Allyl-telechelic polyisobutylene (A-PIB-A) produced by the bis-benzocyclobutane dichloride (bBCB-diCl) initiator contains the bis-benzocyclobutane (bBCB) fragment at the center of the macromolecule (A-PIB-bBCB-PIB-A). Thermolysis of A-PIB-bBCB-PIB-A quantitatively converts the central bBCB fragment to a substituted conjugated tetraene (A-PIB-tetraene-PIB-A). The structure of A-PIB-tetraene-PIB-A was anticipated from small molecule models and identified/quantitated by H-1 NMR spectroscopy. This is the first time a reactive functional group was introduced at the statistical center of a (telechelic) PIB. Subsequently, the A-PIB-tetraene-PIB-A was peroxidized to an epoxy derivative. Reaction of the A-PIB-tetraene-PIB-A with HSCH2CH2OH produced HOCH2-telechelic PIB containing a central -CH2OH function, and hydrosilation with HSi(Me-2)-O-Si(Me-2)H produced SiH-telechelic PIB with a central -SiH function. Reactions with maleic anhydride, tetracyanoethylene, butyl lithium, and potassium permanganate have also been examined. In sum, A-PIB-bBCB-PIB-A and A-PIB-tetraene-PIB-A are useful intermediates for the synthesis of novel PIB-based materials for various end uses under investigation. (C) 2018 Wiley Periodicals, Inc.