Polymer crosslink density

The presence of these ionic materials at the interface, as well as the corresponding reduction of polymer crosslink density associated with this degradative process, likely contribute to the observed reduction in bond durability. 

Acrylic polymers have the advantage that they can be formulated to be inherently tacky. However, for certain applications it may be desirable to adjust the rheological properties of the PSA beyond what can be obtained by selecting the right polymer composition and crosslink density. 

Fluorosilicones consist of PDMS backbones with some degree of fluoro-aliphatic side chains. The fluorinated group can be trifluoropropyl, nonafluorohexylmethyl, or fluorinated ether side group [78,28,79]. These polymers differ not only in substituent group, but also in the amount of fluoro-substitution relative to PDMS, the overall molecular weight and crosslink density, and the amount of branching. In most commercially available cases, these polymers are addition cure systems and the reactions are those discussed previously for silicone networks. 

An EB-curable struetural adhesive formulation usually eonsists of one or more crosslinkable oligomeric resins or prepolymers, along with such additives as reactive diluents, plasticizers, and wetting agents. The oligomer is an important component in terms of the development of mechanical properties. The adhesive and cohesive properties depend on the crosslink density, chemical group substitution, and molecular organization within the polymer matrix. Adhesion is achieved... 

Crosslinked polymers are rather peculiar materials in that they never melt and they exhibit entropic elasticity at elevated temperatures. The present review on the influence of crosslink density is structured around model polymers of uniform composition but with widely varying numbers of crosslinks. The degree of crosslinking in the polymers was verified by use of the theory of rubber elasticity. 

Therefore, a different approach was followed in the present paper in order to improve the understanding of the relationship between the structure and the behavior of crosslinked polymers. A series of directly comparable model polymers were prepared with crosslink densities varying from high (thermoset) to zero (thermoplastic). Five polymers with well defined crosslink densities [11] were tested at various levels of deformation. This approach produced a small but assessable and fairly consistant body of results. Basic relationships derived from these results were related to corresponding results from the literature. 

The activation volume of the three polymers turned out to be v 2 nm3, independent of their crosslink density. In the crosslinked polymer A the strands are short and about five of them fit into the activation volume. In contrast, one strand of polymer E requires a volume five times larger than the activation volume ... 

Once P(F ° ) and P(Fg° ) have been calculated, it is possible to calculate a number of network structure parameters including the weight fraction of sol, wg, and the "effective" crosslink density. A given polymer or crosslinker will be part of the sol only if all of its groups are attached to finite chains. Thus, the weight of the sol is given by... 

It is possible to calculate a number of different kinds of "effective" crosslink densities. Bauer et al have used a quantity they termed the "elastically effective crosslink density " (Cel) correlate cure with solvent resistance and other physical properties of coatings (7-10). The correlation was basically empirical. Formally, the is a calculation of the number of functional groups attached to the infinite network for which there are at least two other paths out to the network on the given polymer or crosslinker. Thus, chains with only one or two paths to the infinite network are excluded. The following expression can be written for... 

Crosslihkinq Density Distribution. Let us consider the statistical copolymerization of vinyl/divinyl monomers without chain transfer to polymer for simplicity. In this case the crosslinking density p is defined as follows. 

Using Equation 5 and 6, it is possible to calculate the crosslinking density distribution as a function of the birth conversion (0). Figure 1 shows one of the calculation results. Though it is quite often assumed that the crosslinking density is the same for all polymer molecules, this assumption is not valid for free radical polymerization. Generally, this distribution becomes significant when the conditions deviate from the idealized Flory s conditions, namely, 1) the reactivities of all types of... 

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