Crosslinked fractions crosslinking

Suppose the un-cross-linked polymer chain has a molecular weight M which, upon crosslinking, is divided into subchains of molecular weight M, . This means that each subchain is a fraction of the original chain. Since the crosslink... 

An important application of Eq. (3.39) is the evaluation of M, . Flory et al.t measured the tensile force required for 100% elongation of synthetic rubber with variable crosslinking at 25°C. The molecular weight of the un-cross-linked polymer was 225,000, its density was 0.92 g cm , and the average molecular weight of a repeat unit was 68. Use Eq. (3.39) to estimate M. for each of the following samples and compare the calculated value with that obtained from the known fraction of repeat units cross-linked ... 

Between T j, and Tg, depending on the regularity of the polymer and on the experimental conditions, this domain may be anything from almost 100% crystalline to 100% amorphous. The amorphous fraction, whatever its abundance, behaves like a supercooled liquid in this region. The presence of a certain degree of crystallinity mimics the effect of crosslinking with respect to the mechanical behavior of a sample. 

Tirrell et al. [42,43] studied the role of interfacial chains in a more detailed fashion. Tirrell et al. [42,43] used a crosslinked PDMS cap in contact with a silicon wafer on to which a,o)-hydroxyl terminated PDMS chains are tethered by adsorption from a solution. The molecular weight of the narrow disperse PDMS samples was in the range of 20,000-700,000. The surface chain density was given by27 yj g e 0 is the volume fraction of PDMS in solution. 

It is basically a fractionation process that depends not only on molecular size, but also on chemical composition, stereo-configuration, branching, and crosslinking. For multicomponent systems, fractionation with different ion polymolecularity, chemical heterogeneity and sequence length distribution, solubility or elution fractionation is of primary importance. Therefore, gel permeation chromatography or size exclusion chromatography is used as an important tool for the characterization of PBAs. 

PF.O)l, crosslinked network, t (Polyin), various polymers, t Current fraction. 

Fig. 19. Selective bonding of novobiocin by crosslinked polyelectrolytes ARA-3p-T-40 (1 and 4) and ARA-lp-T-40 (2 and 3) with different grain sizes I) and 2) 10 pm 3) and 4) 200 pm. Nrmolar fraction of novobiocine in the ion exchanger...

Serious deviations of the polymer network structure from the ideal one can have several causes. One of them is the crosslinking agent involvement in intramolecular cycle formation. The contribution of this reaction grows with the system dilution as well as when the crosslinker units in the chain are close one to the other, i.e. its fraction in the copolymer increases. All this is in good agreement with the observed trend. 

The second reason is of kinetic nature and due to a substantially lower reactivity of the pendant acrylic groups. Some experimental facts may be considered a direct evidence of this possibility. Thus, the absorption in the region of 280 nm in the UV spectrum points to a growth of the residual concentration of acrylamide groups with an increasing fraction of the crosslinker [25]. The same groups can... 

The free volume model seems to be more adequate to describe the plasticization behaviour of the systems of lower amine content. According to Eq. (5), the higher is the change of the expansion coefficient the lower is the influence of the diluent volume fraction. The three TGDDM-DDS mixtures cured with 20, 30 and 50 PHR of hardener were characterized l2) by changes of the expansion coefficient at the glass transition, respectively, of 0.63, 1.08 and 2.94x 10 3 °C l. The more dense and stiffer resin crosslinked with 50 PHR of DDS should be, in principle, the less... 

The pre-gel model calculates the weight average molecular weight of the reaction mixture, while the post-gel model calculates the weight of the sol fraction and the effective crosslink density. A simple computer program using the derived expressions has been written in BASIC and runs on IBM-PC compatible computers. The importance of secondary reactions on cure in typical coatings is discussed. 

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... 

If the mixture has gelled, the program proceeds to calculate P(Fa° ) and P(Fg° ) using a binary search method (lines 2510-2770). This method is more convenient that the earlier approach of Bauer and Budde (10) who used Newton s method, since derivatives of the functions are not required. The program also calculates the probability generating functions used to calculate sol fractions and the two crosslink densities (lines 2800-3150). Finally, the sol fraction and crosslink densities are calculated and printed out (lines 3160-3340). The program then asks for a new percents of reaction for the A and B groups. To quit enter a percent reaction for A of >100. 

PRINT "THE WEIGHT FRACTION OF CROSSLINKER IN THE MIXTURE - " WB 2090 PRINT... 

PRINT "THE FRACTION OF B SELF-CONDENSATION CROSSLINKS - " FRAC 3270 PRINT 3280 PRINT... 

For this low mole fraction of divinyl monomer (f2o 1-52 xlO ) the effect of cyclization should not be significant, and the calculated results for weight fraction of gel agree with experimental data satisfactorily. But to accurately calculate the structural properties of the gel such as crosslinking density, it will be necessary to consider the effect of cyclization. 

Repeated addition of MDC to Q11 did occur, but the dominant product was Q11 with a single MDC. The fraction of Qll with higher numbers of attached MDC decreased for increasing MDC number. Separately, a lysine peptide that contained the bioactive RGD [73] sequence ( -dansyl-GLKGGRGDS-Am) was successfully TGase crosslinked with self-assembled Qll five distinct Qll-dansyl RGD were detected by mass spectrometry. 

Rat liver nuclei (chromato-graphically separated DNA fractions) DNA-protein crosslinks No data Keller and Heck 1988 =... 

Further indications for an additional subunit were provided by a crosslinking analysis of C Eg solubilized H,K-ATPase, which exhibited ATPase and phosphatase activities, and ligand affinities comparable to the native enzyme [70]. Glutar-aldehyde treatment of soluble protein fractions resolved on a linear glycerol gradient revealed no active fraction enriched in monomeric (A/p = 94 kDa) H,K-ATPase. Instead, K -ATPase activity was only obtained in fractions enriched in particles of Mr = 175 kDa. This size also suggested that the functional H,K-ATPase unit is a heterodimer of a catalytic subunit and an additional subunit, since the apparent molecular mass of 175 kDa is probably too small to be a homodimer of the catalytic subunit. 

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