Prepolymer variations

Polyurethane foams may be rigid, semi-rigid or flexible. They may be made from polyesters, polyethers or natural polyols such as castor oil (which contains approximately three hydroxyl groups in each molecule). Three general processes are available known as one-shot, prepolymer or quasi-prepolymer processes. These variations lead to 27 basic types of product or process, all of which have been used commercially. This section deals only with flexible foams (which are made only from polyesters and polyethers). Since prepolymers and... 

In all calculations the molar masses given in the top of Table I were used. First of all, the effects of variations in the concentration of trifunctional monomers were determined, as exemplified by the nine formulations of Table I and the resulting prepolymer characteristics after full conversion given in Table II. Formulations FIO to F40 result in branched prepolymers, which are cured in the third stage by difunctional monomers. On the other hand, formulations FOO to F04 result in the same linear prepolymer, which is subsequently cured with various mixtures of di- and trifunctional monomers. The number average functionalities of PI (and P2) and of the mixtures of E and F monomers are varied systematically between 2.0 and 2.4. Therefore, the only difference between formulations FjO and FOj is the stage in which the branching units are added. 

Figure 5.23 Variation in the concentration of carboxylic end groups and intrinsic viscosity during the postcondensation of PET powder produced from DMT (1) and TPA (2) prepolymers (7, 240 °C) [49]. From Gerking, L., Modifications of fiber properties by polymer and within spinning line, presentation (Paper 52b) given at the 32nd International Man-Made Fibre Congress, 22-24 September, 1993, Dornbirn, Austria, and reproduced with permission of EMS Inventa-Fischer, GmbH Co. KG...

First and most importantly, real-time NIR monitoring enabled real-time control of the process. For a given product, the molecular weight and end-group balance in the prepolymer exiting the front end or melt part of the process must be controlled at specified levels in order for the back end or solid-phase part of the process to successfully produce the intended polymer composition. In addition, the variability in prepolymer composition must be controlled with very tight tolerances to keep the variation in final product composition within specification limits. Since the process dynamics in the front end were more rapid than those in conventional PET processes, the conventional analytical approach involving off-line analysis of samples obtained every 2-A hours was not sufficient to achieve the desired product quality. 

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. 

Using the above techniques, satisfactory reproducibility of CTPB propellant mechanical properties has been achieved. The reproducibility of the mechanical properties of a production CTPB propellant which is controlled by this method is shown in Table XIX. In this case, the standard deviations of the mechanical properties shown are 10% or less of the measured values. The data include differences arising from lot-to-lot variations in raw materials (27 lots of CTPB) and two sources for the prepolymer. 

An interesting variation on the use of azo groups-containing polymers is the use of polyacrylamide prepolymers as both initiator and emulsifying agent for the emulsion polymerization of vinyl acetate. The observed reaction kinetics were typical (see Fig. 4.7) for an emulsion polymerization and, in particular, the slope (a = 1) of the plot of lg Rp vs lg CPrep confirms the double function of these prepolymers very clearly. 

The high exotherm and the number of feeds have led to the popularity of the quasiprepolymer variation of the one-shot technique. Quasiprepolymers are a version of the standard prepolymer method, where some of the polyol is reacted with an excess of diisocyanate. This is later reacted with the remainder of the polyols, including the chain extender and some catalysts. The advantage of this scheme is that the exotherm is spread between the preparation of the quasiprepolymer and the final cured part. In MD1 systems, BDO is often used as the curative. As the molecular weight of BDOs is low, the amount added is low. By dissolving it in the polyol, a more even mix ratio can be obtained. 

In this variation of high performance liquid chromatography (HPLC), the columns are packed with material that will hold back molecules dependent on the molecular size. Using the correct solvent system and column types, the molecular weight and distribution of the polyols can be determined. Standard samples are needed to calibrate the system. The molecular weight distribution of prepolymers can also be determined. This will enable an estimation to be made of the number of soft segment chains there are. 

Finally, in the reaction injection-molding (RIM) process, low-viscosity reacting monomers or prepolymers are intimately mixed just before being injected into a hot cavity, where they react further and solidify. The RIM process, then, is a variation of the casting process, where highly reactive liquid systems are injected quickly, rather than being allowed to flow by gravity, into complex shape cavities, where they quickly react and solidify. 

The structural variations possible in R and R make it possible to vary the toughness and elasticity of the polyurethane adhesive. Polyesters or polyethers are prepared with terminal hydroxyl groups that can then be reacted with difunctional or polyfunctional isocyanates. Polyurethane prepolymers can be formed in Reaction 1, with the desired terminal group produced by using one or other of the diol and diisocyanate reactants in excess. 

In conclusion, the temperature dependence of shift factors for the networks studied here do not follow the WLF equation, but rather an Arrhenius-type relationship. The apparent activation energies are independent of stoichiometric variation [as they are when is varied by changing prepolymer molecular weight (13)]. ... 

Figure 4. Variation of solution viscosity as a function of BCB-2 prepolymer in xylene.

In previous studies [3, 4], we had pointed out that the interphase formation mechanisms result from dissolution of the metallic surface layers, concomitantly with ion diffusion through the liquid prepolymer. In order to detect the dissolution phenomenon, pure amine (either DETA or IPDA) was previously applied to chemically etched metallic sheets (either A1 or Ti alloys were used, and had hydroxidic surfaces). After 3 h, the metallic surfaces were scraped with a PTFE spatula. The modified amine (i.e., the amine reacted with the metal) was analyzed. Whatever the natures of the amine and the metal were, metal ions were detected in the modified amines by ICP analysis and new peaks were detected by infrared spectroscopy [5]. To indicate hydroxide dissolution, a very thin layer of liquid amine was applied to chemically etched aluminum, and Infrared Reflection - Absorption Spectroscopy (IRRAS) spectra were recorded every 5 min (the hydroxide band intensity variation at ca. 3430 cm was followed). The OH group peak intensity decreased when the amine-metal contact time increased [5]. Conversely, if pure DGEBA monomer was apphed to the metal surfaces, even after 3 h in contact with the metallic surfaces, no metal ion was detected by ICP in the DGEBA recovered, and the infrared spectra remained identical before and after the contact with the metal. Finally, if pure amine monomer was applied to gold-coated substrates, no chemical reaction was observed (by either IGP or FTIR analyses). 

Two network systans were prepared (l) Epon 828/MDA networks, in which the reactant ratios were varied and (2) stoichiometric Epon resin/DDS networks incorporating variations in the prepolymer %. The more latent amine DDS was used for curing the... 

The reactions by which urethane foam are produced can be carried out in a single stage (one-shot process) or in a sequence of several stages (prepolymer process and quasi-prepolymer process.) These variations led to 27 basic types of products or processes, all of which have been used commercially. 

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