Molecular weight alkyd

Substituted nonheat-reactive resins do not form a film and are not reactive by themselves, but are exceUent modifier resins for oleoresinous varnishes and alkyds. Thein high glass-transition temperature and molecular weight provide initial hardness and reduce tack oxygen-initiated cross-linking reactions take place with the unsaturated oils. 

Fatty Acid Process. When free fatty acids are used instead of oil as the starting component, the alcoholysis step is avoided. AH of the ingredients can therefore be charged into the reactor to start a batch. The reactants are heated together, under agitation and an inert gas blanket, until the desired endpoint is reached. Alkyds prepared by the fatty acid process have narrower molecular weight distribution and give films with better dynamic mechanical properties (34). 

One of the important attributes of alkyds is their good compatibiUty with a wide variety of other coating polymers. This good compatibiUty comes from the relatively low molecular weight of the alkyds, and the fact that the resin stmcture contains, on the one hand, a relatively polar and aromatic backbone, and, on the other hand, many aUphatic side chains with low polarity. An alkyd resin in a blend with another coating polymer may serve as a modifier for the other film-former, or it may be the principal film-former and the other polymer may serve as the modifier for the alkyd to enhance certain properties. Examples of compatible blends foUow. 

Epoxy ester Epoxy esters are a type of alkyd where a high molecular weight resin is reacted with alkyd resin. The curing mechanism remains primarily through the oil-oxidation reaction and their properties are in no way similar to the chemically reacted epoxies. They have similar properties to alkyds although with improved chemical resistance but inferior appearance. They form a reasonably hard, oil-resistant coating, which can sometimes be suitable for machinery enamels, but are primarily for interior use, since they tend to chalk rapidly on exteriors. Their best use is for chemical or water resistance where circumstances dictate that finishes that are more superior cannot be used. 

Modified alkyd resins In this group one finds styrenated alkyds, vinyl toluenated alkyds, oil-modified vinyl resins, acrylic alkyds, silicone alkyds and polyurethane alkyds. The modifying component usually has a number of effects. It always increases the molecular weight of the alkyd polymer, and may impart hardness, durability, or chemical resistance. It also affects the solubility of the polymer in solvents. 

Chemoenzymatic synthesis of alkyds (oil-based polyester resins) was demonstrated. PPL-catalyzed transesterification of triglycerides with an excess of 1,4-cyclohexanedimethanol mainly produced 2-monoglycerides, followed by thermal polymerization with phthalic anhydride to give the alkyd resins with molecular weight of several thousands. The reaction of the enzymatically obtained alcoholysis product with toluene diisocyanate produced the alkyd-urethane. 

Covalent polymeric networks which are completely disordered. Continuity of structure is provided by an irregular three-dimensional network of covalent links, some of which are crosslinks. The network is uninterrupted and has an infinite molecular weight. Examples are vulcanized rubbers, condensation polymers, vinyl-divinyl copolymers, alkyd and phenolic resins. 

Decreasing the viscosity of the currently applied synthetic alkyd resins reduces the amount of organic solvent that is needed in these paints for optimal performance. This could either be accomplished by decreasing the molecular weight of the applied alkyd resin, or by using polymers having a narrower... 

Pettersson and Sorensen have described a number of different thermoset resin structures based on hyperbranched aliphatic polyesters [123]. Their results can best be exemplified by a study on hyperbranched alkyd coating resins. A comparative study was performed between an alkyd resin based on a hyperbranched aliphatic polyester and a conventional high solid alkyd, which is a less branched structure. The hyperbranched resin had a substantially lower viscosity than the conventional resin of comparable molecular weight, that is, less solvent was needed to obtain a suitable application viscosity. The hyperbranched resin also exhibited much shorter drying times than the conventional resin, although the oil content was similar. These achievements would not have been possible without a change in architecture of the backbone structure of the resins (Figs. 12,13). 

From an industrial point of view, not only the high-molecular-weight linear polyesters are of interest. Also, a series of low-molecular-weight linear or branched polyesters (Example 4-1) find application in surface coating systems (alkyd resins), as coreactants in unsaturated polyester resins (Example 4-8), or in polyurethane foams (Examples 5-28 and 5-29). 

Since carbocations are involved in cationic polymerization, a possible side reaction is their isomerization through hydride (alkyde) migration to more stable (less reactive) carbocations. This can lead to a polymer of broad molecular weight distribution or, if the isomerization is irreversible, to termination. 

FIGURE 2-17. Contribution of molecular weight to polymer properties, (a) Molecular weight distribution profile of a typical polymer. (b) Quality control of an alkyd resin. It was determined that a good paint resulted only when the ratio of the peak heights was between 0.6 and 0.8. Detector refractive index. 

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