Oligomers isocyanate terminated

ABA type poly(hydroxyethyl methacrylate) (HEMA) and PDMS copolymers were synthesized by the coupling reactions of preformed a,co-isocyanate terminated PDMS oligomers and amine-terminated HEMA macromonomers312). Polymerization reactions were conducted in DMF solution at 0 °C. Products were purified by precipitation in diethyl ether to remove unreacted PDMS oligomers. After dissolving in DMF/toluene mixture, copolymers were reprecipitated in methanol/water mixture to remove unreacted HEMA oligomers. Microphase separated structures were observed under transmission electron microscope, using osmium tetroxide stained thin copolymer films. 

We can make polyurethanes via one- or two-step operations. In the single-stage process, diols and isocyanates react directly to form polymers. If we wish to make thermoplastic linear polymers, we use only diisocyanates. When thermosets are required, we use a mixture of diisocyanates and tri- or polyisocyanates residues of the latter becoming crosslinks between chains. In the first step of the two-stage process, we make oligomers known as prepolymers, which are terminated either by isocyanate or hydroxyl groups. Polymers are formed in the second step, when the isocyanate terminated prepolymers react with diol chain extenders, or the hydroxyl terminated prepolymers react with di- or polyisocyanates. 

Reactive oligomers such as epoxy resins, isocyanate-terminated compounds, and urethane-acrylates are extremely useful in the adhesive, coating, reaction injection molding (RIM), sealant and... 

It is common in acrylic structural adhesives to use oligomers that have a desirable backbone and are terminated with free-radical-polymerizable bonds. A variety of isocyanate-terminated polyurethanes can be adapted to use in acrylic structural adhesives by reacting the terminal isocyanates with a hydroxy functional acrylic monomer such as 2-hydroxyethyl methacrylate.76,92 93... 

Polyol and Isocyanate components may be reacted to afford Isocyanate-terminated oligomers which can then be subjected to the general reaction Illustrated in equation 1 above. Together with other synthetic modifications, this permits the preparation of a wide variety of oligomers. One may vary, for example ... 

The elastic textile fiber Spandex (Du Pont s Lycra) is an excellent example of a successful TPE material (U.S. Patent 2,692,873 issued in 1954, but not commercialized by Du Pont until 1962). Another example is the development of Du Pont s Adiprene PU rubber, which is formed by the reaction of 3 parts of PTMEG (an oligomer of 9—11 tetramethylene ether units) with 4.3 parts of TDI to give an isocyanate-terminated prepolymer that is subsequently treated with 0.3 part of TDI and some water to form an urea-linked end product. 

A series of polyurethane polyacrylates were prepared by reaction of toluene diisocyanate (XVIII), other isocyanates, and isocyanate-terminated oligomers with hydroxyalkyl methacrylates [24]. These monomers could be tailored to provide the... 

An alternative route starts with a carboxy-terminated oligomer [36], This is reacted with glycidyl methacrylate to provide the methacrylate-terminated polymer. The resulting linkage is susceptible to hydrolysis, so the hydroxy group may be reacted with an isocyanate to improve environmental resistance (Scheme 3). 

Waste PETP was depolymerised by glycolysis to give hydroxyl-terminated oligomers(DPET), which were used in the synthesis of urethane oils. The effect of depolymerisation temps., the type of glycol and the amount of catalyst on the yield and composition of the depolymerisation products was studied. The physical properties of the urethane oils were compared with those of a commercially-available product. The reaction of DPET with isocyanates produced random linkage between different molecules with or without terephthaloyl groups. 15 refs. 

The anionic method of polymerization is most useful for the synthesis of low molecular weight hydroxy-terminated oligomers and polymers that are to be further processed. For example, the treatment of hydroxy-terminated oligomers with isocyanates has been used to obtain polyester-urethanes (9,20), while triblock copolymers (PCL-PEG-PCL) are prepared by initiating the polymerization of e-caprolactone with the disodium alcoholate from polyethylene glycol (26). 

Michael addition reactions are particularly useful when linear aliphatic bis-nitramines are used because the products contain two terminal functional groups like in the diester (182). The terminal functionality of such products can be used, or modified by simple functional group conversion, to provide oligomers for the synthesis of energetic polymers such oligomers often use terminal alcohol, isocyanate or carboxy functionality for this purpose. 

The volatility of difunctional isocyanates (such as tolylene diisocyanates, hexamethylene diisocyanate, etc.) creates many environmental problems in the urethane industry. These difficulties can be overcome by preparation of NCO-terminated oligomers with low vapor pressure. One approach is the preparation of NCO-ter-minated oligomers by partial cyclotrimerization of difunctional isocyanates. Usually this is achieved by a multi-step process which includes also deactivation of the catalyst at a certain conversion. During our work on cyclotrimerization of isocyanates we found that cyclic sulfonium zwitterions are very active cyclotrimerization catalysts (2). Recently we found that cyclic sulfonium zwitterions under certain reaction conditions act as anionic initiators. This behavior of cyclic sulfonium zwitterions permits preparation of isocyanate oligomers containing isocyanurate rings by a one-step procedure, eliminating the deactivation step. 

During the initial stages of cyclotrimerization of difunctional isocyanates, the formation of polyfunc-tional NCO-terminated oligomers takes place ... 

When a diol is used, an a, oo-dihydroxy-terminated polymer is obtained. With a triol, a branched triol polymer results. Oligomers with molar masses in the range of 250 8000 gmol 1 are prepared with this reaction for uses in isocyanate or acrylate chemistries. 

Urethane-Based Hybrid Foams. Hydroxyl-terminated ester oligomers or vinyl esters which have terminal vinyl groups and pendant hydroxyl groups can react simultaneously with isocyanate groups and vinyl monomers in the presence of catalysts to obtain crosslinked hybrid polymers. 

In the same way, Oishi et al. [256] used IEM to functionalize oligomers carrying an acid function obtained by polymerization of chiral acrylamides. Chiral polyacrylamide macromonomers were synthesized from 2-methacryloyloxyethyl isocyanate and prepolymers, i.e., poly[(S)-methyl-benzyl acrylamide] or poly(L-phenylalanine ethylester acrylamide) with a terminal carboxylic acid or hydroxyl group. Radical homopolymerizations of polyacrylamide macromonomers were carried out under different conditions to obtain the corresponding optically active polymers, as shown in Scheme 52. 

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