Crosslink crystallinity

KM Lee, M Blaghen, J-P Samama, J-F Biellmann. Crosslinked crystalline horse liver alcohol dehydrogenase as a redox catalyst activity and stability toward organic solvent. Bioorg Chem 14 202-210, 1986. 

Aqueous dispersions of crosslinked crystalline polymers containing both hydrophobic and hydrophilic components have been prepared. The hydrophobic components consist of Cg-, Ci2-, C14-, and Cig-acrylates while methyacryhc acid constituted the hydrophilic comonomer. These dispersions are useful as coatings, particularly on human hair. 

Fig. 4. The five regions of viscoelastic behavior. All polymers exhibit these five regions, but crosslinking, crystallinity, and varying molecular weight alter the appearance of this generalized curve. The loss modulus Tg peak appears just after the storage modulus enters the glass transition region.

HDPE/EEDPE RT air X 100 DCP Crosslinking, crystallinity, tensile and yield strength, abrasion, modulus, DSC measurements 3... 

HDPE/NR 2 RT air, Nj 7, 1000 DCP Crosslinking, crystallinity, tensile strength, stress, elongation, SEM 40... 

Crystallinity, Stereochemistry, and Crosslinking Crystallinity has an effect on the glass transition temperature of the amorphous fraction. In most cases, Tg increases with increasing crystallinity, because crystallites immobilize the amorphous chains (they behave as physical crosslinks). But there are rare cases where Tg decreases with increasing crystallinity, as observed in bisphenol A polycarbonate (Grimau et al. 1997). 

In summary, the interdiffusion of polymer chains across a polymer/polymer interface requires the polymers (adhesive and substrate) to be mutually soluble and the macromolecules or chain segments to have sufficient mobility. These conditions are usually met in the autohesion of elastomers and in the solvent welding of compatible, amorphous plastics. In both these examples interdiffusion does appear to contribute significantly to the intrinsic adhesion. However, where the solubility parameters of the materials are not similar, or one polymer is highly crosslinked, crystalline or below its glass transition temperature, then interdiffusion is an unlikely mechanism of adhesion. In the case of polymer/metal interfaces it appears that interdiffusion can be induced and an interphase region created. But this effect enhances the interfacial adhesion by improving the adsorption of the polymeric material rather than by a classic diffusion mechanism. 

The counterion/cation effect choice of electrolyte The monomer Chemical polymerization The quest for extra functionality Molecular Structure and Microstructure of Polypyrrole Molecular Weight, Branching and Crosslinking Crystallinity and Molecular Order Surface Morphology and Film Density References... 

Differential scanning calorimetry studies have been ongoing over the past ten years at MMI. The very early work was carried out using a Ferkin-Elmer DSC-IB unit later work has been continued with a DuPont 910 DSC cell in conjunction with either the 990 or 1090 Thermal Analyzer control units. The effects of molecular weight, crosslinking, crystallinity, oxidation, copolymer composition, and tacticity on the strength of the Tu and Tip transitions have been examined. 

Stretching a polymer sample tends to orient chain segments and thereby facilitate crystallization. The incorporation of different polymer chains into small patches of crystallinity is equivalent to additional crosslinking and changes the modulus accordingly. Likewise, the presence of finely subdivided solid particles, such as carbon black in rubber, reinforces the polymer in a way that imitates the effect of crystallites. Spontaneous crystal formation and reinforcement... 

The tightrope situation that arises from balancing high mobility, low crystallinity, and optimum crosslinking is often dealt with by using copolymers rather than homopolymers. With chain composition as an additional variable, molecules can be tailored better for specific application situations. 

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. 

In the last three chapters we have examined the mechanical properties of bulk polymers. Although the structure of individual molecules has not been our primary concern, we have sought to understand the influence of molecular properties on the mechanical behavior of polymeric materials. We have seen, for example, how the viscosity of a liquid polymer depends on the substituents along the chain backbone, how the elasticity depends on crosslinking, and how the crystallinity depends on the stereoregularity of the polymer. In the preceding chapters we took the existence of these polymers for granted and focused attention on their bulk behavior. In the next three chapters these priorities are reversed Our main concern is some of the reactions which produce polymers and the structures of the products formed. 

Fig. 22. Nomialized pull-off energy measured for polyethylene-polyethylene contact measured using the SFA. (a) P versus rate of crack propagation for PE-PE contact. Change in the rate of separation does not seem to affect the measured pull-off force, (b) Normalized pull-off energy, Pn as a function of contact time for PE-PE contact. At shorter contact times, P does not significantly depend on contact time. However, as the surfaces remain in contact for long times, the pull-off energy increases with time. In seinicrystalline PE, the crystalline domains act as physical crosslinks for the relatively mobile amorphous domains. These amorphous domains can interdiffuse across the interface and thereby increase the adhesion of the interface. This time dependence of the adhesion strength is different from viscoelastic behavior in the sense that it is independent of rate of crack propagation.

TPEs from blends of rubber and plastics constitute an important category of TPEs. These can be prepared either by the melt mixing of plastics and rubbers in an internal mixer or by solvent casting from a suitable solvent. The commonly used plastics and rubbers include polypropylene (PP), polyethylene (PE), polystyrene (PS), nylon, ethylene propylene diene monomer rubber (EPDM), natural rubber (NR), butyl rubber, nitrile rubber, etc. TPEs from blends of rubbers and plastics have certain typical advantages over the other TPEs. In this case, the required properties can easily be achieved by the proper selection of rubbers and plastics and by the proper change in their ratios. The overall performance of the resultant TPEs can be improved by changing the phase structure and crystallinity of plastics and also by the proper incorporation of suitable fillers, crosslinkers, and interfacial agents. 

Homopolymerization of macroazoinimers and co-polymerization of macroinimers with a vinyl monomer yield crosslinked polyethyleneglycol or polyethyleneglycol-vinyl polymer-crosslinked block copolymer, respectively. The homopolymers and block copolymers having PEG units with molecular weights of 1000 and 1500 still showed crystallinity of the PEG units in the network structure [48] and the second heating thermograms of polymers having PEG-1000 and PEG-1500 units showed that the recrystallization rates were very fast (Fig. 3). 

Finkelmann et al. 256 274,2781 have also investigated the synthesis and the characteristics of siloxane based, crosslinked, liquid crystalline polymers. This new type of materials displays both liquid crystallinity and rubber elasticity. The synthesis of these networks is achieved by the hydrosilation of dimethylsiloxane-(hydrogen, methyl)siloxane copolymers and vinyl terminated mesogenic molecules in the presence of low molecular weight a,co-vinyl terminated dimethylsiloxane crosslinking agents156 ... 

Covalently crosslinked siloxane containing liquid crystalline networks with elastic properties were prepared 349). In all of the networks liquid crystalline phases of the linear precursors were retained. For low degrees of crosslinking the phase transition temperatures remained nearly unchanged, whereas higher degrees of crosslinking reduced the phase transition temperatures. 

Crosslinking is not the only feature that may influence solubility. Such features as crystallinity, hydrogen bonding, or the absence of chain branching may all increase the resistance of a given specimen of polymer to dissolve. Some of these features are discussed later in the chapter. 

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