Molecular Weight Distribution Modeling of Radical Polymerization in a CSTR with Long Chain Branching through Transfer to Polymer and Terminal Double Bond (TDB) Propagation

2003 ◽  
Vol 36 (2) ◽  
pp. 458-476 ◽  
Author(s):  
Piet D. Iedema ◽  
Snezana Grcev ◽  
Huub C. J. Hoefsloot
Keyword(s):  
Molecular Weight ◽  
Double Bond ◽  
Radical Polymerization ◽  
Molecular Weight Distribution ◽  
Weight Distribution ◽  
Chain Branching ◽  
Long Chain Branching ◽  
Terminal Double Bond ◽  
Distribution Modeling ◽  
Long Chain

Rheological Properties of cis-Polybutadiene

1965 ◽  
Vol 38 (4) ◽  
pp. 907-920
Author(s):  
Gerard Kraus ◽  
J. T. Gruver
Keyword(s):  
Molecular Weight ◽  
Molecular Weight Distribution ◽  
Weight Distribution ◽  
Average Molecular Weight ◽  
Tensile Creep ◽  
Capillary Viscometer ◽  
Chain Branching ◽  
Long Chain Branching ◽  
Long Chain ◽  
Newtonian Behavior

Abstract The steady-state viscosity of a number of cis-polybutadienes was determined as a function of shear rate and temperature by use of a capillary rheometer. Polymers investigated differed in molecular weight distribution and long chain branching. None of the polymers exhibited Newtonian behavior, even at the lowest shear rates attainable. Nevertheless, for polymers of similar molecular weight distribution and minimum branching, all the capillary viscometer data could be reduced to a single curve by a reduced variable treatment. The molecular weight shift function was found to be the same as for polymers exhibiting a Newtonian flow range, i.e., a 3.4th power law in weight-average molecular weight. Broadening the molecular weight distribution or increasing the degree of long-chain branching led to increasingly pronounced non-Newtonian behavior. Tensile creep experiments showed nonlinear viscoelastic behavior for all polymers studied, even at small strains. This behavior was most pronounced in the more highly branched polymers. At very low stresses some of these polymers exhibited extremely high viscosities, the strain being almost completely recoverable. Under larger stresses the viscosity of these rubbers dropped several decades and in the capillary extrusion experiments these polymers flowed readily. This is the same behavior observed previously in high molecular weight branched (multichain) narrow distribution polybutadienes. It is tentatively explained by a constraint of the branch points on the slippage of chain entanglements. The fact that all cis-polybutadienes exhibit this behavior, while linear polybutadienes made by organolithium initiation do not, suggests that all cis-polybutadienes may be branched to some extent.

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