Polyethylene polymerization kinetics

Keywords Ethylene polymerization mechanisms Heterogeneous model catalysts Homogeneous model catalysts Molecular modeling Phillips Cr/silica catalyst Polyethylene Polymerization kinetics... 

Polymerization inhibitors miscellaneous, 23 383 in styrene manufacture, 23 338 Polymerization initiators alkyllithiums as, 74 251 cerium application, 5 687 peroxydicarbonates as, 74 290 Polymerization kinetics, in PVC polymerization, 25 666-667 Polymerization mechanism, for low density polyethylene, 20 218 Polymerization methods, choice of,... 

Yet Chien demostrated that it would be possible to obtain polyethylene with a Q value near the theoretical 2, with the homogeneous (CjH5)2TiCl2—A1(CH3)2C1 catalytic system, only if carefully controlled pseudosteady-state conditions are employed. In fact he showed mathematically that the relatively high experimental polydispersiiy (<,) tfom 2 to 5 in function of reaction time), is a natural consequence of a polymerization kinetic model based on non stationary first order initiation, chain propagation and bimolecular chain termination by recombination. 

Keywords Catalysis intercalation polymerization kinetics layered clay nanocomposite oxidation polyethylene thermal degradation... 

Catalyst Polymerization Kinetics and Polyethylene Particle Morphology... 

Buchelli, A., Call, M., Brown, A., Bokis, C Ramanathan, S., and Franjione, J. (2002) Physical properties, reactor modebng and polymerization kinetics in the low-density polyethylene tubular reactor process. Industrial S. Engineering Chemistry Research, 41 (5), 1017-1030. 

The difficulties met in dedudng chain-transfer and P-sdssion rate coeffidents from experimental quantities are due to the fact that the individual kinetic steps contribute in a complex fashion to polyethylene properties. A brief survey on the correlation of fundamental polymerization kinetics to process design and to the prediction of polymer properties has been presented by Bauer et al. ... 

It is noteworthy that there is a strong suggestion of steric hindrance or steric control of the chain-transfer reaction involving a polyethylene growing chain (6 ). Specific mention is made here of this observation for emphasis inasmuch as this factor has been seldom considered in polymerization kinetics. The microstructure of polyethylene is also believed to be strongly influenced by steric factors. 

The molecular weight distribution (MWD) of polyethylene, like its structure and number average molecular wdght, is, of course, controlled by the polymerization kinetics. Any adequate reaction modd must therefore account for the MWD which is usually broad. For commerdal polyethylenes, made in CSTR or tubular reactors, ratios of weight to number average molecular wd t, M jM, of less than 5 are rare and values far in excess of 10 are often obtained, even when care is taken to remove all insoluble material (703, 704). 

Polyethylene (Section 6 21) A polymer of ethylene Polymer (Section 6 21) Large molecule formed by the repeti tive combination of many smaller molecules (monomers) Polymerase chain reaction (Section 28 16) A laboratory method for making multiple copies of DNA Polymerization (Section 6 21) Process by which a polymer is prepared The principal processes include free radical cationic coordination and condensation polymerization Polypeptide (Section 27 1) A polymer made up of many (more than eight to ten) amino acid residues Polypropylene (Section 6 21) A polymer of propene Polysaccharide (Sections 25 1 and 25 15) A carbohydrate that yields many monosacchande units on hydrolysis Potential energy (Section 2 18) The energy a system has ex elusive of Its kinetic energy... 

Gas phase olefin polymerizations are becoming important as manufacturing processes for high density polyethylene (HOPE) and polypropylene (PP). An understanding of the kinetics of these gas-powder polymerization reactions using a highly active TiCi s catalyst is vital to the careful operation of these processes. Well-proven models for both the hexane slurry process and the bulk process have been published. This article describes an extension of these models to gas phase polymerization in semibatch and continuous backmix reactors. 

Structurally, plastomers straddle the property range between elastomers and plastics. Plastomers inherently contain some level of crystallinity due to the predominant monomer in a crystalline sequence within the polymer chains. The most common type of this residual crystallinity is ethylene (for ethylene-predominant plastomers or E-plastomers) or isotactic propylene in meso (or m) sequences (for propylene-predominant plastomers or P-plastomers). Uninterrupted sequences of these monomers crystallize into periodic strucmres, which form crystalline lamellae. Plastomers contain in addition at least one monomer, which interrupts this sequencing of crystalline mers. This may be a monomer too large to fit into the crystal lattice. An example is the incorporation of 1-octene into a polyethylene chain. The residual hexyl side chain provides a site for the dislocation of the periodic structure required for crystals to be formed. Another example would be the incorporation of a stereo error in the insertion of propylene. Thus, a propylene insertion with an r dyad leads similarly to a dislocation in the periodic structure required for the formation of an iPP crystal. In uniformly back-mixed polymerization processes, with a single discrete polymerization catalyst, the incorporation of these intermptions is statistical and controlled by the kinetics of the polymerization process. These statistics are known as reactivity ratios. 

The most famous mechanism, namely Cossets mechanism, in which the alkene inserts itself directly into the metal-carbon bond (Eq. 5), has been proposed, based on the kinetic study [134-136], This mechanism involves the intermediacy of ethylene coordinated to a metal-alkyl center and the following insertion of ethylene into the metal-carbon bond via a four-centered transition state. The olefin coordination to such a catalytically active metal center in this intermediate must be weak so that the olefin can readily insert itself into the M-C bond without forming any meta-stable intermediate. Similar alkyl-olefin complexes such as Cp2NbR( /2-ethylene) have been easily isolated and found not to be the active catalyst precursor of polymerization [31-33, 137]. In support of this, theoretical calculations recently showed the presence of a weakly ethylene-coordinated intermediate (vide infra) [12,13]. The stereochemistry of ethylene insertion was definitely shown to be cis by the evidence that the polymerization of cis- and trans-dideutero-ethylene afforded stereoselectively deuterated polyethylenes [138]. 

Linear combination of atomic orbitals (LCAO) method, 16 736 Linear condensation, in silanol polycondensation, 22 557-558 Linear congruential generator (LCG), 26 1002-1003 Linear copolymers, 7 610t Linear density, 19 742 of fibers, 11 166, 182 Linear dielectrics, 11 91 Linear elastic fracture mechanics (LEFM), 1 509-510 16 184 20 350 Linear ethoxylates, 23 537 Linear ethylene copolymers, 20 179-180 Linear-flow reactor (LFR) polymerization process, 23 394, 395, 396 Linear free energy relationship (LFER) methods, 16 753, 754 Linear higher a-olefins, 20 429 Linear internal olefins (LIOs), 17 724 Linear ion traps, 15 662 Linear kinetics, 9 612 Linear low density polyethylene (LLDPE), 10 596 17 724-725 20 179-211 24 267, 268. See also LLDPE entries a-olefin content in, 20 185-186 analytical and test methods for,... 

Wu, D., Chen, F. and Li, R., Reaction kinetics and simulations for solid-state polymerization of polyethylene terephthalate), Macromolecules, 30, 6737-6742 (1997). 

The workhorse polyester is polyethylene terephthalate) (PET) which is used for packaging, stretch-blown bottles and for the production of fibre for textile products. The mechanism, catalysis and kinetics of PET polymerization are described in Chapter 2. Newer polymerization techniques involving the ring-opening of cyclic polyester oligomers is providing another route to the production of commercial thermoplastic polyesters (see Chapter 3). 

---