Trifunctional

Difunctional, Trifunctional, and OligofuuGtianal Open-Chain Reagents... 

Open-chain trifunctional compounds containing no other elements than... 

We close the section on open-chain molecules with an example of a trifunctional target molecule. This does not include any fundamentally new problem. In antithetic analysis one simply chooses an appropriate difunctional starting material, which may be further disconnected into monofunctional starting materials. 

Mono-, di-, and trialkylboranes may be obtained from olefins and the trifunctional borane molecule. Simple unhindered alkenes yield trialkylboranes and it is not possible to halt the reaction at the mono- or dialkylborane stage. With more hindered and trisubstituted alkenes the reaction can be controlled to stop at the dialkylborane stage. 

More recendy, molecular molybdenum-sulfur complexes and clusters have been used as soluble precursors for M0S2 in the formulation of lubricating oils for a variety of appHcations (70). Presumably, the oil-soluble molybdenum—sulfur-containing precursors decompose under shear, pressure, or temperature stress at the wear surface to give beneficial coatings. In several cases it has been shown that the soluble precursors are trifunctional in that they not only display antifriction properties, but have antiwear and antioxidant characteristics as weU. In most cases, the ligands for the Mo are of the 1,1-dithiolate type, including dithiocarbamates, dithiophosphates, and xanthates (55,71). 

Another significant use of 3-methylphenol is in the production of herbicides and insecticides. 2-/ f2 -Butyl-5-methylphenol is converted to the dinitro acetate derivative, 2-/ f2 -butyl-5-methyl-4,6-dinitrophenyl acetate [2487-01 -6] which is used as both a pre- and postemergent herbicide to control broad leaf weeds (42). Carbamate derivatives of 3-methylphenol based compounds are used as insecticides. The condensation of 3-methylphenol with formaldehyde yields a curable phenoHc resin. Since 3-methylphenol is trifunctional with respect to its reaction with formaldehyde, it is possible to form a thermosetting resin by the reaction of a prepolymer with paraformaldehyde or other suitable formaldehyde sources. 3-Methylphenol is also used in the production of fragrances and flavors. It is reduced with hydrogen under nickel catalysis and the corresponding esters are used as synthetic musk (see Table 3). 

Silicone Fluids. Sihcone fluids are used in a wide variety of appHcations, including damping fluids, dielectric fluids, poHshes, cosmetic and personal care additives, textile finishes, hydraiflic fluids, paint additives, and heat-transfer oils. Polydimethylsiloxane oils are manufactured by the equihbrium polymerisation of cycHc or linear dimethyl silicone precursors. Trifunctional organosilane end groups, typically trimethylsilyl (M), are used, and the ratio of end group to chain units (D), ie, M/D, controls the ultimate average molecular weight and viscosity (112). Low viscosity fluids,... 

Fig. 2. Polytitanosiloxane polymers, where M is Ti/Zr and X is Cl. (a) Monofunctional, (b) dihinctional, (c) trifunctional, and (d) tetrafunctional polymers.

Hyperbranched polyurethanes are constmcted using phenol-blocked trifunctional monomers in combination with 4-methylbenzyl alcohol for end capping (11). Polyurethane interpenetrating polymer networks (IPNs) are mixtures of two cross-linked polymer networks, prepared by latex blending, sequential polymerization, or simultaneous polymerization. IPNs have improved mechanical properties, as weU as thermal stabiHties, compared to the single cross-linked polymers. In pseudo-IPNs, only one of the involved polymers is cross-linked. Numerous polymers are involved in the formation of polyurethane-derived IPNs (12). 

An example of the importance of free-volume availabiUty on cross-linking has been reported in the evaluation of a trifunctional derivative of an ahphatic isocyanate which contains an aromatic ring, y -tetramethylxyUdene diisocyanate (TMXDI) [2778-42-9] C 4H N202, as a cross-linking agent for hydroxy-functional resins (15). 

Because of steric effects, TMXDI is less reactive than the trifunctional derivatives of hexamethylene diisocyanate (HDI) (1,6-diisocyanatohexane)... 

In the case of trifunctional monomers the situation is more complex. From the schematic diagrams (Figure 2.26) it will be seen that the polymers have more functional groups than the monomers. 

Figure 8.13. Schematic diagram of a trifunctional monomer (a) and its dimer (b) and trimer (c). The monomer has three reactive points and the dimer and trimer four and five respectively. In general, an...

Figure 8.14. Typical curve for viscosity against time of condensation of essentially trifunctional monomer systems under isothermal conditions...

Use of trifunctional acids or amines to give branched structures. 

In general it is considered essential that the bulk of the phenol used initially should not be substituted, i.e. should be reactive, at the o- and p-positions and is thus trifunctional with respect to the reaction with formaldehyde. 

Rather similar are the 5.5-dimethylhydantoin derivatives shown in Figure 26.18 (b, e). These resins are said to eonfer improved weathering resistance but also exhibit higher water absorption. Another trifunctional material is p-glycidyl-oxy-A,A/-diglycidylaniline. This has been recommended for adhesive systems in conjunction with benzophenonetetracarboxylic acid dianhydride, which is a room temperature curing agent in this case. 

As with the flexible foams there has been a shift to the use of polyethers. These are largely adducts based either on trifunctional hydroxy compounds, on tetrafunctional materials such as pentaerythritol or a hexafunctional material such as sorbitol. Ethylene diamine and, it is understood, domestic sugar are also employed. Where trifunctional materials are used these are of lower molecular weight (-500) than with the polyethers for flexible foams in order to reduce the distance between hydroxyl groups and hence increase the degree of cross-linking. 

Products intermediate to the flexible and rigid foams may be obtained from castor oil (a trihydroxyl molecule), synthetic triols of moderate molecular weight and polyesters with a moderate amount of trifunctional hydroxyl compound in the strueture. Current practice, however, is to use tipped polyols of the type used for flexible foams with MDI. Semi-rigid foams are used for such purposes as crash pads, car steering wheels and packaging equipment. 

The elastomers consist of very high moleculcU weight (-0.5 X 10 ) linecu gums cross-linked after fabrication. In order to achieve such polymers it is necessary that very pure difunctional monomers be employed since the presence of monofunctional material will limit the molecular weight while trifunctional material will lead to cross-linking. Where dimethylsilicone rubbers are being prepared, the cyclic tetramer, octamethylcyclotetrasiloxane, which may be obtained free from mono- and trifunctional impurities, is often used. This tetramer occurs to the extent of about 25% during the hydrolysis of dichlorosilanes into polymers. 

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