Stereo- and enantioselective alternating copolymerization of [alpha]-olefins with carbon monoxide -- Synthesis of chiral polymers

Journal Article · Mon May 09 04:00:00 EDT 1994 · Macromolecules; (United States)

DOI:https://doi.org/10.1021/ma00088a007· OSTI ID:7288325

Jiang, Z; Adams, S E; Sen, A ^[1]

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1. Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry

Palladium(II) compounds of the type [PdL[sub 2](MeCN)[sub 2](MeCN)[sub 2]](BF[sub 4])[sub 2](L[sub 2] = chiral bidentate ligand) have been used as catalysts for the synthesis of chiral alternating [alpha]-olefin-carbon monoxide copolymers. For the synthesis of the chiral propylene-carbon monoxide copolymer and the ethylene-propylene-carbon monoxide terpolymer, chiral bidentate phosphines were employed as the ligand. The alternating styrene-carbon monoxide copolymers made thus far have been highly syndiotactic and since isotactic segments in the polymer backbone were required for chirality, a new ligand system was needed. When 2-pyridinecarboxaldehydeimine derivatives were used as the bidentate ligand, the ratio of isotactic to syndiotactic segments in the styrene-carbon monoxide copolymers was found to increase with increasing steric size of the substituent on the imine nitrogen, and when the enantiomerically pure 2-pyridinecarboxaldehyde-N-[alpha]-methylbenzylimine was employed, chiral alternating styrene-carbon monoxide copolymers were obtained. Finally, it appears that the optical rotations of the chiral copolymers were primarily due to the presence of stereogenic tertiary carbon centers in the polymer backbone with only minimal contribution from polymer conformation.

• DOE Contract Number: FG02-84ER13295
• OSTI ID: 7288325
• Journal Information: Macromolecules; (United States), Journal Name: Macromolecules; (United States) Vol. 27:10; ISSN MAMOBX; ISSN 0024-9297
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTIONS
COPOLYMERIZATION
ENANTIOMORPHS
HYDROCARBONS
ISOMERS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PALLADIUM COMPOUNDS
POLYMERIZATION
STEREOCHEMISTRY
TRANSITION ELEMENT COMPOUNDS