Polymerisation of Vinyl Monomers from an Insoluble PSDVB Matrix

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Polymerisation of Vinyl Monomers from an
Insoluble PS-DVB Matrix

• Neil Ayres
• University of Warwick
• n.ayres_at_warwick.ac.uk www.warwick.ac.uk/polymers

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Outline of Presentation

• Introduction
• Initiator Synthesis
• Synthesis of Polymers
• Synthesis of Block Copolymers
• Conclusions

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Metal Mediated Living Radical Polymerisation
A dynamic equilibrium exists between the
dormant and active state The polymer retains
the halogen end group
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Metal Mediated Living Radical Polymerisation
A dynamic equilibrium exists between the
dormant and active state The polymer retains
the halogen end group
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Wang Resin
Wang resin is a PS-DVB resin with the shown
linker It is transformed into an initiator with
2-bromoisobutyryl bromide
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Wang Resin
Wang resin is a PS-DVB resin with the shown
linker It is transformed into an initiator with
2-bromoisobutyryl bromide
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Aims of the Project

• Functionalise and Characterize Polystyrene
  supported Initiators for Living Radical
  Polymerisation
• Polymerisation of monomers from a PSty support
• Harvest and characterisation of Polymers from
  support
• Investigate potential applications of modified
  resins

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Polymerisation Procedure

• Transformation of Wang resin into an LRP
  initiator
• Polymerisation from the resin
• Cleavage of polymer
• Analysis

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Initiator Synthesis
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Monomers
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Synthesis of Polymers

• In order to investigate each polymerisation, each
  reaction was carried out several times, over
  different time periods
• The weight increase of the resin and the Mn and
  PDi of each polymer was recorded

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Polymerisation Analysis I
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Polymerisation Analysis I
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Polymerisation Analysis II
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Polymer Analysis II
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Removal of Copper (II) From Resin

• Passing a DCM solution of this EDTA salt through
  the resin will remove most of the
  copper(II)bromide.

After treatment with the salt solution the copper
content of a sample of resin ( w/w)
decreased from 0.2 to 9.4 x10-3
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Block Copolymers

• MMA polymerised from Wang resin was reinitiated
  with BzMA and block copolymers were produced
• Polymerisation of the block was observed by SEC
  of the cleaved polymer and gel phase 13C NMR of
  the resin

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Block Copolymer Analysis I

• Homopolymer Mn 18 500, PDi 1.06
• Block Copolymer Mn 28 200, PDi 1.24

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Block Copolymer Analysis II
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Hydrophilic Resins

• We have demonstrated the polymerisation of the
  amine containing monomers N,N-dimethylacrylamide
  (DMAc) and N-Acryloyl Sarcosine Methyl Ester
  (NASM) from PSty resin
• The resins obtained showed little deformity or
  breakage and demonstrated swelling over a range
  of solvents

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Hydrophilic Resins II
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Hydrophilic Resins III

• We plan to use the same chemistry to polymerise
  DMAc and NASM from an acrylamide resin. We will
  then functionalise the sarcosine groups and test
  these resins applicability as scavengers.

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Conclusions

• Wang resin is easily transformed into an LRP
  initiator
• We can graft methacrylate monomers in a
  controlled fashion (PDi 1.40) and form block
  copolymers
• By using resin based techniques this chemistry
  could be applied to high throughput /
  combinatorial methods

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Acknowledgements

• Prof. David Haddleton
• Avecia Limited David Pears and Andrew Shooter
• Warwick Polymer Group