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In this study, the viscoelastic and morphological properties of molded foams were investigated to determine the influence of the presence or absence of reinforcing particulate copolymer polyols (CPP). The molded foams were based on toluene diisocyanate (TDI) and glycerol‐initiated ethylene‐oxide endcapped polypropylene oxide and, in most samples, some amount of copolymer polyol. Two series of foams were studied. In Series 1, as CPP is added to the formulation, the amount of TDI fed is kept constant. This results in a constant amount of hard‐segment content as the filler in the system displaces, by weight, the polyether polyol in the foam, and it increases the hard segment to soft segment ratio (HS/SS). In Series 2, the amount of hard‐segment material is proportionally decreased as CPP is added, resulting in a constant HS/SS ratio. Structural investigations of the foams displayed rather similar textures. The cellular structures of a CPP‐containing foam was very similar to a foam lacking the copolymer polyols. Transmission electron microscopy revealed that the CPP particles were well dispersed and that they possessed significant rigidity even at high temperature and under high compression. Although all of the foams were microphase‐separated, they varied slightly in that the copolymer polyol containing foams exhibited higher weight fractions of extractables in both Series 1 and Series 2. This suggests that not all of the CPP material is covalently bonded into the polyol matrix. It was found that temperatures above ambient as well as humidity plasticized the viscoelastic behavior of all the molded foams evaluated. It was also found that the copolymer polyol particles, as added to the molded foams of Series 1, increased load‐bearing capabilities but had a negative effect on the stress relaxation, creep, and compression set properties. In particular, the viscoelastic properties of the CPP‐containing foam were distinctly more time‐dependent than those of the foam lacking these particles. However, the Series 2 foams show that most of these effects are a result of the increased HS/SS ratio and not a result of the CPP particulate. It was shown that adding CPP while maintaining a constant HS/SS ratio improves percent load loss and load bearing under high‐humidity conditions, two important properties in flexible polyurethane foams. Finally, it was shown that at high temperatures (ca. 100°C), an additional relaxation mechanism occurs which cannot be attributed to changes in the HS/SS ratio, but must be a result of the CPP components themselves. This additional mechanism results in higher rates of load relaxation and creep in foams containing CPP at high temperatures for foams of both series. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 766–786, 2000

ABSTRACT:The effect of toluene diisocyanate (TDI) index on the physical properties, structure, and morphology of flexible slabstock polyurethane foams was investigated. Foams based on a 2700 molecular weight triol, 6 pph water, and varying amounts of an 80/20 mixture of 2,4-and 2,6-TDIs were characterized using a number of physical property and morphological measurements. Extraction experiments using dimethyl formamide (DMF) showed that increasing the index increased the level of covalent crosslinking with perhaps a maximum being reached at an index ca. 100. Viscoelastic measurements also supported the claim of increased crosslinking with TDI index. The initial load in load relaxation experiments at 65% strain systematically increased with increasing TDI while the percent decay in a 3-h period decreased. Temperature and/or humidity ''plasticized'' the load relaxation behavior in all the foams studied, indicating that the hard segment domain physical ''crosslinks'' play a significant role in the properties of these materials. Interestingly, compression set measurements appeared to be independent of the index, likely due to some level of hard segment continuity, but the induced recovery of the compression set at elevated temperatures was indeed sensitive to the index. The amount of recovery systematically increased with increasing TDI index due to the more enhanced ''recoverable'' covalent network. Scanning electron microscopy (SEM) studies of the foams showed that the cellular structure was not significantly affected by the index. However, SEM also showed that the structure of the high index foam was not greatly altered by the extraction process while the lowest index foam's cellular structure was severely disfigured. The fine structure of the foams was found to be influenced by the TDI index. Small angle X-ray scattering, differential scanning calorimetry, and dynamic mechanical analysis all provided evidence that an increase in the TDI index promoted some phase mixing of the soft and hard segments. FTIR showed that the short-range ordering within the hard segment domains displayed a maximum at an index of 100. This was attributed to the concentration of hard segment domains being lower at a lower index and their ordering being disrupted at higher indexes due to more extensive covalent crosslinking prior to completion of phase separation. Wide angle X-ray scattering results also confirmed that for the highest index level, the short-range ordering of the TDI moieties was decreased.

ABSTRACT:We investigated the synthesis and structureproperty behaviors of two types of vegetable-oil polyols (soy oil and castor oil) and their use in viscoelastic (VE) polyurethane foams (PUFs). This article is the first in a two-part series. In this initial part, we principally address the dynamic mechanical analysis (DMA) behavior of these foams in conjunction with information on the cellular morphology, sol fraction, and rise and reaction temperature profile behavior (the latter two parameters were determined during the foaming process). Particular emphasis is placed on the DMA damping characteristics, which represent one of the most critical parameters in the application of VE PUFs. It is also shown that the damping characteristics could be modified in such foams by the variation of the isocyanate/hydroxyl (Â100) index, the addition of plasticizer, and in the case of soy polyols, the soy content. The frequency dependence of the VE PUFs is also briefly addressed. In the second article in this series, which directly follows this article, we further address the details of other relevant physical properties of these same foams in view of their applied nature.

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