New Method for the Synthesis of Fully Aliphatic Telechelic α,ω-dihydroxy Polyisobutylene


Marcela Castano1,   Matthew L. Becker1,   Judit E. Puskas1,2

Department of Polymer Science The University of Akron, Akron, USA

Department of Chemical and Biomolecular Engineering, The University of Akron, Akron, USA


This paper reports a new method for the synthesis of α,​ω-​primary-​dihydroxy PIBs (HO-​PIB-​OH) with a fully aliph. backbone.  Three aliph. difunctional initiators with tertiary-​methoxy, tertiary-​chloride and tertiary-​hydroxyl end groups (TMHDiOMe, TMHDiCl and TMHDiOH) were screened in conjunction with TiCl4 and DMA in a soln. system (hexane-​CH3Cl, 60​/40, vol.​/vol.)​.  TMHDiOMe yielded only traces of PIB, while TMHDiOH and TMHDiCl yielded PIBs with a mixt. of end group structures.  The same initiators were also screened in heterogeneous systems (CH3Cl or CH2Cl2)​.  TMHDiOMe​/TiCl4 yielded no polymer in either diluent, CH3Cl, and TMHDiOH​/TiCl4 led to olefinic end groups.  While TMHDiCl​/TiCl4 resulted in clean Cl-​PIB-​Cl in CH3Cl, the Ieff values were low and TMHDiCl was very unstable and difficult to isolate.  Premixing TMHDiOH with TiCl4 in CH3Cl led to the in situ formation of TMHDiCl.  Addn. of hexane and IB, followed by end-​capping with allyltrimethylsilane resulted in the formation of allyl-​PIB-​allyl.  Click chem. with HS-​CH2-​CH2-​OH yielded α,​ω-​primary-​dihydroxy-​PIB (HO-​PIB-​OH) with Mn = 4085 g mol-​1 and DM = 1.2. 1H-​NMR anal. verified the structure of the HO-​PIB-​OH.

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