Control strategies for the simultaneous control of microstructural properties of copolymer latexes (copolymer composition and molecular weight distribution) are presented. For linear polymers, on-line control strategies based on calorimetric measurements allowed to produce styrene/n-butyl acrylate emulsion polymers of predefined copolymer compositions and MWDs. The strategy failed for nonlinear polymers because the polymer produced at a certain process time might later in the process become active varying its molecular weight. Alternative open-loop control policies were developed for nonlinear polymers. These strategies required a mathematical model of the process that is used in an off-line optimization to determine the trajectories of the manipulated variables (feed flow rates of monomer and CTA) that allow producing the desired copolymers. The implementation of the open-loop control allowed the production of nonlinear MMA/n-BA emulsion copolymers of well-defined copolymer composition and MWD. 相似文献
It is well‐known that the final end‐use properties of polymer resins depend on the shape of the molecular‐weight distribution (MWD) very strongly. Particularly, polymer resins with bimodal MWDs are required for certain special applications, as they may simultaneously present enhanced mechanical and flow properties. A theoretical framework for the characterization of bimodality (or multimodality) of MWDs of polymers produced through linear polymerizations at steady‐state or quasi‐steady‐state conditions is developed and presented here. Conditions for the development of bimodality in generalized NS‐Schulz–Flory distributions are characterized for different forms of presentation of the MWDs. It is shown that the bimodal character of the MWD depends on the particular form used to represent it, which can then be used to generate an index of bimodality of the MWD. The theoretical results are finally used to compute the index of bimodality of actual polymer materials obtained at plant site. 相似文献
<正>The copolymerization of 4-vinylbenzyl chloride(VBC) and vinyl acetate(VAC) was carried out in toluene at 75℃via radical polymerization using 2,2'-azo-bis-(isobutyronitrile)(AIBN) as an initiator.The random copolymers of poly(4-vinylbenzyl chloride-co-vinyl acetate)(P(VBC-co-VAC)) with number average molecular weight(M_n) from 2000 to 6900,relatively narrow molecular weight distribution(MWD,M_w/M_n ca.2.0) and with different copolymer composition of 4-vinylbenzyl chloride(VBC) from 17 mol%to 62 mol%could be obtained.The P(VBC-co-VAC) copolymers with an average number of 7 to 13 initiating sites of benzyl chloride per macromolecule could be used for the cationic polymerization of isobutylene(IB).The cationic polymerizations of IB were further conducted by using P(VBC-co-VAC) copolymers as macroinitiators in conjunction with TiCl_4 at -40℃in CH_2Cl_2.The effects of VBC/TiCl_4(molar ratio) on monomer conversion,M_n and MWD of the resultant copolymers were investigated under 3 sets of conditions.It is found that P(VBC-co-VAC)-g-PIB copolymers with relatively narrow MWD(M_w/M_n ca.2.0) and with terminal tert-chlorine functional groups in branched PIB chains could be successfully synthesized when VBC/TiCl_4(molar ratio) was set in the range from 0.10 to 1.12.The unimodal GPC curve of the P(VBC-co-VAC)-g-PIB copolymers by RI detector was almost in harmony with the GPC curve by UV detector.The TEM image of the P(VBC-co-VAC)-g-PIB copolymer stained by RuO indicated that the copolymer formed a two-phase morphology with P(VBC-co-VAC)-rich domains of 20-100 nm in size tethered by PIB branch segments. 相似文献
A simple and general algorithm, convenient for computer implementation, for calculation of the copolymer molecular weight distribution (MWD), its moments, copolymer composition, etc. from standard data has been developed describing copolymerization as a Markovian process. The algorithm is applicable for simulations of multimonomer copolymerization with monomolecular, bimolecular and mixed termination. It can be used for calculating the MWD of copolymers prepared under non-stationary conditions. Explicit formulae have been derived for the above parameters. They are exact even for low-molecular-weight oligomers. The calculation procedure involves nothing but plain matrix operations as matrix multiplication and inversion. For high-molecular-weight copolymers, even simpler dependencies that resemble those used for homopolymers can be used. A very simple numerical test has been proposed for checking their correctness. 相似文献
Although size exclusion chromatography (SEC) has been used successfully to determine the molecular weight distribution (MWD) of statistical poly[(N-vinyl pyrrolidone)-co-(vinyl acetate)]s [PVPVAs], SEC cannot separate the copolymers according to their chemical composition. In this article, the separation of commercial PVPVAs with varying chemical compositions is reported, by aqueous reversed-phase gradient liquid chromatography (RPLC) using polystyrene-divinylbenzene-based wide pore columns. RPLC-SEC cross-fractionation indicates the presence of molar mass dependant effects during RPLC separation due to broad MWD for the copolymer studied; therefore the width of the RPLC peak could not be associated entirely with chemical composition distribution of the copolymer. Coupling of RPLC with online FTIR spectroscopy reveals the increase of VA content with increasing THF gradient, an indication of interaction mechanism between VA repeating units and the stationary phase for water soluble PVPVAs. Separation of water insoluble PVPVAs and PVAs by the RPLC are possibly based on both interaction and precipitation/redissolution mechanisms. 相似文献
The elution curves of size exclusion chromatography (SEC) for branched polymers formed through free‐radical polymerization that involves chain transfer to polymer were theoretically investigated by using a Monte Carlo method. We considered two types of measured molecular weight distribution (MWD), (1) the calibrated MWD relative to standard linear polymers, and (2) the MWD obtained by using a light scattering photometer (LS) in which the weight‐average molecular weight of polymers within the elution volume is determined directly. It was found that the calibrated MWD clearly underestimates the high molecular weight tail, and the measured distributions are narrower than the true MWD. On the other hand, the present simulation results showed that the LS method gives reasonable estimates of the true MWDs. The mean square radius of gyration of the polymer molecules having the same molecular weight was also investigated. The radii of gyration showed clear deviation from the Zimm‐Stockmayer equation[1] because of the non‐random nature of branched structure and the difference in the primary chain length distribution. 相似文献
The kinetic differential equations for the anionic copolymerization with constant monomer ratio are treated by Laplace transformation and a graphical technique. A theoretical method is established by which all molecular parameters of the copolymers, such as the molecular distribution (MWD), the average molecular weight and the polydispersity, can be calculated from reaction rate constants, initial conditions and polymerization time. Three-dimensional plots obtained by numerical computation are presented to illustrate the influence of the reaction conditions on the MWD's of the copolymers. 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
Summary: The deconvolution of molecular weight distributions (MWDs) may be useful for obtaining information about the polymerization kinetics and properties of catalytic systems. However, deconvolution techniques are normally based on steady‐state assumptions and very little has been reported about the use of non‐stationary approaches for the deconvolution of MWDs. In spite of this, polymerization reactions are often performed in batch or semi‐batch modes. For this reason, dynamic solutions are proposed here for simple kinetic models and are then used for deconvolution of actual MWD data. Deconvolution results obtained with dynamic models are compared to deconvolution results obtained with the standard stationary Flory‐Schulz distributions. For coordination polymerizations, results show that dynamic MWD models are able to describe experimental data with fewer catalytic sites, which indicates that the proper interpretation of the reaction dynamics may be of fundamental importance for kinetic characterization. On the other hand, reaction dynamics induced by modification of chain transfer agent concentration seem to play a minor role in the shape of the MWD in free‐radical polymerizations.
This Figure illustrates that MWDs obtained at unsteady conditions should not be deconvoluted with standard steady‐state Flory‐Schulz distributions. 相似文献
Emulsion copolymerization of Tribromophenyl Maleimide (TBPMI) and styrene was conducted by semi-batch and batch processes. The effects of monomer composition and copolymerization method on copolymerization rate, molecular weight and molecular weight distribution, latex particle size and size distribution, glass transition temperature (Tg), thermal stability and mechanical properties were investigated. A kinetic study has shown that the rate of copolymerization in the batch process increased with increasing TBPMI content in the monomer feed. For the semi-batch polymerized samples, molecular weight decreased and molecular weight distribution increased with increasing TBPMI content in the monomer feed. For the batch polymerized samples, molecular weight also decreased but no obvious tendency was observed for the molecular weight distribution when TBPMI content increased. Compared with the batch copolymers, the semi-batch copolymers have a higher molecular weight at the same initial monomer mixture composition. Latex particle size decreased, while particle size distribution slightly increased with increasing TBPMI content in both semi-batch and batch latices. The semi-batch samples exhibit only a single Tg, the value of which increses linearly with increasing TBPMI content. For the batch copolymers, two Tgs were found, reflecting a mixture of styrene-rich and TBPMI-rich copolymer chains. TGA results indicate that the thermal stability of the semi-batch copolymers increased with increasing TBPMI concentration. Young's and flexural moduli increased, while tensile and flexural strengths decreased by increasing the TBPMI content for both the semi-batch and batch specimens. The semi-batch specimens have higher tensile and flexural strenghts than the batch ones. 相似文献
Abstract The effects of instrumental broadening and of polymer/solvent/packing interactions (secondary broadening) are separately investigated in the context of chromatography experiments, for the characterization of linear copolymers with two types of repeating units. The problems associated to the estimation of: a) the joint molecular weight distribution - chemical composition distribution (MWD-CCD) through orthogonal chromatography; and of b) the average MWD - average CCD through standard size exclusion chromatography (SEC) with dual detection are considered. The main difficulty with the secondary broadening correction, is the calibration for this effect. In the case of standard SEC with dual detection, a simple solution was found to the instrumental broadening problem, that involves a direct extension of the calibration and deconvolution techniques developed for linear homopolymers and mass detectors. 相似文献
The problem of preparation of a block copolymer of precise molecular-weight distribution (MWD) and with heterogeneous composition on the basis of gel-permeation chromatography (GPC) data has been investigated. It has been shown that in MWD calculations the distribution f(p) of the composition p in individual GPC fractions should be taken into account. The type of the f(p) functions can be simultaneously established by an independent method, such as use of adsorption-column or thin-layer chromatography sensitive to the composition of the copolymer. It has also been shown that the actual f(p) may be replaced by a corresponding piecewise distribution, of simple form, without decrease in the precision of calculation of the MWD and average molecular weights of most known block copolymers. 相似文献