Polyfunctional

Nuzzo R G, Dubois L FI and Allara D L 1990 Fundamental-studies of microscopic wetting on organic-surfaces. 1. formation and structural characterization of a self-consistent series of polyfunctional organic monolayers J. Am. Chem. Soc. 112 558-69... 

The modem era of biochemistry and molecular biology has been shaped not least by the isolation and characterization of individual molecules. Recently, however, more and more polyfunctional macromolecular complexes are being discovered, including nonrandomly codistributed membrane-bound proteins [41], These are made up of several individual proteins, which can assemble spontaneously, possibly in the presence of a lipid membrane or an element of the cytoskeleton [42] which are themselves supramolecular complexes. Some of these complexes, e.g. snail haemocyanin [4o], are merely assembled from a very large number of identical subunits vimses are much larger and more elaborate and we are still some way from understanding the processes controlling the assembly of the wonderfully intricate and beautiful stmctures responsible for the iridescent colours of butterflies and moths [44]. 

Polyfunctional molecules (glycols, dibasic acids, hydroxy acids, diamides, etc.). 

If the target molecule is polyfunctional the synthons must contain more than one functional group. 

Table III-IO6 Thiazoles substituted by one polyfunctional group Table III-107 Thiazoles substituted by several polyfunctional groups...

Alkyds are formulated from polyester resins, cross-linking monomers, and fillers of mineral or glass. The unsaturated polyester resins used for thermosetting alkyds are the reaction products of polyfunctional organic alcohols (glycols) and dibasic organic acids. 

The common method of naming aldehydes corresponds very closely to that of the related acids (see Carboxylic acids), in that the term aldehyde is added to the base name of the acid. For example, formaldehyde (qv) comes from formic acid, acetaldehyde (qv) from acetic acid, and butyraldehyde (qv) from butyric acid. If the compound contains more than two aldehyde groups, or is cycHc, the name is formed using carbaldehyde to indicate the functionaUty. The lUPAC system of aldehyde nomenclature drops the final e from the name of the parent acycHc hydrocarbon and adds al If two aldehyde functional groups are present, the suffix -dialis used. The prefix formjlis used with polyfunctional compounds. Examples of nomenclature types are shown in Table 1. 

Haloall lation. Haloalkyl groups can be introduced directiy by processes similar to Friedel-Crafts alkylation into aromatic and, to some extent, ahphatic compounds. Because halo alkylations involve bi- or polyfunctional alkylating agents, they must be performed under conditions that promote the initial halo alkylation but not, to any substantial degree, subsequent further alkylations with the initially formed haloalkylated products. 

Another use is of minor proportions of polyfunctional aHyl esters, eg, diaHyl maleate, ttiaHyl cyanurate, and ttiaHyl isocyanurate, for cross-linking or curing preformed vinyl-type polymers such as polyethylene and vinyl chlotide copolymers. These reactions ate examples of graft copolymerization in which specific added peroxides or high energy radiation achieve optimum cross-linking (see Copolymers). 

The DADC monomer has been copolymerized with small amounts of polyfunctional methacryflc or acryflc monomers. For example, 3% triethylene glycol dimethacrylate was used as a flexibiflzing, cross-linking agent with a percarbonate as initiator (26). CR-39 and diethylene glycol diacrylate containing isopropyl percarbonate were irradiated with a mercury lamp to a 92% conversion and then cured at 150°C (27). By a similar two-step process DADC was copolymerized with methyl methacrylate and tetraethylene glycol dimethacrylate (28). 

Theoretical calculations to predict the conversions at which gelation of polyfunctional monomers occur are reviewed in reference 40. The gelations of DAP, DAIP, and diallyl terephthalate (DATP) near 25% conversion are Httle affected by conditions and are much higher than predicted. 

In studies of the polymerization kinetics of triaUyl citrate [6299-73-6] the cyclization constant was found to be intermediate between that of diaUyl succinate and DAP (86). Copolymerization reactivity ratios with vinyl monomers have been reported (87). At 60°C with benzoyl peroxide as initiator, triaUyl citrate retards polymerization of styrene, acrylonitrile, vinyl choloride, and vinyl acetate. Properties of polyfunctional aUyl esters are given in Table 7 some of these esters have sharp odors and cause skin irritation. 

DiaUyl fumarate polymerizes much more rapidly than diaUyl maleate. Because of its moderate reactivity, DAM is favored as a cross-linking and branching agent with some vinyl-type monomers (1). Cyclization from homopolymerizations in different concentrations in benzene has been investigated (91). DiaUyl itaconate and several other polyfunctional aUyl—vinyl monomers are available. 

Small amounts of TAIC together with DAP have been used to cure unsaturated polyesters in glass-reinforced thermo sets (131). It has been used with polyfunctional methacrylate esters in anaerobic adhesives (132). TAIC and vinyl acetate are copolymerized in aqueous suspension, and vinyl alcohol copolymer gels are made from the products (133). Electron cure of poly(ethylene terephthalate) moldings containing TAIC improves heat resistance and transparency (134). 

Coacrete can also be made water-repeUent by the polymerisation of vinyl monomers on the surface (85). Polymerisation can be iaitiated with peroxides, and polyfunctional methacrjiates can be used as crosslinking agents. These treatments have a tendency to produce changes ia color and gloss. 

Optimization of the ATP—hemoglobin reaction conditions produced a preparation having a markedly reduced oxygen affinity. Five fractions from a reaction mixture, when isolated, were found to have P q values ranging from 1.1 to 5.0 kPa (8 to 38 torr), most withUtfle cooperativity (118). These results are consistent with those found with other polyfunctional reagents that react on the surface of hemoglobin. 

Ammonium acetate and sodium methoxide are effective catalysts for the ammonolysis of soybean oil (49). Polyfunctional amines and amino alcohols such as ethylenediamine, ethanolamine, and diethanolamine react to give useful intermediates. Ethylenediamine can form either a monoamide or a diamide depending on the mole ratio of reactants. With an equimolar ratio of reactants and a temperature of >250° C, a cyclization reaction occurs to give imidazolines with ethylenediamine (48) ... 

For some years, this type of vehicle was used in anionic electro deposition primers. However for automobiles cationic electro deposition primers are now preferred. The vehicles for cationic primers are proprietary but probably consist of the reaction product of epoxy resins and polyfunctional amines solubilized by the conversion of amine groups into salts using an acid such as lactic acid (2-hydroxypropanoic acid) [50-21-5] Alcohol-blocked... 

Polyfunctional 2-hydtoxyalk5iamides can serve as cross-linkers for carboxyHc acid-terrninated polyester or acryHc resins (65). The hydroxyl group is activated by the neighboring amide linkage (66). SoHd grades of hydroxyamides are finding use as cross-linkers for powder coatings (67). 

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