Poly polyTHF

An amine-terminated poly ether (ATPE) is prepared as follows. Charge poly(tetramethylene oxide) diol (PolyTHF 1000, BASF, 75.96 g, 0.0759 m) to a 500-mL three-neck round-bottom flask fitted with a thermocouple, a mechanical stirrer, and a vacuum port. Add tert-butylacetoacetate (24.04 g, 0.1582 m) and apply vacuum. Heat at 175° C for 4 h, Fourier transform infrared (FTIR) analysis should indicate complete loss of the polyol OH absorption at 3300 cm. The room temperature viscosity of the product should be about 520 mPa-s. React this acetoacetylated product (85.5 g, 0.0649 m) with cyclohexylamine (14.5 g, 0.1465 m) at 110° C under vacuum for several hours. Cool the resultant cyclohexylaminocrotonate poly ether product to room temperature (1790 mPa-s at room temperature). 

Lastly, living polyTHF has been shown to react rapidly and efficiently with the pendant pyridine units of an AB poly(styrene-b-4-vlnylpyrldlne) which had been prepared anlonlcally. The resulting graft copolymer possessed distinctly different solubility characteristics from Its parent block copolymer and Its composition and hence Its properties could be closely controlled by suitable selection of the relative reagent concentrations. 

The synthesis of high-molecular-weight poly THF became possible after the discovery of the living nature of THF polymerization. This discovery started with the work of Meerwein u and the observations were then formulated in, terms of a living process simultaneously and independently by Rosenberg et al. 1,) Dreyfuss and Drey-fuss 3) and Vofsi and Tobolsky 4) (cf. Adv. Pol. Sci. 37). Further development at DuPont, BASF and other companies led eventually to commercialization of polyTHF... 

With more nucleophilic active sites only grafting onto is possible. In this way Franta et al. grafted polyTHF onto poly(N,N-dimethylaminostyrene) and poly(2-vinylpyridine)154). The grafting process was in both cases quantitative, yielding polymeric quaternary ammonium salts ... 

In a similar way Richards et al. have grafted polyTHF onto poly(4-vinyl pyridine)... 

Due to the low solubility of poly(4-vinyl pyridine) in THF, a block copolymer of 4-vinyl pyridine with styrene has been used (Mn = 13,500). Living polyTHF (Mn = 3,300) has been grafted with efficiencies higher than 95 %. About 20 % of the pyridine units were consumed, yielding a graft copolymer with 80% polyTHF. No further data on this product were reported. 

Asami has reported grafting of living polyTHF on polymer with pendant alkali phenolates 157). Poly(p-hydroxystyrene-co-styrene) gave 100% grafting efficiency at 0 °C with Na countercations extraction with isopropanol gave 30 %-78 % copolymer the rest being insoluble gel. 

Poly (tetramethylene terephthalate). See Polybutylene terephthalate Polytex 10. See Stearamide DIBA-stearate Poly-Tex 950. See Hydroxypropyl methacrylate Poly-Tex 975, Poly-Tex 9008. See Acrylic resin Polythene. See Polyethylene PolyTHF 25a, PolyTHF 650. See Polytetramethylene ether glycol PolyTHF 100a, PolyTHF 2000. See Polyether-polycarbonate diol... 

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