The rheological behavior, thermal properties and foam morphology of linear polypropylene and long chain branching polypropylene prepared through UV irradiation reactive extrusion were studied by rheological test, melt...The rheological behavior, thermal properties and foam morphology of linear polypropylene and long chain branching polypropylene prepared through UV irradiation reactive extrusion were studied by rheological test, melt index test, DSC and supercritical carbon dioxide foaming technology. Rheological test and melt index test confirmed that under UV irradiation and extrusion, adding photo-initiator and cross- linking agent could achieve the purpose of branching, thus improved the melt strength of polypropylene effectively. The DSC results revealed that with the introducing of long chain branching, the melting range of the polypropylene broadened and the crystallization temperature increased. Owing to the introduction of long chain branches, polypropylene exhibited higher melt strength and strain hardening behavior. Compared with linear polypropylene, the foam morphologies of long chain branching polypropylene were more uniform.展开更多
The long chain branching(LCB)polyglycolide(PGA)was successfully prepared by the successive reactions of the terminal hydroxyl groups of PGA with triglycidyl isocyanurate(TGIC)and pyromellitic dianhydride(PMDA).The inf...The long chain branching(LCB)polyglycolide(PGA)was successfully prepared by the successive reactions of the terminal hydroxyl groups of PGA with triglycidyl isocyanurate(TGIC)and pyromellitic dianhydride(PMDA).The influence of LCB produced by functional group reaction on rheological and crystallization behavior was studied and discussed through linear rheology,uniaxial elongation and DSC(differential scanning calorimetry).The much higher viscosity and the more notable strain hardening behavior of modified PGA indicates the LCB with high degree of entanglements are created.The melt strength of PGA is finally improved greatly and can make su re that the supercritical CO_(2)foaming can be carried out successfully.展开更多
Long chain branched polypropylene random copolymers （LCB-PPRs） were prepared via reactive extrusion with the addition of dicumyl peroxide （DCP） and various amounts of 1,6-hexanediol diacrylate （HDDA） into PPR. F...Long chain branched polypropylene random copolymers （LCB-PPRs） were prepared via reactive extrusion with the addition of dicumyl peroxide （DCP） and various amounts of 1,6-hexanediol diacrylate （HDDA） into PPR. Fourier transform infrared spectrometer （FTIR） was applied to confirm the existence of branching and（ investigate the grafting degree for the modified PPRs. Melt flow index （MFI） and oscillatory shear rheological properties including complex viscosity, storage modulus, loss tangent and the Cole-Cole plots were studied to differentiate the LCB-PPRs from linear PPR. Differential scanning calorimetry （DSC） and polarized light microscopy （PLM） were used to study the melting and crystallization behavior and the spherulite morphology, respectively. Qualitative and quantitative analyses of rheological curves demonstrated the existence of LCB. The effect of the LCB on crystalline morphology, crystallization behavior and molecular mobility, and, thereby, the mechanical properties were studied and analyzed. Due to the entanglements between molecular chains and the nucleating effect of LCB, LCB-PPRs showed higher crystallization temperature and crystallinity, higher crystallization rate, more uniformly dispersed and much smaller crystallite compared with virgin PPR, thus giving rise to significantly improve impact strength. Moreover, the LCB-PPRs exhibited the improved yield strength. The mobility of the molecular chain segments, as demonstrated by dynamic mechanical analysis （DMA）, was improved for the modified PPRs, which also contributed to the improvement of their mechanical properties.展开更多
Comb-like polyethylene（PE） was prepared via anionic polymerization combined with ＂graft-onto＂ process. The polybutadiene（PB） backbone underwent hydroxylation at 1,2-vinyl groups to obtain a controlled number of ...Comb-like polyethylene（PE） was prepared via anionic polymerization combined with ＂graft-onto＂ process. The polybutadiene（PB） backbone underwent hydroxylation at 1,2-vinyl groups to obtain a controlled number of hydroxyl groups along the main chain. After the translation of hydroxyl groups to tosyl groups, a nucleophilic substitution by living anionic PB chains was achieved. The comb PE was finally obtained by the hydrogenation of the obtained unsaturated comb polymer. Since the living anionic polymerization was used to prepare the backbones and the branch chains, molecular weight to molecular weight distribution（Mw/Mn〈1.5） can be well-controlled in the final comb polymer, including the average number and length of branches.展开更多
The isothermal and non-isothermal crystallization kinetics of LCBPP and linear-iPP was investigated by optical microscopy and differential scanning calorimetry (DSC). The optical microscopy results in the isothermal c...The isothermal and non-isothermal crystallization kinetics of LCBPP and linear-iPP was investigated by optical microscopy and differential scanning calorimetry (DSC). The optical microscopy results in the isothermal crystallization process show that the crystals of LCBPP grow slower than the crystals of the linear-iPP. This originates from the low chain mobility, or in other words, the lower chain diffusion rate of LCBPP due to the existence of long side chains. The DSC results in the isothermal crystallization process show that the LCBPP exhibits, however, a higher overall crystallization rate with respect to the linear-iPP. This is related to the higher nucleation ability of LCBPP since the isothermal crystallization process of both LCBPP and linear-iPP are nucleation-dominated. Avrami analysis indicates that the nucleation nature and crystal growth manner of LCBPP and linear-iPP are about the same. The analy- ses of the non-isothermal crystallization processes indicate an increment in crystallization rate with increasing cooling rate. But at any cooling rate, the linear-iPP crystallizes more quickly than the LCBPP. This implies that the non-isothermal crystallization processes of LCBPP and linear-iPP are diffu- sion-dominated, in which the lower chain diffusion rate of LCBPP results in the slower crystallization of it.展开更多
The detection of long-chain branches（LCB） in polyethylene is of considerable importance as the processing properties of polyethylene are strongly affected by even a small amount of LCB. While the conventional charac...The detection of long-chain branches（LCB） in polyethylene is of considerable importance as the processing properties of polyethylene are strongly affected by even a small amount of LCB. While the conventional characterization techniques such as GPC-MALS and13 C NMR fail or take very long time to detect low content of LCB, we turn to the rheological method, which is more sensitive to LCB. In our study, we performed oscillatory shear test, creep test and stress relaxation test on two series of metallocene linear low density polyethylene（LLDPE）, revealing that the resins with LCB show higher zero-shear-rate viscosity, retarded relaxation and higher flow activation energy than those without or with less LCB. The resins with LCB showed shear thinning at very low shear rate and their zero-shear-rate viscosities were obtained via creep test. The content of LCB was quantitatively estimated from the flow activation energy. In addition, the modulus-time curves during stress relaxation of melt of the different resins obeyed the power law. The exponent of the resins with more LCB was 0.7, different from that of the resins with less LCB, around 1.7.展开更多
基金Funded by the National Natural Science Foundation of China(No.51103091)Scientific Research Foundation for the Returned Overseas Chinese Scholars State Education Ministry(No.20101174-4-3)the Opening Project of the Key Laboratory of Polymer Processing Engineering,Ministry of Education,China and the Fundamental Research Funds for the Central Universities(No.2012ZM0074)
文摘The rheological behavior, thermal properties and foam morphology of linear polypropylene and long chain branching polypropylene prepared through UV irradiation reactive extrusion were studied by rheological test, melt index test, DSC and supercritical carbon dioxide foaming technology. Rheological test and melt index test confirmed that under UV irradiation and extrusion, adding photo-initiator and cross- linking agent could achieve the purpose of branching, thus improved the melt strength of polypropylene effectively. The DSC results revealed that with the introducing of long chain branching, the melting range of the polypropylene broadened and the crystallization temperature increased. Owing to the introduction of long chain branches, polypropylene exhibited higher melt strength and strain hardening behavior. Compared with linear polypropylene, the foam morphologies of long chain branching polypropylene were more uniform.
文摘The long chain branching(LCB)polyglycolide(PGA)was successfully prepared by the successive reactions of the terminal hydroxyl groups of PGA with triglycidyl isocyanurate(TGIC)and pyromellitic dianhydride(PMDA).The influence of LCB produced by functional group reaction on rheological and crystallization behavior was studied and discussed through linear rheology,uniaxial elongation and DSC(differential scanning calorimetry).The much higher viscosity and the more notable strain hardening behavior of modified PGA indicates the LCB with high degree of entanglements are created.The melt strength of PGA is finally improved greatly and can make su re that the supercritical CO_(2)foaming can be carried out successfully.
基金financially supported by the Foundation for Development of Science and Technology of Fuzhou University(No.2011-XY-1)
文摘Long chain branched polypropylene random copolymers （LCB-PPRs） were prepared via reactive extrusion with the addition of dicumyl peroxide （DCP） and various amounts of 1,6-hexanediol diacrylate （HDDA） into PPR. Fourier transform infrared spectrometer （FTIR） was applied to confirm the existence of branching and（ investigate the grafting degree for the modified PPRs. Melt flow index （MFI） and oscillatory shear rheological properties including complex viscosity, storage modulus, loss tangent and the Cole-Cole plots were studied to differentiate the LCB-PPRs from linear PPR. Differential scanning calorimetry （DSC） and polarized light microscopy （PLM） were used to study the melting and crystallization behavior and the spherulite morphology, respectively. Qualitative and quantitative analyses of rheological curves demonstrated the existence of LCB. The effect of the LCB on crystalline morphology, crystallization behavior and molecular mobility, and, thereby, the mechanical properties were studied and analyzed. Due to the entanglements between molecular chains and the nucleating effect of LCB, LCB-PPRs showed higher crystallization temperature and crystallinity, higher crystallization rate, more uniformly dispersed and much smaller crystallite compared with virgin PPR, thus giving rise to significantly improve impact strength. Moreover, the LCB-PPRs exhibited the improved yield strength. The mobility of the molecular chain segments, as demonstrated by dynamic mechanical analysis （DMA）, was improved for the modified PPRs, which also contributed to the improvement of their mechanical properties.
基金Supported by the National Natural Science Foundation of China（Nos.51073149, 51233005）.
文摘Comb-like polyethylene（PE） was prepared via anionic polymerization combined with ＂graft-onto＂ process. The polybutadiene（PB） backbone underwent hydroxylation at 1,2-vinyl groups to obtain a controlled number of hydroxyl groups along the main chain. After the translation of hydroxyl groups to tosyl groups, a nucleophilic substitution by living anionic PB chains was achieved. The comb PE was finally obtained by the hydrogenation of the obtained unsaturated comb polymer. Since the living anionic polymerization was used to prepare the backbones and the branch chains, molecular weight to molecular weight distribution（Mw/Mn〈1.5） can be well-controlled in the final comb polymer, including the average number and length of branches.
基金the Outstanding Youth Fund and the National Natural Science Founda-tion of China (Grant Nos. 50521302, 20574079 and 20423003)
文摘The isothermal and non-isothermal crystallization kinetics of LCBPP and linear-iPP was investigated by optical microscopy and differential scanning calorimetry (DSC). The optical microscopy results in the isothermal crystallization process show that the crystals of LCBPP grow slower than the crystals of the linear-iPP. This originates from the low chain mobility, or in other words, the lower chain diffusion rate of LCBPP due to the existence of long side chains. The DSC results in the isothermal crystallization process show that the LCBPP exhibits, however, a higher overall crystallization rate with respect to the linear-iPP. This is related to the higher nucleation ability of LCBPP since the isothermal crystallization process of both LCBPP and linear-iPP are nucleation-dominated. Avrami analysis indicates that the nucleation nature and crystal growth manner of LCBPP and linear-iPP are about the same. The analy- ses of the non-isothermal crystallization processes indicate an increment in crystallization rate with increasing cooling rate. But at any cooling rate, the linear-iPP crystallizes more quickly than the LCBPP. This implies that the non-isothermal crystallization processes of LCBPP and linear-iPP are diffu- sion-dominated, in which the lower chain diffusion rate of LCBPP results in the slower crystallization of it.
基金supported by the National Natural Science Foundation of China (No. 21374054)the Sino-GermanCenter for Research Promotion
文摘The detection of long-chain branches（LCB） in polyethylene is of considerable importance as the processing properties of polyethylene are strongly affected by even a small amount of LCB. While the conventional characterization techniques such as GPC-MALS and13 C NMR fail or take very long time to detect low content of LCB, we turn to the rheological method, which is more sensitive to LCB. In our study, we performed oscillatory shear test, creep test and stress relaxation test on two series of metallocene linear low density polyethylene（LLDPE）, revealing that the resins with LCB show higher zero-shear-rate viscosity, retarded relaxation and higher flow activation energy than those without or with less LCB. The resins with LCB showed shear thinning at very low shear rate and their zero-shear-rate viscosities were obtained via creep test. The content of LCB was quantitatively estimated from the flow activation energy. In addition, the modulus-time curves during stress relaxation of melt of the different resins obeyed the power law. The exponent of the resins with more LCB was 0.7, different from that of the resins with less LCB, around 1.7.
