Polymeric chain entanglement

Song and coworkers [8] established a double-network model, which consisted of the segments, E and A-constituent chains, the polymeric chains entangled with other ones by multi-entanglement and polymeric chains connected to a great number of destructible particles by multi-adsorption, based on which the E and A-constituent chains could be recreated and released dynamically. 

In the literature there is only one serious attempt to develop a detailed mechanistic model of free radical polymerization at high conversions (l. > ) This model after Cardenas and 0 Driscoll is discussed in some detail pointing out its important limitations. The present authors then describe the development of a semi-empirical model based on the free volume theory and show that this model adequately accounts for chain entanglements and glassy-state transition in bulk and solution polymerization of methyl methacrylate over wide ranges of temperature and solvent concentration. 

In applying equation (l) Cardenas and 0 Driscoll use Xq as the critical chain length for chain entanglement and permit Xq to decrease as ( )p increases during the polymerization according to equation (l). Therefore, during the course of polymerization they note three kinds of termination reactions ... 

This is a theoretical study on the entanglement architecture and mechanical properties of an ideal two-component interpenetrating polymer network (IPN) composed of flexible chains (Fig. la). In this system molecular interaction between different polymer species is accomplished by the simultaneous or sequential polymerization of the polymeric precursors [1 ]. Chains which are thermodynamically incompatible are permanently interlocked in a composite network due to the presence of chemical crosslinks. The network structure is thus reinforced by chain entanglements trapped between permanent junctions [2,3]. It is evident that, entanglements between identical chains lie further apart in an IPN than in a one-component network (Fig. lb) and entanglements associating heterogeneous polymers are formed in between homopolymer junctions. In the present study the density of the various interchain associations in the composite network is evaluated as a function of the properties of the pure network components. This information is used to estimate the equilibrium rubber elasticity modulus of the IPN. 

Branched polymeric materials have different properties than their linear counterparts. In the case of star-branched polymers (multiple branches radiating from a single site), enhanced engineering properties are possible from increased chain entanglements. The initial goal of this research was to create a material with enhanced performance properties via a star-branched network. 

Note 2 A model network is not necessarily a perfect network. If a non-linear polymerization is used to prepare the network, non-stoichiometric amounts of reactants or incomplete reaction can lead to network containing loose ends. If the crosslinking of existing polymer chains is used to prepare the network, then two loose ends per existing polymer chain result. In the absence of chain entanglements, loose ends can never be elastically active network chains. 

In this relation, 2C2 provides a correction for departure of the polymeric network from ideality, which results from chain entanglements and from the restricted extensibility of the elastomer strands. For filled vulcanizates, this equation can still be applied if it can be assumed that the major function of the dispersed phase is to increase the effective strain of the rubber matrix. In other words, because of the rigidity of the filler, the strain locally applied to the matrix may be larger than the measured overall strain. Various strain amplification functions have been proposed. Mullins and Tobin33), among others, suggested the use of the volume concentration factor of the Guth equation to estimate the effective strain U in the rubber matrix ... 

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