Synthesis of Hydroxy-Functionalized Cyclic Olefin Copolymer and Its Block Copolymers with Semicrystalline Polyolefin Segments

Abstract

Synthesis of hydroxy-functionalized cyclic olefin copolymer (COC) is achieved with remarkably high activity (up to 5.96 × 10 g-polymer mol-Ti h ) and controlled hydroxy group in a wide range (≈17.1 mol%) by using ansa-dimethylsilylene (fluorenyl)(amido)titanium complex. The catalyst also promotes living/controlled copolymerization to afford novel diblock copolymers consisting of hydroxy-functionalized COC and semicrystalline polyolefin sequence such as polyethylene and syndiotactic polypropylene, where the glass transition temperature of the norbornene/10-undecen-1-ol segment and each block length are controlled by comonomer composition and copolymerization time, respectively.

Optically Transparent Functional Polyolefin Elastomer with Excellent Mechanical and Thermal Properties

“…The T g of poly­(NB- co -U–OH) copolymer segment was not observed by DSC analysis due to its relatively low content in the copolymer, which could be found in our previous work . The 13 C NMR spectrum (see Supporting Information) indicated that the resonances corresponding to PNB and random PP sequences were observed together with those of the sequences of the NB/U–OH copolymer, respectively, testifying the formation of expected triblock copolymers.…”

Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

“…Table 1) To remove any catalyst poisons from the reactor vessel, a bomb reactor (125 mL) was charged with a solution of Me3Al (14.4 mg, 200 μmol-Al) in methylcyclohexane (17.0 g), stirred for 1 h at 100 Table 1) To remove any catalyst poisons from the reactor vessel, a bomb reactor (125 mL) was charged with a solution of Me 3 Al (14.4 mg, 200 µmol-Al) in methylcyclohexane (17.0 g), stirred for 1 h at 100 • C using a heating mantle, and the solution removed from the reactor vessel using a cannula. After completing this washing step, the reactor was charged with a solution of (CH 2 =CHC 6 H 4 CH 2 CH 2 ) 2 .0 g). This catalyst stock solution (648 mg, 4.0 µmol-Hf complex) was subsequently injected into the reactor vessel using a syringe, and the system was immediately charged with a gaseous mixture of ethylene/propylene at 20 bar pressure, which resulted in a temperature increase to~125 • C within 5 min due to the exothermic reaction, despite cooling of the reactor with a fan.…”

“…Following the development of a suitable strategy for the synthesis of PS-block-PO-block-PS, the CCTP reaction was performed in the presence of 3 (150 µmol) using 4 (4.0 µmol) activated with [(C 18 H 37 ) 2 MeNH] + [B(C 6 F 5 ) 4 ] − (1.0 equiv) as the catalyst. During this process, a ethylene/propylene gas mixture was fed into the system, and the polymerization temperature was maintained at 95-110 • C to prevent precipitation of the generated polymers.…”

“…Because the conversion of Me 3 SiCH 2 Li·(pmdeta) to styryl-Li·(pmdeta) was observed to some degree, we investigated whether styryl-Li·(pmdeta) could also trigger PS chain growth from R 2 Zn. Thus, when styrene polymerization was performed by the addition of a model compound of the styryl anion (i.e., CH 3 CH(Ph)-Li·(pmdeta), 0.50 equiv/Zn) to a methylcyclohexane solution containing styrene (500 equiv/Zn) and (hexyl) 2 Zn, the generation of PS with a narrow molecular weight distribution (M w /M n = 1.25) was observed, where Immediately following the introduction of Me3SiCH2Li·(pmdeta), the original colorless solution developed a deep yellow color due to generation of the styryl anion, which was caused by Me3SiCH2Li·(pmdeta) attacking the styrene moieties at the ends of the PO chains. However, this yellow color decreased in intensity with time, likely due to the formation of a zincate species through attack of the generated styryl anions at the Zn centers [50].…”

“…The subtle architecture of the PO chains is of particular interest in the bulk polyolefin industry. For example, sequence control to form olefin block copolymers (OBCs) is a formidable task in olefin polymerizations [1][2][3][4][5]. Following the commercialization of OBCs by the Dow Chemical Company [6][7][8], Coates et al recently reported the preparation of PE/iPP (iPP = isotactic polypropylene) multiblock copolymers to enhance capabilities of plastic recycling [1].…”