Elastomers chain extenders

An entirely new concept was iatroduced iato mbber technology with the idea of "castable" elastomers, ie, the use of Hquid, low molecular-weight polymers that could be linked together (chain-extended) and cross-linked iato mbbery networks. This was an appealing idea because it avoided the use of heavy machinery to masticate and mix a high viscosity mbber prior to mol ding and vulcanization. In this development three types of polymers have played a dominant role, ie, polyurethanes, polysulftdes, and thermoplastic elastomers. 

Example 1. One-Shot Cast Elastomer. This is an example of a one-shot cast elastomer using a PMDI, two polyols, and a chain extender. It is a good formulation to begin with because it is simple and uses low-viscosity ingredients that can be blended and cast at room temperature. 

Singer S.M. and Allot M.T., Thermoplastic polyurethane elastomer based on a saturated hydroxyl terminated polyol, difunctional aromatic chain extender and 1,5-naphthalene diisocyanate, US Patent 5 599 874, 1997. 

Skaija GA and Woodhouse KA. S3mthesis and characteization of degradable pol)oirethane elastomers containing an amino acid based chain extender. J Biomater Sci Polym Ed, 1998, 9, 271-295. 

In a polyurethane elastomer analysed by isobutane CI-MS and CI-MS/MS in TD/Py-CIMS (TD, 20-200°C Py, 200-300 °C) mode MDI (diisocyanate), BDO (chain extender), Stabaxol P (stabiliser), AA/ BDO/HDO (cyclic adipate) and residual cyclic ester oligomers were identified [65]. 

Chain extenders Diols and diamines are generally used as chain extenders in PU industry and choice of chain extender influences elastomer properties considerably. The standard diol chain extender used for the synthesis of PU elastomer is 1,4-butane diol (BDO). Compared with a diol, better physical properties usually result when a diamine is employed as an extender. This is probably due to the introduction of urea linkages which enter into strong hydrogen bonded interactions. A diamine is usually chosen as the chain extender when a relatively unsymmetrical diisocyanate is employed. Diamines also function as efficient catalysts in addition to chain extenders. 

To obtain elastomers, one or two diols can be reacted with the isocyanate. When two diols are used, the first one is a macrodiol with a molar mass in the range 500-10000 g mol-1, and the second one is a short diol, typically 1,4-butanediol. The PU may be prepared by either the one-shot process (three components reacting together), or the prepolymer approach a prepolymer is prepared first (Eq. 2.36) and then reacted with the short diol (chain extender) ... 

Flexible PU foams are prepared from basically the same raw materials as PU elastomers. Instead of a short-chain extender, water is used. Water reacts with isocyanates to form an amine and C02 (Eq. (2.22)), which results in foaming. The diamine thus created can then react with isocyanate groups giving polyurea short segments. A surfactant is also introduced as a cell control agent. 

PU elastomers based on a polyester diol as the soft block and isocyanate groups coupled via a chain extender as the rigid block, have been investigated. The role of the chain extender is to induce some mobility and disorder within the hard microdomains. The elastomers are selectively deuterated in the rigid block. 2H NMR spectra show the coexistence of a solid and a mobile fraction [89]. The solid fraction shows no onset of fast molecular motions at all, while the mobile fraction increases with temperature. These results suggest that some of the hard microdomains (perhaps the most disordered ones) melt successively when temperature is raised. 

Thermoset polyurethanes are cross-linked polymers, which are produced by casting or reaction injection molding (RIM). For cast elastomers, TDI in combination with 3,3,-dichloro-4,4,-diphen5lmethanediamine (MOCA) are often used. In the RIM technology, aromatic diamine chain extenders, such as diethyltoluenediamine (DETDA), are used to produce poly(urethane ureas) (47), and replacement of the polyether polyols with amine-terminated polyols produces polyureas (48). The aromatic diamines are soluble in the polyol and provide fast reaction rates. In 1985, internal mold release agents based on zinc stearate compatibilized with primary amines were introduced to the RIM process to minimize mold preparation and scrap from parts tom at demold. Some physical properties of RIM systems are listed in Table 7. 

TPU elastomers are usually made from three chemicals (1) a diisocyanate, (2) a high-molecular-weight macroglycol, and (3) a low-molecular-weight chain extender glycol. Examples of these three compounds and their structures are shown in Figure 1. 

Hard Segments. The hard segments are the linear reaction products of the diisocyanate component and the third monomer type in the TPU elastomer recipe, the small glycol-chain-extender component. In Figure 5 we see a typical TPU hard-segment structure which is formed from MDI and 1,4-BDO (1,4-butanediol). 

Several types of diisocyanates (aromatic, aliphatic, cyclo aliphatic) and many different glycol-chain extenders (open-chain aliphatic, cyclo aliphatic, aromatic aliphatic) can be used to produce TPU-elastomer hard segments. In the more conventional and practical formulations only a single diisocyanate component is used to make a TPU, so the diisocyanate is common to both the hard and soft segments. The polymer chemist makes his diisocyanate and glycol-chain-extender component selections based on such considerations as desired TPU mechanical properties, upper service temperature, environmental resistance, solubility characteristics, and economics. 

Polymers Elastomers (rubbers) Soft plastics (e.g. low density PE) Isotropic hard plastics ( Amorphous [ Semi-crystalline Conventional fibres (nylon, PETP) "Extended chain" fibres (Extended zig-zag chains (Extended helical chains ( Glassy. Cross-linked (Tg < 275 K lTg> 325 K 0.001 0.2 2.5- 3 2.5- 5 1-3 3 5-15 250fl ca 50fl... 

The production of polyurethane involves the controlled polymerization of an isocyanate, a long-chain-backbone polyol and a shorter-chain extender or cross-linker. The reaction rates can be controlled through the use of specific catalyst compounds, well known in the industry, to provide sufficient time to pour or otherwise transfer the mix and to cure the polymer sufficiently to allow handling of the freshly demolded part. The use of blowing agents allows the formation of a definite cellular core (thus the term microcellular elastomer ) as well as a non-porous skin, producing an integral sandwich-type cross section. 

Preparation of Microcellular Foams. The major polyols for microcellular elastomers include aliphatic polyester diols having a molecular weight of about 1,000 to 3,000, and poly-epsilon-caprolactones. Poly(oxytetramethylene) glycols (PTMEG) can also be used. The polyisocyanates to be used for microcellular elastomers are TDI-prepolymers and liquid MDI, i.e., carbodiimide-modified MDI or urethane-modified MDI. Low-molecular-weight, active-hydrogen compounds such as chain extenders (difunctional compounds) and... 

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