Long chain branching polymerization

Indeed this leads to more short-chain branches in the case of the shorter alkenylsilanes but the efficiency of the long-chain branch (polymeric branch) is higher for the longer alkenylsilanes. Thus, the gel permeation chromatography multiangle laser light scattering (GPC-MALLS)-derived LCB data indicate that the ratio of LCB to total branch content increases in the order... 

Components of a highly short chain branched (scb) waxymaize and a more long chain branched (Icb) amylomaize were separated on the semipreparative Sephacryl S-1000 system. Both samples contained high dp components that eluted in the exclusion volume, but the percentage of these components was quite different 90% for the scb waxymaize starch and approximately 10% for the Icb amylomaize starch (Fig. 16.6). The degree of polymerization averages for these samples was determined utilizing the previously established linear... 

Sharkey, W. H. Polymerizations Through the Carbon-Sulphur Double Bond. VoL 17, pp. 73-103. Shimidzu, T. Cooperative Actions in the Nucleophile-Containing Polymers. Vol. 23, pp. 55-102. Slichter, W. P. The Study of High Polymers by Nuclear Magnetic Resonance. VoL 1, pp. 35-74. Small, P. A. Long-Chain Branching in Polymers. VoL 18,pp. 1-64. 

The presence of long chain branches in low density polyethylene (LDPE) accounts for the difference in properties e.g. higher melt strength, greater toughness for the same average molecular weight) between LDPE and linear low density polyethylene (LLDPE, made by coordination polymerization). 

Copolymerization of macromonomers formed by backbiting and fragmentation is a second mechanism for long chain branch formation during acrylate polymerization (Section 4.4.3.3). The extents of long and short chain branching in acrylate polymers in emulsion polymerization as a function of conditions have been quantified.20 ... 

SOLUTION OF KINETIC EQUATIONS FOR LONG CHAIN BRANCHING IN BULK VINYL ACETATE POLYMERIZATION ... 

We can create crosslinks during chain growth polymerization by copolymerizing dienes with vinyl monomers. When the two vinyl functions of the diene are incorporated into separate chains, a crosslink is formed. This process is shown in Fig. 2.18. When we use a low concentration of dienes, we produce a long chain branched polymer, while high concentrations of dienes create a highly crosslinked polymer network... 

Figure 5.13 Example of backbiting reaction to form a long chain branch during the high pressure polymerization of polyethylene...

Research on the modelling, optimization and control of emulsion polymerization (latex) reactors and processes has been expanding rapidly as the chemistry and physics of these systems become better understood, and as the demand for new and improved latex products increases. The objectives are usually to optimize production rates and/or to control product quality variables such as polymer particle size distribution (PSD), particle morphology, copolymer composition, molecular weights (MW s), long chain branching (LCB), crosslinking frequency and gel content. 

One chapter in this series deals with the newer use of cationic polymerization to form polymers and copolymers with controlled long-chain branched struc-... 

Note 2 A polymeric side-chain may be termed a long-chain branch. 

Radical chain polymerization of ethylene to polyethylene is carried out at high pressures of 120-300 MPa (17,000-43,000 psi) and at temperatures above the Tm of polyethylene (Fig. 3-18) [Doak, 1986]. Batch processes are not useful since the long residence time gives relatively poor control of product properties. Long-chain branching due to intermolecular chain transfer becomes excessive with deleterious effects on the physical properties. Continuous processes allow better control of the polymerization. 

Long-chain branching (LCB), generally less than 0.1 branch per 1000 carbons, has been observed in some metallocene polymerizations of ethylene and propene [Nele and Soares, 2002 Soares, 2002 Weng et al., 2002]. The presence of even small amounts of LCB improves melt strength and melt processability of narrow PDI polymers. Thus, it is often useful to choose conditions, such as the metallocene, temperature, and other reaction conditions, that deliberately introduce long chain branching. 

Long-chain branching via the in situ formation of vinyl macromonomers is also accessible with CpA initiators. A key feature of CpA initiators is that polymerizations can be carried out at higher temperatures (>100°C) to generate the vinyl macromonomer without loss of activity. 

Both Ni and Pd initiators polymerize propene to give a combination of different microstructures, including 1,2- and 3,1-placements as well as methyl branches (via 2,3-placement) and long-chain branching. Room-temperature polymerizations with both Ni and Pd initiators yield atactic polypropene. Low temperature polymerizations proceed by chain end control to yield moderate syndioselectivity, (rr) as high as 0.8, but usually less [Busico and Cipullo, 2001 McCord et al, 2001 Pappalardo et al., 2000 Zambelli et al., 2001]. 

The chain transfer to polymer process that produces long-chain branching is also a graft polymerization process (Sec. 3-6d). 

The second possible route is called grafting from . This means that active sites are generated at the polymer backbone A which initiate the polymerization of monomer B, thus leading to long-chain branches ... 

They are able to polymerize a large variety of vinyl monomers. The polymer microstructure can be controlled by the symmetry of the catalyst precursor. Prochiral alkenes such as propylene can be polymerized to give stereospecific polymers,554 572-574 allowing production of polyolefin elastomers. They can give polyolefins with regularly distributed short- and long-chain branches which are new materials for new applications. 

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