylene-1-octene copolymers are satisfactorily predicted by the two-site model M/M,in whichthe copolymerization proceeds according to first-order Markovian statistics at the two differentsites.展开更多
Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and but...Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gra- vimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir(DL)model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory(IAST),the IAST-DL model was applied to model the butene-1(1)/n-butane(2)binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorp- tion over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.展开更多
A mathematical model for analyzing and simulating selective hydrogenation of butyne-1 and 1,3-bu-tadiene in industrial trickle bed reactors operated to obtain high purity butene-1 is presented in this work.Fromthe ana...A mathematical model for analyzing and simulating selective hydrogenation of butyne-1 and 1,3-bu-tadiene in industrial trickle bed reactors operated to obtain high purity butene-1 is presented in this work.Fromthe analysis of typical operating conditions,only the relevant phenomena are finally retained in the model formu-lation.The model is then employed to analyze the effect of operating variables and catalyst selectivity in processperformance.In particular,the search for the minimum hydrogen flow rate necessary to fulfil butene-1 purityspecifications is undertaken.展开更多
1 INTRODUCTIONSelective hydrogenatioll of small amounts of butynes and butadiene is industrially employedfor obtaining high purity butene-l used as co-monomer in the production of linear low-densitypolyethyene.For thi...1 INTRODUCTIONSelective hydrogenatioll of small amounts of butynes and butadiene is industrially employedfor obtaining high purity butene-l used as co-monomer in the production of linear low-densitypolyethyene.For this purpose,the content of vinylacetylene.butyne-l and 1,3-butadiene presentin the process stream should be reduced to a few tens of ppm.展开更多
Optically active copolymers of pairs of three monomers, triphenyl (methyl methacrylate)and one or two pyridyl substituted methyl methacrylate homologues, were obtained by helix-sense-selective copolymerization using c...Optically active copolymers of pairs of three monomers, triphenyl (methyl methacrylate)and one or two pyridyl substituted methyl methacrylate homologues, were obtained by helix-sense-selective copolymerization using complexes of organolithium with chiral ligand as anionicinitiators in toluene at low temperature. The copolymers obtained with (-)-sparteine (Sp) and(S,S)-(+)-and (R, R)-(-)-2, 3-dimethoxy-1, 4-bis (dimethylamino) butanes((+)-and (-)-DDB) complexes of organolithium showed low optical activity, but PMP complex with N, N-diphenylethyleneamine monolithium amide (PMP-DPEDA-Li) was effective in synthesizingcopolymers of high optical rotation ([α]_D^(25) about+320～1370°)which were comparable to thoseof relative homopolymers with one-handed helical structure.展开更多
基金supported by the National Natural Science Foundation of China(Nos.51573132 and 51633009)Tianjin Natural Science Foundation(No.16JCQNJC02700)
文摘The phase transition from tetragonal form II to hexagonal form I was studied for the butene-1/ethylene and butene-1/1,5- hexadiene random copolymers, which have comparable molecular weight but distinct linear ethylene and ringlike methylene-1,3- cyclopentane （MCP） structural co-units, respectively. It is known that this solid phase transition follows the nucleation-growth mechanism, so the stepwise annealing protocol was utilized to investigate the influences of co-units on the optimal nucleation and growth temperatures. Compared with optimal nucleation and growth temperatures of-10 and 3 5 ℃, respectively, in polybutene-1 homopolymer, two butene-1/ethylene copolymers with 1.5 mol% and 4.3 mol% co-units have the slightly lower optimal nucleation temperature of-15 ℃ but much higher optimal growth temperature of 50 ℃. Clearly, the effect of ethylene co-unit is more significant on varying optimal temperature for growth than for nucleation. Furthermore, when the incorporated co-unit is ringlike MCP, the optimal nucleation temperature is -15 ℃ for 2.15 mol% co-units, the same with above BE copolymers, but -13 ℃ for a very low concentration of 0.65 mol%. Interestingly, the optimal growth temperature of butene-1/1,5-hexadiene copolymers with 0.65 mo1%-2.15 mol% MCP co- units increases to 55 ℃, which is also independent on co-unit concentration. These obtained values of optimal temperatures provide crucial parameters for rapid II-I phase transition.
基金financially supported by the National Natural Science Foundation of China (Nos. 52022065 and 51873151)。
文摘In the present work,a series of poly(ethylene glycol) grafted polybutene-1 copolymers(PB-g-PEG) were designed and successfully synthesized with reaction intermediate method,of which the branch densities and length could be tuned independently.The branch density varied from 0.39 mol% to 1.23 mol% and the branch length was tuned by employing PEG number-averaged molecular weight(Mn) from 350 Da to 750 Da and 1000 Da.The non-isothermal crystallization and phase transition behaviors of these butene-1 copolymers with varying branches were systematically explored by differential scanning calorimeter.The results first showed that compared with the linear polybutene-1 homopolymer,presence of steric 4-[4-(trimethylsilylalkynyl)-phenyl]-1-butene(TMS) groups suppressed crystallization and phase transition of copolymers.Interestingly,the introduction of long poly(ethylene glycol)(PEG) branches with M_(n)=350-1000 Da not only elevated the peak temperature of the non-isothermal crystallization but also enhanced the Ⅱ-Ⅰ phase transition,with respect to copolymers with TMS groups.Furthermore,the quantitative correlations between phase transition kinetics with the branch parameters(density and length) were explored.It was found that the phase transition presents a non-monotonic trend with increasing branch density and branch length.In this case,the optimal branch density and length obtained were 0.77 mol% and 750 Da,respectively.Employing the small angle X-ray scattering and transmission electron microscopy,a direct correlation between the phase transition kinetics and the long periodicity of separated phase was obtained,which may be due to the increased internal stress and facilitated stress transport.
基金This work was supported by the National Basic Research Program of China(No.2003.CB615705)the National Natural Science Foundation of China(No.50433010).
文摘Propene/1-decene copolymers （P-co-D） were synthesized by means of slurry polymerization process under atmospheric pressure using Ziegler-Natta catalyst （MgCl2/TiCl4/AlEt3）. The random P-co-Ds were elastic, low-crystalline, thermally stable and therefore suitable to be used as membrane materials in organophilic pervaporation with chloroform/water mixture. Its mechanical strength is better than polydimethylsiloxane （PDMS）. The correlation between structural parameters （glass transition temperature and crystallinity） and properties of organophilic pervaporation were investigated.
基金This work was supported by the National Natural Science Foundation of China
文摘A ^(13)C-NMR method is presented for a quantitative determination of the respective monomercomposition and sequence distributions in ethylene-1-octene copolymers prepared with supportedtitanium/magnesium catalyst. On the basis of the sequence distributions, the ethylene-1-octenecopolymerization mechanism was studied. It was found that the observed sequence distributions inethylene-1-octene copolymers are satisfactorily predicted by the two-site model M/M,in whichthe copolymerization proceeds according to first-order Markovian statistics at the two differentsites.
基金Supported by the National Natural Science Foundation of China （Nos.20236010,20476004） and China Petroleum ＆ Chemical Corporation （No.X504023）.
文摘Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gra- vimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir(DL)model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory(IAST),the IAST-DL model was applied to model the butene-1(1)/n-butane(2)binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorp- tion over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.
文摘A mathematical model for analyzing and simulating selective hydrogenation of butyne-1 and 1,3-bu-tadiene in industrial trickle bed reactors operated to obtain high purity butene-1 is presented in this work.Fromthe analysis of typical operating conditions,only the relevant phenomena are finally retained in the model formu-lation.The model is then employed to analyze the effect of operating variables and catalyst selectivity in processperformance.In particular,the search for the minimum hydrogen flow rate necessary to fulfil butene-1 purityspecifications is undertaken.
文摘1 INTRODUCTIONSelective hydrogenatioll of small amounts of butynes and butadiene is industrially employedfor obtaining high purity butene-l used as co-monomer in the production of linear low-densitypolyethyene.For this purpose,the content of vinylacetylene.butyne-l and 1,3-butadiene presentin the process stream should be reduced to a few tens of ppm.
基金This project is supported by the National Natural Science Foundation of China and the President Foundation of Academia Sinica
文摘Optically active copolymers of pairs of three monomers, triphenyl (methyl methacrylate)and one or two pyridyl substituted methyl methacrylate homologues, were obtained by helix-sense-selective copolymerization using complexes of organolithium with chiral ligand as anionicinitiators in toluene at low temperature. The copolymers obtained with (-)-sparteine (Sp) and(S,S)-(+)-and (R, R)-(-)-2, 3-dimethoxy-1, 4-bis (dimethylamino) butanes((+)-and (-)-DDB) complexes of organolithium showed low optical activity, but PMP complex with N, N-diphenylethyleneamine monolithium amide (PMP-DPEDA-Li) was effective in synthesizingcopolymers of high optical rotation ([α]_D^(25) about+320～1370°)which were comparable to thoseof relative homopolymers with one-handed helical structure.
