Converting Step-Growth to Chain Growth Condensation Polymerization

Akihiro Yokoyama & Tsutomu Yokozawa

Macromolecules, 2007
April Fogel Dahlia Amato

Authors
Akihiro Yokoyama Associate Professor of Material and Life Chemistry at Kanagawa 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 3D structure
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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

Introduction
Step growth:
Polymerization that occurs in a stepwise manner between the function groups of monomers

Monomer A Monomer B

Step Growth Polymer Characteristics

Definite functionality of end 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

Differences in step and chain growth

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(1) Amato, D. LATENT CYSTEINE RESIDUES FROM POLYMERS PREPARED VIA FREE AND CONTROLLED RADICAL POLYMERIZATIONS, California Polytechnic State University, San Luis Obispo.

Differences in step and living

Monomer in living is unreactive with other monomers! Only active site can be polymerized.

*
Active Site Monomer
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Big Idea
If step growth monomers could only react with propagating polymer then step growth would become similar to chain growth!

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Their Goal
Synthesize condensation polymers in chain growth manner from an initiator
Posses controlled MW Narrow PDI and definite end group

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Approach
1. Change substituent effect 2. Selective transfer of catalysts to polymer end group 3. 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

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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.

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.

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Substituent Effect - Polyester

*5:1 Monomer : Initiator; using CH2Cl2, R.T.

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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.

Inductive Effect - Polyester

5:1 (M:I) 10:1 (M:I) 20:1 (M:I)

Increased transesterification at higher M:I leads to decreased control

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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.

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
Polymerization of 2 with 0.4 mol % of Ni(dppp)Cl2 in THF at room temperature ([2]0 ) 0.12 M)

Polymerization is fast!

Still living!

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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.

Biphasic System

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Biphasic System

Mn and Mw/Mn values of polymerization obtained with 18-crown-6 in acetone at 25 C

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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.

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
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