Polypropylenes borane-terminated

Lu, B., Chung, T. C. Maleic anhydride modified polypropylene with controllable molecular structure New synthetic route via borane-terminated polypropylene. Macromolecules, 31, 5943-5946 (1998). 

One such reported example is the synthesis of polypropylene-6-polymethyl-methacrylate (PP-6-PMMA) copolymers utilizing metallocene catalysis and the borane chemistry. In the initial step, PP with chain-end olefinic unsaturations was prepared using metallocene catalysts such as Et(Ind)2ZrCl2/MAO. The unsaturation sites were then hydroborated by 9-borabicyclo[3.3.1]nonane (9-BBN) to produce borane-terminated PP (43) (Fig. 30), which was selectively oxidized and interconverted to a... 

In a recent development, a new process of preparing borane-terminated isotactic polypropylene (z -PPs) via an in situ chain-transfer reaction was achieved by a styrene/hydrogen consecutive chain-transfer reagent, which avoids the use of a B—H containing chain-transfer agent.74 This has resulted in the utilization of milder polymerization conditions due to the use of the alkylaluminoxane cocatalyst (MAO) (50) (Fig. 33), which cannot normally be used in the presence of a B—H chain-transferring... 

Block copolymers can be produced from terminally borane-containing polyolefins. These borane-containing POs can be synthesized by the metallocene-catalyzed (co)polymerization of olefin(s) monomer with 9-BBN as a chain transfer agent or by the metallocene catalyzed copolymerization of olefins with allyl-9-BBN [55,56], as referred to above. Alternatively, borane-containing POs were prepared by hydroboration of terminally unsaturated PO, for instance, terminally vinyl PE and terminally vinylidene PP [33-35,57]. Such method could produce diblock copolymers, such as polyethylene-block-poly(methyl methacrylate) (PE-fo-PMMA), polypropylene-foZock-poly(methyl methacrylate) (PP-fc-PMMA), polypropylene-foZock-poly(butyl methacrylate) (PP-fc-PBMA), and PP-fc-PS. 

SCHEME 11.4 Preparation of polypropylenes with (a) terminal and (b) pendant borane functional groups (R = aUcyl). 

In the absence of hydrogen, metallocene-based catalyst systems produce well-defined polymers which are olefin- or aluminum-terminated. Miilhaupt has polymerized propylene with a chiral metallocene and MAO under conditions where P-hydrogen elimination was the predominant chain transfer process. In a post-polymerization functionalization, the olefin endgroups of the highly isotactic polypropylene chains were converted to bromo-, epoxy-, anhydride-, ester-, amine-, carboxylic acid-, silane-, borane-, hydroxy-, thiol-terminated polymers as intermediates for the preparation of block copolymers. Using olefin-terminated atactic and isotactic polypropylene formed with MAO-activated Cp2ZrCl2 and (EBTHI)ZrCl2 Shiono has synthesized amine- and aluminum-terminated polymers." ... 

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