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Converting Step-Growth to ChainGrowth Condensation Polymerization
April FogelDahlia Amato
Akihiro Yokoyama & Tsutomu YokozawaMacromolecules, 2007
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Authors Akihiro Yokoyama
Associate Professor of Material and Life Chemistry atKanagawa University, Japan
H-index : 20 PhD in Pharmaceutical Science from University of Tokyo
Postdoctoral research at Osaka Prefecture University
Interests: Development of novel polymerization
Syntheses of polymers and supermolecules with 3Dstructure
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Authors Tsutomu Yokozawa
Professor at Dept. of Material & Life Chemistry Kanagawa
University, Japan
H-index : 18
PhD in Organic Chemistry from Tokyo Institute of Technology
Visiting Scientist at University of Illinois at Urbana-Champaign
Researcher for PRESTO JST
Interests: Controlled synthesis of polymers
Supramolecular chemistry of polymers, and dynamic
covalent chemistry
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Department of Materials and Life Chemistry
Kanagawa University, Japan
Graduate Program
13 research groups
3 courses or specialized fields
Resources
Energy and the environment
Structural and functional materials and bimolecular
engineering
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Step growth: Polymerization that occurs in a stepwise manner
between the function groups of monomers
Introduction
Monomer A
Monomer B
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Step Growth Polymer Characteristics Definite functionality ofend group
Strong intermolecular interaction in the
backbone
High thermal and chemical resistance
PDI close to 2 (too broad distribution).
Hard to control MW
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Living Polymerization Easy control MW
Narrow PDI
Various shapes and properties
Applicable only to addition to vinyl monomers,
ring opening of cyclic monomers
Not: polycondensation
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Differences in step and chain growth
(1) Amato, D. LATENT CYSTEINE RESIDUES FROM POLYMERS PREPARED VIA FREE AND CONTROLLED RADICAL POLYMERIZATIONS, California Polytechnic State University, San Luis Obispo.
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Differences in step and living Monomer in living is unreactive with other
monomers!
Only active site can be polymerized.
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*
Active Site Monomer
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Big Idea
If step growth monomers could only react
with propagating polymer then step growthwould become similar to chain growth!
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Their Goal Synthesize condensation polymers in chain
growth mannerfrom an initiator
Posses controlled MW Narrow PDI and definite end group
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Approach1. Change substituent effect
2. Selective transfer of catalysts to polymer end
group3. Transfer monomer from an unpolymerizable
solid phase to polymerizable solution phase
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Substituent effect
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Resonance Effect
Typical step growth
Yokozawa, T.; Asai, T.; Sugi, R.; Ishigooka, S.; Hiraoka, S. Chain-Growth Polycondensation for Nonbiological Polyamides of Defined Architecture.
J. Am. Chem. Soc. 2000, 122, 83138314.
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Applications
Kevlar block co-polymer
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Inductive Effect Polyamide
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Substituent Effect - Polyester
Yokoyama, A.; Iwashita, K.-I.; Hirabayashi, K.; Aiyama, K.; Yokozawa, T. Investigation of aromatic polyester synthesis by the chain-growth polycondensation method. Macromolecules 2003, 36, 43284336.17
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Substituent Effect - Polyester
*5:1 Monomer : Initiator; using CH2Cl2, R.T.
Yokoyama, A.; Iwashita, K.-I.; Hirabayashi, K.; Aiyama, K.; Yokozawa, T. Investigation of aromatic polyester synthesis by the chain-growth polycondensation method. Macromolecules 2003, 36, 43284336.
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Inductive Effect - Polyester
5:1 (M:I) 10:1 (M:I) 20:1 (M:I)
Yokoyama, A.; Iwashita, K.-I.; Hirabayashi, K.; Aiyama, K.; Yokozawa, T. Investigation of aromatic polyester synthesis by the chain-growth polycondensation method. Macromolecules 2003, 36, 43284336.
Increased transesterification at higher M:I leads to decreased control
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Substituent Effect - Polyether
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Substituent Effect - Polyether Higher molecular weight polymer is not soluble in the
polymerization solvent
Suzuki, Y.; Hiraoka, S.; Yokoyama, A.; Yokozawa, T. Chain-Growth Polycondensation for Aromatic Polyethers with Low Polydispersities: Living Polymerization Nature in Polycondensation.
Macromolecules 2003, 36, 47564765.
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Catalyst-Transfer Condensation
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Catalyst-Transfer Condensation
Yokoyama, A.; Miyakoshi, R.; Yokozawa, T. Chain-growth polymerization for poly (3-hexylthiophene) with a defined molecular weight and a low polydispersity. Macromolecules 2004, 37, 11691171.
Polymerization
is fast!
Still living!
Polymerization of2 with 0.4 mol %
of Ni(dppp)Cl2 in THF at room
temperature ([2]0 ) 0.12 M)
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Biphasic System
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Biphasic System
Yokozawa, T.; Suzuki, H. Condensative chain polymerization in solid-liquid phase. Synthesis of polyesters with a defined molecular weight and a narrow molecular weight distribution by polycondensation. J.
Am. Chem. Soc. 1999, 121, 1157311574.
Mn andMw/Mn values of polymerization obtained with
18-crown-6 in acetone at 25 C
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Summary
Chain-growth condensation polymerization
achieved through:
Substituent effect-assistance
Aromatic polyamides
Aromatic polyesters
Aromatic polyethers
Intramolecular catalyst transfer
Biphasic system
Future work Chain-growth condensation polymerization with
nonaromatic monomers 26