A variety of linear and 3-arm star polyethylene (PE) model polymers covering a wide range of molecular weight are synthesized by the living polymerization of butadiene and the subsequent hydrogenation. Several rheological parameters of these model linear and 3-arm star PE samples are analyzed for detecting the long chain branching (LCB) structure. It is found that the analyses based on zero shear viscosity, vGP plot and flow activation energy are very sensitive to the 3-arm star PEs. The information on the presence of LCB can be obtained with these methods even for low molecular weight samples, which can not be determined by GPC-MALLS. However the information about the LCB structure can not be obtained by the rheological methods alone. 相似文献
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. 相似文献
Dissipative particle dynamics (DPD), a mesoscopic simulation approach, has been used to investigate the chain length effect on the structural property of the immiscible polyethylene (PE)/poly(L-lactide) (PLLA) polymer in a polymer blend and in a system with their diblock copolymer. In this work, the interaction parameter in DPD simulation, related to the Flory-Huggins interaction parameter chi, is estimated by the calculation of mixing energy for each pair of components in molecular dynamics simulation. The immiscibility property of PE and PLLA polymers induces the phase separation and exhibits different architectures at different volume fractions. In order to observe the structural property, the radius of gyration is used to observe the detailed arrangement of the polymer chains. It shows that the structure arrangement of a polymer chain is dependent on the phase structure and has a significantly different structural arrangement character for the very short chains in the homopolymer and copolymers. The chain length effect on the degree of stretching or extension of polymers has also been observed. As the chain length increases, the chain exhibits more stretching behavior at lamellae, perforated lamellae, and cylindrical configurations, whereas the chain exhibits a similar degree of stretching or extension at the cluster configuration. 相似文献
Summary: Heterogeneity of active centers (AC) of titanium-magnesium catalysts (TMC) and vanadium-magnesium catalyst (VMC) in ethylene-hexene-1 copolymerization has been studied on the base of data of polymer molecular weight distribution (MWD) deconvolution technique and copolymer fractionation onto narrow fractions. It was found that 3 and 4 Flory components (groups of active centers) are required to describe experimental MWD curves of copolymers produced over TMC with different Ti content. In the case of VMC MWD of homopolymer and copolymer are characterized by set of 5 Flory components (5 groups of AC). Different character of inter-relationship between MW and short chain branching (SCB) was found for ethylene-hexene-1 copolymers produced over different catalysts: heterogeneous type in the case of TMC and more uniform for copolymer prepared over VMC. The content of Ti affects on the slope of that profile in copolymers produced over TMC. The results indicated that TMC and VMC are different greatly on the heterogeneity of active centers to the formation of polymers with different molecular weights and to formation of copolymers with different inter-relationship between MW and short chain branching. TMC produces polymers with more narrow MWD but it contains highly heterogeneous centers regarding comonomer reactivity ratios. VMC produces polymers with broad and bimodal MWD but it contains more homogeneous centers regarding comonomer reactivity ratios. 相似文献
Crystallization analysis fractionation (CRYSTAF) was used for the first time to investigate the solution crystallization behavior of ethylene homopolymers and copolymers made with Phillips CrOx/SiO2 catalyst. Interestingly, the crystallization peak temperatures (Tp) of copolymers of ethylene and cyclopentene increased with increasing cyclopentene molar fraction in the copolymer. Comparing two factors (short chain branches (SCBs) and cyclopentene incorporation), decreasing SCB frequency is proposed as the dominant factor to explain the increase of crystallization peak temperatures with increasing cyclopentene incorporation. In addition, SCB frequency and molecular weight might be the two significant factors determining the crystallization temperature of polyethylene made with Phillips CrOx/SiO2 catalyst with different cocatalysts (triethylaluminum and diethylaluminum ethoxide). 相似文献
Fractions of two cellulose tricarbanilate samples were characterized by light-scattering (weight-average molecular weight, second virial coefficient, mean-square radius of gyration), gel permeation chromatography (polydispersity index), and viscometry (intrinsic viscosity) in tetrahydrofuran and acetone. The intrinsic viscosity data were analyzed in terms of the theory developed for the continuous wormlike cylinder model, and the chain parameters (Kuhn statistical segment length λ?1, chain diameter d, and shift factor ML) were evaluated. The molecular-weight dependence of the mean-square radius of gyration in tetrahydrofuran was calculated for the Kratky—Porod chain model and compared with the experimental results. Data on the intrinsic viscosity and radii of gyration for other solvents at temperatures from 0 to 100°C were analyzed in the same way, and the effects of solvent and temperature on the statistical segment length were evaluated. Polymer—solvent interaction parameters were estimated from the second virial coefficients. 相似文献
Summary: The influences of short chain branching (SCB) and molecular (Mw) weight of low density polyethylene (LDPE) on the solid state properties of polypropylene (PP)-LDPE blends were investigated by mechanical and thermal techniques. DSC analysis of all blends exhibit a double melting peak at all compositions studied thus suggesting that both PP and LDPE crystals exist separately in the solid state. It was found that the SCB and Mw of LDPE influenced the modulus and ultimate tensile strength of the blends. However, elongation at break seems to be independent of the molecular characteristics of the pure homopolymer especially at PP blend composition greater than 50%. LDPE with high SCB showed broader melting peaks. Addition of a small amount of a low Mw LDPE (10%) resulted in a higher elongation at break than a high Mw LDPE. There is likely a correlation between the presence of a new peak in the thermograms of PP-rich blends and the observed poor elongation at break. 相似文献
Two polymer molecules of the same length (n) and the same number of branch points (N) can have different properties, since they may possess distinct architectures. In this paper we present a conditional Monte Carlo algorithm for the virtual synthesis of metallocene‐catalyzed polyethylene (PE) in a continuous stirred tank reactor (CSTR). The condition for the Monte Carlo method consists of a fixed chain length distribution (CLD) and a degree of branching distribution (DBD). These distributions are calculated with a Galerkin finite element method. The synthesis method is a recursive algorithm that subsequently creates insertions of sub‐structures containing numbers of branch points according to a certain probability density function. This provides an adjacency matrix describing the connectivity between the branch points, while separately a vector containing the length of segments between branch points and terminal segments is generated. Characterization of the architectures proceeds by rheological features, seniorities and priorities, and molecular properties like the radius of gyration. Comparing the radii of gyration of metallocene polyethylene and low density PE (ldPE) shows the former to possess a more comb‐like structure on average. This is confirmed by the rheological characterization. The found bivariate seniority/priority distribution agrees well to the results of an analytical study of the same chemical system.
The recently developed methods of characterizing branching in polymers from gelpermeation chromatography and intrinsic viscosity data are verified experimentally. An iterative computer program was written to calculate the degree of branching in whole polymers. Long-chain branching in several low-density polyethylene samples was determined by both the fraction and whole polymer methods. The two methods gave consistent ranking of the branching in the samples although absolute branching indices differed. Effects of various experimental errors and the particular model used for branching were investigated. For polyethylene, the data show that the effect of branching on intrinsic viscosity is best described by the relation 〈g3〉W1/2 = [η]br/[η]1 where 〈g3〉w is the weight-average ratio of mean-square molecular radii of gyration of linear and trifunctionally branched polymers of the same weight-average molecular weight. 相似文献
The research about the polymerization reaction mechanism of long chain branched polymer provides a method to simulate the generation of LCB mPE (long chain branched metallocene polyethylene).[1-3] In this work, after simulating the generation of one million LCB mPE molecules, we calculate the sizes (i.e. radii of gyration) of molecules in good solvents to obtain the molecular size distributions. Then we simulate the fractionation in GPC (gel permeation chromatography) measurement and the different GPC detector responses to obtain simulated GPC MWDs (molecular weight distributions). The simulated MWDs are compared to the real GPC results provided by the Dow Chemical Company. 相似文献
A series of star polymers consisting of poly(tert‐butyl acrylate) arms and an ethyleneglycol dimethacrylate (EGDMA) microgel core were synthesized using anionic polymerization. The effect of various parameters (precursor length, ratio [[EGDMA]/[Initiator], reaction time, and overall concentrations) on the average number of arms was investigated. Molecular weights were determined using GPC coupled with an online viscometer and MALLS. The exponents for the relation between intrinsic viscosity or radius of gyration and molecular weight, respectively, are extremely low, indicating that the dimensions of the star polymers only slightly increase with the number of arms. After a certain number of arms is reached the intrinsic viscosity even decreases with molecular weight. Computer simulations for star polymers were carried out where the radius of gyration was calculated as a function of the number of arms. The results are in good agreement with the experimental data. 相似文献