Diols chain extenders

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. 

This prepolymer (Scheme 1.10) is then reacted with a chain-extender diol or diamine to give the final polyurethane or polyurethane-polyurea block copolymer, respectively. The diversity in properties that the final urethane block copolymers exhibit is governed by the nature of the three building blocks the diol-terminated polyester, the di-isocyanate-terminated polyurethane and the chain extender (Hepburn, 1982). As shown in Figure 1.17, these form flexible blocks (from the polyester) that undergo phase segregation as structures of size 1000-2000 nm. 

Practically, for better control, PUs are synthesized using three different components Dls (ahphatic or aromatic), polyols (mostly diols or triols), and chain extenders (diols or diamines). 

The PUs are synthesized using three components diisocyanates, polyols and chain extenders (diols or diamines), as shown in Figure 12.11. A chain extender is used to improve the mechanical properties of the polymer by connecting the hard (composed by -NH-COO- and chain extender) and soft (polyol part) segments of the PUs (Figure 12.12). Generally a low molecular weight diamine or diols are used to accomplish this function. 

In the second step, a papermaking method is also used for the fine fibers, less than 0.1 tex (1 den). This process is usually followed by a high pressure water jet process instead of the third step. In the fourth step, to obtain the required properties in specific appHcations, a polyurethane is selected out of the segmented polyurethanes, which comprises a polymer diol, a diisocyanate, and a chain extender (see Urethane polymers). A DMF—water bath for coagulation is also controlled to create the adequate pore stmcture in combination with fibers. 

Step-Growth Gopolymerization. A sample of a block copolymer prepared by condensation polymerisation is shown in equation 30 (37). In this process, a prepolymer diol (HO—Z—OH) is capped with isocyanate end groups and chain extended with a low molecular-weight diol (HO—E—OH) to give a so-called segmented block copolymer, containing polyurethane hard blocks and O—Z—O soft blocks. 

Derivatives of CPD have also been incorporated into these resins. CPD and 2-butene-l,4-diol have been condensed in ethanol and catalyticaHy hydrogenated in situ to give 2,3-bis(hydroxymethyl)bicyclo[2.2.1]heptane (51). This latter compound is used as a chain extender in polyesters for engineering plastics (52). 

Chain extenders are usually low molecular weight symmetrical diols or diamines. Chain extenders react with isocyanates in the same way as polyols do, but because they are low molecular weight, a high concentration of hydrogen-bonded molecules can associate and phase out of the polyol to form plastic-like domains called hard segments . Hard segments will be discussed in Section 4. Some of the more common diol and diamine chain extenders are shown in Table 3. 

In a second step, the prepolymer was then reacted with a low molecular weight difunctional alcohol, commonly referred to as a diol or a diamine, to connect the prepolymer oligomers into a high molecular weight polyurethane. This step was referred to as the chain extension , resulting in the use of the term chain extenders to describe the low molecular weight diols or diamines that reacted with the prepolymer oligomers. 

TPU is usually made from hydroxyl-terminated polyether or polyester diols, diisocyanates, and bifunctional chain extenders. Since the composition, the synthetic method, molecular weight, and its distribution are all changeable, there are numerous types of TPUs available, and their prices and properties vary significantly. 

Chain extenders in thermoplastic PUs are typically low-molecular weight diols. There are several degradable chain extenders that have been previously developed which incorporate amino acids. These degradable chain extenders are diamines (see, e.g.. Figure 8.2). 

Goma K and Gogolewski S. Biodegradable polyurethane implants U in vitro degradadon and calcification of materials from poly (e-caprolactone)-polyethylene) diols and various chain extenders. J Biomater Res, 2002, 60, 592-606. 

To obtain the polyurethanes, typically a prepolymer was first prepared by reacting the diisocyanate with various diols in dimethylformamide or dimethylacetamide in a two to one molar ratio at 100-110°C for two hours under nitrogen atmosphere. A solution of chain extenders, such as BEP, was then added to the prepolymer reaction mixture and further reacted another three hours. The polymer was isolated by quenching the reaction mixture in cold water. Fine white powder was obtained with a typical yield of around 90%. 

The above prepolymer on treatment with 2 as the chain extender in dry DMF did not proceed at ambient temperature. The mixture had to be heated to 60°C for 3 h before the reaction was complete. After curing at 60°C for 24 h, the yellow, translucent block polyurethane film (BPUR2) again showed the absence of the —NCO peak in the IR spectrum indicating that curing had been complete. The fact that a higher temperature had to be used in the case of 2 as the chain extender compared to 1 is in keeping with the lower order of reactivity of diols with diisocyanates as compared to diamines with diisocyanates. 

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. 

The hot curing process normally uses polyether diol precursors with molecular weights of 3,000 to 5,000 g/mole. We can control the stiffness of the foam by adjusting the average number of isocyanate groups on the chain extender molecules. The higher the functionality of the isocyanate molecules, the more crosslinked, and hence stiffer, will be the product. 

Typical chain extenders that are used are MOCA (4,4-methylene bis orthochloro- aniline), butane diol or trimethylolpropane. 

Chain Extendable Urethane Modified Epoxy Oligomer. The chain extendable urethane modified oligomers were prepared by combining equimolar amounts of epoxy-diol adduct and half-blocked diisocyanates, and heating the resulting mixture at 80°C for 4-6 hours until the isocyanate Infrared band disappeared. 

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. 

Chain Extension of -U-Polystyrene Hiols. A two-stage chain extension of the. -kJ -polystyrene diols was accomplished by carboxylation of the diols with succinic anhydride followed by chain extension with a diepoxide. The succinic anhydride reaction was carried out 120-130°C under nitrogen. The reaction was monitored bj changes in the carbonyl bands at 1715 and 1740 cm in the infrared spectra of the reaction mixtures. The resulting dicarboxylic acid polymers were chain-extended in bulk at 130°C for 9 hours with Sow s HER diepoxide, equivalent weight =171, using bis( 3,5-diisopropylsalicylato)Cr (III) as the catalyst. 

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