New macromolecular architecture and functionality from living radical polymerisation

1
New macromolecular architecture and functionality
from living radical polymerisation
Dave Haddleton http//www.warwick.ac.uk/polymers
Australian Polymer Symposium February 2002
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Control over Polymer Architecture

• Graft Copolymers
• Star copolymers
• Dendrimers
• Non covalent crosslinking
• Branching
• Narrow MWD
• Blocks

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Transition metal mediated radical polymerisation
1995 Matyjaszewski, JACS (1995),
p5614 citations 504 Sawamoto,
Macromolecules (1995), p1721 citations 435
RuCl2(PPh3)3 / CCl4 / Al(OiPr)3
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Polymerisation Chemistry
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Copper Mediated LRP

• Inert to most Functional groups
• e.g. OH, NR2, NH2, ROR, H2O
• Easy to carry out
• Acceptable Process
• Scale up easy
• Process Patent Protected (WEP Ltd)

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Catalyst removal on basic alumina column
No work up
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Reaction underway
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Mn 10,500 Pdi 1.15
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Methacrylates
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Water soluble monomers
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Methacrylates
Over 250 commercially available
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New Polymers
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Synthesis of Initiators from alcohols
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Hydrophobic Fluorinated Initiator
PMMA
PMMA - Di Fluoroinitiator
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Surfactant Molecules

• CMC 0.089 g mol-1

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Synthesis of Block Copolymers
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Kinetics for Kraton-b-P(DMAEMA)
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Preparation of PDMS macroinitiators
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Tri-block copolymers from di-functional PDMS
initiators
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Critical micelle concentration by fluorimetry
CMC 0.1 g / L
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Adenosine and uridine derived initiators and
monomers
Dr Andrew Marsh, Warwick
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Polymers containing bio-recognition sites
Mn 12 600, PDi 1.06
Dr Andrew Marsh, Warwick
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Adenosine and uridine derived initiators and
monomers
Dr Andrew Marsh, Warwick
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Synthesis of Oligosaccharide-Carrying Initiator
Ac2O, DMAP
H2SO4
in Pyridine, at r.t.
in Ac2O, at 55 oC
Benzylamine
in THF, at r.t.
Triethylamine
in CH2Cl2, at 0 oC
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ATP of MMA by AcMH-Br
MMA0/AcMH-Br0/Cu(I)Br0/Ligand0
100/1/1/2, 50 vol MMA in Toluene, at 90 oC
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Oligosaccharide terminated Polymers
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Sugar terminated amphiphilic block copolymers
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Hydrophobic
Hydrophilic
Sugar
SEC Trace
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HPLC traces of sugar bearing block copolymers
micelles from RCA-1 Lectin immobilized column
Glucose-PEGMA-b-PBzMA
Flow rate 0.8 mL/min Detection UV -254 nm
Protected Galactose-PEGMA-b-PBzMA
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pH 3.60
sigmoidal fit 1st derivative 2nd derivative
CAC 0.16 gL-1
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Dendrimer initiators for atom transfer
Neldes J. Hovestad, Johann T.B.H. Jastrzebski and
Gerard van Koten Utrecht University,, The
Netherlands.
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Polyamide Synthesis
Temperature Ambient
S Monge Poster P13 Page 39
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Supported Initiator Synthesis
Commercial Wang resin load 1 to 4 mmol.g-1
of 4-hydroxybenzyl alcohol functions

ONE STEP PROCEDURE PURIFICATION BY WASHING
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• SEM image of the resin with initiating
  functionality.
• SEM image of the resin after polymerization.

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Summary

• A wide range of polymers are now available
• Polymer Synthesis needs direction with real
  application targets
• Imagination is now the limitation in
  macromolecular architecture

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Acknowledgements
Funding EPSRC (UK Government) EC RTN
(POLYCAT) EC RTN (MIPA) EC Marie Curie
Scheme Univ. of Warwick Unilever Avecia BP Uniqema
/ICI Syngenta Malvern Instruments GelTex Rohm
Haas
Co-Workers past... Dr Andrew Shooter (Avecia) Dr
Dax Kukulj (Unilever) Dr Dave Duncalf (Avecia) Dr
Liz Kelly (Unilever) Dr Carl Waterson
(Infinium) Dr Afzal Khan(Glaxo Wellcome) Dr Alex
Hemming (Syngenta) Arnaud Radigue (Elf) Dr
Stephanie Angot (Flanel) Dr Stuart Jackson (P
G) Dr Stefan Bon (Warwick) Dr Kohji Ohno
(Kyoto) Dr Stuart Morsley Delphine Bethier Dr Kim
Huan (Rhodia) Dr Sebastien Perrier (UNSW) Dr
Sagrario Pascual (LeMans) Ryan Edmonds Dr
Delphine Coutrot (Heriot Watt)
and present Dr Adam Jarvis (Warwick Effect
Polymers) Dr Adrian Carmichael Dr Laurence Bes Dr
Michael Even Dr Delphine Coutrot Dr Andy
Steward Dr Sophie Monge Dr Vincent Darcos Jeetan
Lad Neil Ayres Amilcar Pillay Narrainen Benjamin
Wong Adam Limer Ian Willoughby Francois
LeColley Charlene Wager Dr Simon Harisson Lindsay
Ellis Paul Williams
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(No Transcript)
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New macromolecular architecture and functionality
from living radical polymerisation
Dave Haddleton http//www.warwick.ac.uk/polymers
Australian Polymer Symposium February 2002
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SEM Image of a 21-arm Polystyrene Star

• Film formation in CS2
• Relative humidity 70
• Temperature 19C
• Regular hexagonal distribution of pores 2 µm

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Carbohydrate based star poly(styrene) film SEM
image
Each hole is 0.5 - 1.0 microns
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Removal of Copper (II) From Resin

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

• After treatment with the salt solution the copper
  content of the resin ( w/w) decreased from
  0.2 to 9.4 x10-3 .

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Pentablock Synthesis
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Pentablock Synthesis
Mn 17,500, PDi 1.07
Mn 8,020, PDi 1.08
Mn 21,900, PDi 1.08
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Star Polymers
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Mn 82,500
66 toluene, 90
o
C
1.
2.
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Star polymers based on glucose
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Polymerisation with sucrose derived initiator