New effect polymers from metal mediated living radical polymerization

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New effect polymers from metal mediated living
radical polymerization
Dave Haddleton http//www.warwick.ac.uk/polymers
BPG Annual Meeting 2002 May 17 th 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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Control of Macro-Molecular Structure
Molecular weight Chain Architecture
Functionality Rate/Exotherm
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Commercial impact of living/controlled
polymerisation

• Anionic Polymerisation is the most established
  form of living polymerisation
• Although discovered in 1956 commercial
  applications have probably not lived up to
  expectations
• Notable exception is styrene-diene block/star
  copolymers (Kraton rubbers)
• Generally anionic polymerisation requires low
  temperatures, solvents which do not chain
  transfer and extremely pure solvents and reagents.

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Innovations to Control RP

• Reversible homolytic cleavage
• Nitroxide-Mediated LRP (CSIRO, Georges, Fukuda,
  Hawker,...)
• Transition Metal Mediated LRP (ODriscoll,
  Wayland, Sawamoto, Matyjaszewski, Percec,
  Haddleton,...)
• Chain transfer processes
• Addition Fragmentation (CSIRO)
• RAFT (CSIRO)
• Catalytic Chain Transfer Polymerisation (Smirnov,
  Gridnev, Hawthorne, Janowicz, CSIRO, Haddleton,
  Davis,...)
• Combination of both
• Iniferters (Otsu)

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Transition metal mediated radical polymerisation
1995 Matyjaszewski, JACS (1995),
p5614 citations 571 Sawamoto,
Macromolecules (1995), p1721 citations 485
RuCl2(PPh3)3 / CCl4 / Al(OiPr)3
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Ligand Synthesis
Vacuum distilled, stored under nitrogen
R Et, Pr, Octyl, Octadecyl, etc
US and EP patents to Warwick Effect Polymers
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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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Mechanistic Aspects
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Polymerisation Kinetics
Long relaxation delay (5s) Low pulse angle lt 15
40 C 7h
4
2
5
3
1
90
80
75
60
40
35
25
15
0
ppm
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Mechanistic thoughts
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Solvent Effect
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Solvent Effect
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Solvent Effect
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Solvent Effect
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Solvent Effect
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Solvent Effect
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Solvent Effect
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Solvent Effect
Active Catalyst
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Solvent Effect
Active Catalyst
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Natural Abundance Kinetic Isotope Effects (KIEs)

• KIE k (12C) / k (13C).
• As reaction proceeds, enrichment in 13C
  isotopomers.
• Quantitative 13C nmr (500 MHz, long relaxation)
  used to determine 13C/12C in products vs
  reagents.
• Large KIEs when there is bond formation / change
  in hybridisation in the rate determining step.
• Information about mechanism, transition states.

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Kinetic Isotope Effects
1.045(2)
0.999(2)
1.002(2)
Radical 60C
1.000(2)
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Kinetic Isotope Effects
1.045(2)
0.999(2)
1.002(2)
Radical 60C
1.000(2)
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Kinetic Isotope Effects
1.045(2)
0.999(2)
1.002(2)
Radical 60C
1.000(2)
0.999(3)
1.050(5)
1.010(3)
ATP 60C
1.002(3)
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Kinetic Isotope Effects
1.045(2)
0.999(2)
1.002(2)
Radical 60C
1.000(2)
0.999(3)
1.050(5)
1.010(3)
ATP 60C
1.002(3)
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New Polymers
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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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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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pH 3.60
sigmoidal fit 1st derivative 2nd derivative
CAC 0.16 gL-1
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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
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Polyamide Synthesis
Temperature Ambient
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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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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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Polymerisation from a cotton surface
PMMA
PSt
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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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Playstation molecule
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AND GATE molecule requiring acid AND DMSO
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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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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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New effect polymers from metal mediated living
radical polymerization
Dave Haddleton http//www.warwick.ac.uk/polymers
BPG Annual Meeting 2002 May 17 th 2002