Cross-link tendency

Whereas monoallyl derivatives sdeld thermoplastic polymers, allyl esters containing two or more unsaturated groups yield thermosetting resins. Thus, monoallyl esters of unsaturated acids, e.g., allyl acrylate, allyl methacrylate, allyl crotonate, and allyl itaconate, and diallyl esters of dibasic acids, e.g., diallyl oxalate, diallyl phthalate, and diallyl itaconate, yield thermoset resins, which generally combine solvent resistance, toughness, hardness, transparency, and heat resistance. The cross-linking tendency of the allyl esters makes them useful in copolymerization wherein they impart these properties to normally linear polymers. 

Ethylene-glycidyl methacrylate copolymer (E-GMA) Epoxide 3-8 % GMA Moderate high reactivity with carboxyl group of PA Tg and hardness limit achievable toughness cross-linking tendency... 

Ethene is the principal co-monomer ( 60-80%) in poly(elhene/vinyl acetate) (EVA) copolymers (Zutty et al., 1967). The vinyl acetate (VAC) component reduces crystallinity and increases flexibility (Tg below O C). It also inaeases adhesion and solubility (Appendix 3). The presence of VAC in the copolymer reduces the cross-linking tendency under ultraviolet ageing until at 25% VAC this reaction is negligible (Feller and Curran, 1970). 

On curing, amino resins not only react with the nucleophilic sites (hydroxyl, carboxyl, amide) on the other film formers in the formulation, but also self-condense to some extent. Highly alkylated amino resins have less tendency to self-condense (33,34) and are therefore effective cross-linking agents, but may require the addition of a strong acid catalyst to obtain acceptable cure even at bake temperatures of 120—177°C. 

For increased solubiHty to prevent bloom, shorter-chain carboxyHc acids or zinc carboxylates can be substituted. The use of chain-branched carboxyHc acids reduces the tendency for the formulations to lose sulfur cross-links or revert upon prolonged heating (7). Translucent articles such as crepe soles can use a zinc carboxylate or employ zinc carbonate as a transparent zinc oxide. 

Flame retardant grades usually employ additives (but see below), e.g. sodium 2,4,5-trichlorobenzene sulphonate, sometimes in conjunction with an antidripping agent which, it is claimed, cross-links the polymer as it bums thus reducing the tendency to drip. 

Flame retardant grades may not only use additives such as sodium 2,4,5-trichlorobenzene sulphonate but also an anti-dripping agent which can cause cross-linking as the polymer bums, thus reducing the tendency to drip. 

The general properties of the resins are much as to be expected. They have very good heat resistance but are mechanically much weaker than the corresponding organic cross-linked materials. This weakness may be ascribed to the tendency of the polymers to form ring structures with consequent low cross-linking efficiency and also to the low intermolecular forces. 

Polyisobutylene has a similar chemical backbone to butyl rubber, but does not contain double carbon-carbon bonds (only terminal unsaturation). Many of its characteristics are similar to butyl rubber (ageing and chemical resistance, low water absorption, low permeability). The polymers of the isobutylene family have very little tendency to crystallize. Their strength is reached by cross-linking instead of crystallization. The amorphous structure of these polymers is responsible for their flexibility, permanent tack and resistance to shock. Because the glass transition temperature is low (about —60°C), flexibility is maintained even at temperatures well below ambient temperature. 

Although the picture is far from complete, the available evidence suggests that PBPP is rather different from most polyphosphazenes. The polymer may be induced to be an electronic conductor, but perhaps as a result of this tendency to cross-link, the material is more sensitive and difficult to handle than most polyphosphazenes and the thermal depolymerization reaction is inhibited. 

The elastic contribution to Eq. (5) is a restraining force which opposes tendencies to swell. This constraint is entropic in nature the number of configurations which can accommodate a given extension are reduced as the extension is increased the minimum entropy state would be a fully extended chain, which has only a single configuration. While this picture of rubber elasticity is well established, the best model for use with swollen gels is not. Perhaps the most familiar model is still Flory s model for a network of freely jointed, random-walk chains, cross-linked in the bulk state by connecting four chains at a point [47] ... 

A chiral diphosphine ligand was bound to silica via carbamate links and was used for enantioselective hydrogenation.178 The activity of the neutral catalyst decreased when the loading was increased. It clearly indicates the formation of catalytically inactive chlorine-bridged dimers. At the same time, the cationic diphosphine-Rh catalysts had no tendency to interact with each other (site isolation).179 New cross-linked chiral transition-metal-complexing polymers were used for the chemo- and enantioselective epoxidation of olefins.180... 

An important factor in all these experiments is the choice of bead used to immobilize the probe. Biochemists have considered cross-linked agarose beads to be exceptionally hydrophilic with a low tendency to bind proteins nonspecifically, and these beads have the further attraction of being commercially available in activated forms (succinimidyl esters, epoxides, and maleimides, for example). However, early trials of bead-based chemical proteomics have shown that many proteins in mammalian cell lysates bind tenaciously to agarose beads. This was unimportant in many studies in which protein-protein interactions were detected by coimmunoprecipitation with immunochemical... 

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