Entanglement networks 1,2-polybutadiene

Since the excellent work of Moore and Watson (6, who cross-linked natural rubber with t-butylperoxide, most workers have assumed that physical cross-links contribute to the equilibrium elastic properties of cross-linked elastomers. This idea seems to be fully confirmed in work by Graessley and co-workers who used the Langley method on radiation cross-linked polybutadiene (.7) and ethylene-propylene copolymer (8) to study trapped entanglements. Two-network results on 1,2-polybutadiene (9.10) also indicate that the equilibrium elastic contribution from chain entangling at high degrees of cross-linking is quantitatively equal to the pseudoequilibrium rubber plateau modulus (1 1.) of the uncross-linked polymer. 

The two-network method has been carefully examined. All the previous two-network results were obtained in simple extension for which the Gaussian composite network theory was found to be inadequate. Results obtained on composite networks of 1,2-polybutadiene for three different types of strain, namely equibiaxial extension, pure shear, and simple extension, are discussed in the present paper. The Gaussian composite network elastic free energy relation is found to be adequate in equibiaxial extension and possibly pure shear. Extrapolation to zero strain gives the same result for all three types of strain The contribution from chain entangling at elastic equilibrium is found to be approximately equal to the pseudo-equilibrium rubber plateau modulus and about three times larger than the contribution from chemical cross-links. 

A new stress-relaxation two-network method is used for a more direct measurement of the equilibrium elastic contribution of chain entangling in highly cross-linked 1,2-polybutadiene. The new method shows clearly, without the need of any theory, that the equilibrium contribution is equal to the non-equilibrium stress-relaxation modulus of the uncross-linked polymer immediately prior to cross-linking. The new method also directly confirms six of the eight assumptions required for the original two-network method. 

It is clearly shown that chain entangling plays a major role in networks of 1,2-polybutadiene produced by cross-linking of long linear chains. The two-network method should provide critical tests for new molecular theories of rubber elasticity which take chain entangling into account. 

Kraus,G., Moczygemba,G.A. Chain entanglements and elastic behavior in polybutadiene networks. J. Polymer Sci. Part A 2,277-288 (1964). 

The cross-linking of 1,2-polybutadiene strained in simple extension has been described in previous papers of this series.When a strained sample with stretch ratio X is crosslinked with y irradiation near the glass-transition temperature (T ), the resulting cross-link network traps the entanglemints originally present after release and warming, the sample seeks a state of ease with stretch ratio Xg in which the forces associated with the cross-links and the trapped entanglements act in opposite directions. 

This article presents uniaxial extension measurements on cis-1,4-polybutadiene networks of known junction functionality. The observed values of the reduced force from uniaxial extension measurements conform to the constrained junction theory of Flory. The reduced force intercept at 1/cX = 0 is fully comprehensible in terms of the cycle rank of the network, and can be calculated from chemical considerations. This holds even though the polybutadiene melt has a high plateau modulus. Therefore, discrete topological entanglements do not contribute perceptibly to the equilibrium modulus of polybutadiene networks. 

Hvidt S, Kramer O, Batsberg W, Ferry JD (1980) Contribution of entanglements to the equilibrium modulus of 1,2-polybutadiene networks at small strains and estimate of the fi"ont factor. Macromolecules 13(4) 933-939... 

The different forms of the modulus are still widely disputed and different opinions are expressed in the literature. Hsu and Mark " " prepared networks of polybutadiene by endlinking. According to dynamic measurements polybutadiene has a high plateau modulus in viscoelasticity and one can expect a strong contribution to the modulus from entanglements. In this study experiments have been fitted to the stress-strain relations with the Flory constraint-fluctuation model as in ref. 245. The authors concluded that there is no contribution from entanglements to the modulus. The same conclusion was drawn in refs. 245-248. 

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