Alternating copolymers of functional alkenes with carbon monoxide

Smita Kacker, Zhaozhong Jiang, Ayusman Sen

Research output: Contribution to journalArticle

61 Citations (Scopus)

Abstract

The alternating copolymerization of functional alkenes, CH2=CH(CH2)xOH (x = 2, 3, 4, 9), CH2=CH(CH2)xCOOH (x = 1, 2, 4, 8), and 4-allylanisole, with carbon monoxide was achieved by using [Pd(Me-DUPHOS)(MeCN)2](BF4)2 [Me-DUPHOS = 1,2-bis(2,5-dimethylphospholano)benzene] as the catalyst. The resultant polymers were optically active with isotactic sequences in the backbone. With most alkenes, the polymers had poly(1,4-ketone) and/or "regular" poly(spiroketal) (i.e., 1,6-dioxaspiro-[4.4]nonane) enchainments. However, with 4-penten-1-ol and 3-buten-1-ol, the participation of the pendant hydroxyl group in intrachain reactions led to the formation of unusual polycyclic repeating units in the backbone. A comparison of [Pd(Me-DUPHOS)(MeCN)2](BF4)2 with [Pd(DPPP)(MeCN)2](BF4)2 [DPPP = 1,3-bis(diphenylphosphino)propane] indicated that the former was a significantly better catalyst for the alternating copolymerization of alkenols and alkenoic acids with carbon monoxide.

Original languageEnglish (US)
Pages (from-to)5852-5858
Number of pages7
JournalMacromolecules
Volume29
Issue number18
DOIs
StatePublished - Aug 26 1996

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Alkenes
Carbon Monoxide
Carbon monoxide
Copolymerization
Olefins
Polymers
Copolymers
Catalysts
Benzene
Ketones
Carboxylic acids
Propane
Hydroxyl Radical
nonane
1-penten-3-ol
1,3-bis(diphenylphosphino)propane
spiroketal
estragole

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Kacker, Smita ; Jiang, Zhaozhong ; Sen, Ayusman. / Alternating copolymers of functional alkenes with carbon monoxide. In: Macromolecules. 1996 ; Vol. 29, No. 18. pp. 5852-5858.
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Alternating copolymers of functional alkenes with carbon monoxide. / Kacker, Smita; Jiang, Zhaozhong; Sen, Ayusman.

In: Macromolecules, Vol. 29, No. 18, 26.08.1996, p. 5852-5858.

Research output: Contribution to journalArticle

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AB - The alternating copolymerization of functional alkenes, CH2=CH(CH2)xOH (x = 2, 3, 4, 9), CH2=CH(CH2)xCOOH (x = 1, 2, 4, 8), and 4-allylanisole, with carbon monoxide was achieved by using [Pd(Me-DUPHOS)(MeCN)2](BF4)2 [Me-DUPHOS = 1,2-bis(2,5-dimethylphospholano)benzene] as the catalyst. The resultant polymers were optically active with isotactic sequences in the backbone. With most alkenes, the polymers had poly(1,4-ketone) and/or "regular" poly(spiroketal) (i.e., 1,6-dioxaspiro-[4.4]nonane) enchainments. However, with 4-penten-1-ol and 3-buten-1-ol, the participation of the pendant hydroxyl group in intrachain reactions led to the formation of unusual polycyclic repeating units in the backbone. A comparison of [Pd(Me-DUPHOS)(MeCN)2](BF4)2 with [Pd(DPPP)(MeCN)2](BF4)2 [DPPP = 1,3-bis(diphenylphosphino)propane] indicated that the former was a significantly better catalyst for the alternating copolymerization of alkenols and alkenoic acids with carbon monoxide.

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