Polyurethanes prepolymer synthesis

Fig, 17. (a) Isocyanate-terminated polyurethane prepolymer synthesis, (b) Moisture cure of isocyanate-terminated polyurethane prepolymers, (c) Side reactions of isocyanate-terminated polyurethane prepolymers. 

Gurunathan T, Mohanty S, Nayak SK. Isocyanate terminated castor oil-based polyurethane prepolymer synthesis and characterization. Prog Org Coat 2015 80 39-48. 

The block lengths and the final polymer molecular weight are again determined by the details of the prepolymer synthesis and its subsequent polymerization. An often-used variation of the one-prepolymer method is to react the macrodiol with excess diisocyanate to form an isocyanate-terminated prepolymer. The latter is then chain-extended (i.e., increased in molecular weight) by reaction with a diol. The one- and two-prepolymer methods can in principle yield exactly the same final block copolymer. However, the dispersity of the polyurethane block length (m is an average value as are n and p) is usually narrower when the two-prepolymer method is used. 

Through the synthesis of poly(urethane-imide) films and their carbonization, carbon films were obtained whose macropore structure could be controlled by changing the molecular structure of polyurethane prepolymer [164-166]. Poly(urethane-imide) films were prepared by blending poly(amide acid), which was synthesized from pyromellitic dianhydride (PMDA) and 4,4 -oxydianiline (ODA), and phenol-terminated polyurethane pjrejwlymers, which were synthesized through the reaction of polyester polyol with either hexamethylene diisocyanate (HDI), tolylene-2,4-diisocyanate (TDI) or 4,4 -diphenyknethane-diisocyanate (MDI). The reaction schemes of two components, poly(imide) (PI) and poly(urethane) (PU), are shown in Fig. 46a). 

When symmetrical diisocyanates are chain-extended with diols, elastomers of good strength properties are obtained. Examples of these diisocyanates are CHDI and PPDT. To illustrate their effect on properties, the following case history of synthesizing a polycaprolactone/CHDI/diol elastomer is given. This also serves to record the quasi prepolymer synthesis route and demonstrate the influence of chain-extender aromaticity on polyurethane elastomer properties. 

Fig. 10.5. Nucleophilic ring opening of an oxetone to give a diol for cationic polyurethane-elastomer prepolymer synthesis.

Figure 6.3 Two-step polyurethane synthesis. First step prepolymer synthesis from a diisocyanate and a macrodiol. Second step chain extension.

Catalyst tin catalysts are the most popular In the case of prepolymer synthesis (polyureas), and amines In the case of polycondesa-tlon of polyol and Isocyanate (polyurethane) Abdel Hakim, AA Nassar, M Emam, A Sultan, M, Mater. Chem. Phys., 129, 301-7,2011. 

At a non-stoichiometric ratio of the reagents, one can prepare a crosslinked polymer by two-step synthesis. A different result is obtained in the reaction of the polyurethane prepolymer (PP, dissolved in DMF) with ADMH [19,20]. At a 2-, 5-, and even 10-fold increase of the PP molar fraction, DMF-soluble macromolecular compounds are formed. The respective solution-cast films have mechanical properties similar to those of classical polyurethane elastomers (Table 3). 

Example 2. Two-Shot Cast Elastomer (Prepolymer Method). Synthesis of polyurethane elastomers via the prepolymer method is challenging and requires especial attention to details and techniques. This example is a relatively easy one, using a low-viscosity, 9.6% NCO MDI-based poly(tetramethylene ether) glycol prepolymer. It is adapted from the Bayer Product Information Bulletin for Baytec ME-090 prepolymer. 

Synthesis of Polyurethanes. In the "prepolymer method" employed in this study, MDI (2 equivalents) and PPG (1 equivalent) were reacted at 60°C in the presence of 1% dibutyltin dilaureate as catalyst, in the melt. The course of the polymerizations was followed spectroscopically by observing the intensity of the — NCO peak in the IR (Scheme III). 

Completely aliphatic polyesters, made from aliphatic diacid and aliphatic diol components), are not of major industrial importance because of their low melting temperatures and poor hydrolytic stability. (Low-molecular-weight aliphatic polyesters are used as plasticizers and prepolymer reactants in the synthesis of polyurethanes see Secs. 2-12e, 2-13c-2). 

Much attention has been paid to the synthesis of fluorine-containing condensation polymers because of their unique properties (43) and different classes of polymers including polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, and epoxy prepolymers containing pendent or backbone-incorporated bis-trifluoromethyl groups have been developed. These polymers exhibit promise as film formers, gas separation membranes, seals, soluble polymers, coatings, adhesives, and in other high temperature applications (103,104). Such polymers show increased solubility, glass-transition temperature, flame resistance, thermal stability, oxidation and environmental stability, decreased color, crystallinity, dielectric constant, and water absorption. 

The first part concludes with a discussion of the similarity between the mechanisms of initiation and chain transfer, the appreciation of which led to the inifer concept, which in turn yielded new telechelics, networks, sequential copolymers, etc. The second part of this presentation focuses on practical consequences of understanding details of the mechanism of initiation. The synthesis of a new family of telechelic linear and tri-arm star polyisobutylenes will be described. Among the new prepolymers are telechelic olefins, epoxides, aldehydes, alcohols, and amines. The preparation of new ionomers and polyisobutylene-based polyurethanes will be outlined and some fundamental properties of these new materials will be discussed. 

Segmented polyurethanes were synthesized from the a, to diol polyethers listed in Table I and the diisocyanates IV, V, and VI by the two-step process shown in Figure 1 or the three-step process in Figure 2. In all cases, chain extension of isocyanate-terminated prepolymers was accomplished with ethylenediamine. The synthesis took place in a 2 1 (v/v) mixture of dimethyl sulfoxide and 4-methyl-2-pentanone at 60°C. 

Addition of plasticizer to polyurethanes can be done in several ways in the beginning of synthesis of prepolymer, at the last stages of synthesis, and during adhesive/sealant... 

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