Chain extension with propylene oxide

Only one of the approaches considered here, chain-extension with propylene oxide of hydroxypropyl lignins, allowed for the preparation of networks with substantial elongation at break. Typical of most polyurethanes, an increase in the elongation at break resulted in a corresponding decrease in modulus and strength. This represents the most complex modification procedure of those discussed, although process development could probably simplify this modification for adoption on industrial scale. 

This paper examines two types of hydroxypropyl lignin based macromers, and these are illustrated schematically in Figure 1. Macromers with propylene oxide (PO) are formed by reducing the number of available hydroxyl groups on HPL followed by chain extension with PO and macromers with cellulose triacetate (CTA) are synthesized by attaching a monofunctional CTA chain to a limited number of terminal OH groups on HPL via a suitable grafting reaction. 

Chain extension with PO Partially blocked hydroxypropyl lignin derivatives were reacted with propylene oxide in toluene, using KOH as catalyst, for the purpose of creating extended propyl ether chains. This has been reported elsewhere (13). 

In a recent patent, Reuter (110) describes a polyurethane prepared from PTHF (mol. wt. 1000 to 3000), 1,4-butanediol, and OCN(CH2)6CN0. In another case Murbach and Adicoff (67) interrupted the regularity of PTHF by copolymerization with ethylene oxide before chain extension with diphenyl-methane-4,4 -disiocyanate. Dickinson (99) prepared a series of polyurethane elastomers from THF-PO copolymer diols and 2,4-tolylene diisocyanate. He found that the use of copolymers with approximately 75 wt.-% THF led to polyurethanes with very good properties relative to the use of propylene oxide homopolymer. 

The process is the same as for the normal block co-polymers the hydrophilic block is first made by adding ethylene oxide to ethylene glycol in the normal conditions to produce a sufficiently long chain molecule which is then capped with propylene oxide to produce the hydrophobic blocks. A similar but less extensive series is available offering an even broader selection of surfactant properties from this type of chemistry. 

In the polyurethane industry, the polymeric glycols are prepared by anionic polymerization of epoxides such as ethylene oxide and propylene oxide. Poly(tetra-methylene glycol), which was prepared by polymerization of tetrahydrofuran, was subjected to chain extension by reaction with diisocyanate (polyurethane formation) and with dimethyl terephthalate (polyester by alcoholysis). 

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