Exploitation of the Strathclyde methodology in synthesizing branched vinyl polymers

David C. Sherrington, Marc-Henri Bouhier, Peter A. G. Cormack, Susan. Graham

Research output: Contribution to conferenceAbstract

Abstract

The 'Strathclyde Route' to branched vinyl polymers involves the conventional free radical soln. polymn. of a monovinyl monomer with a multi-functional monomer in the presence of an appropriate level of a chain transfer agent to suppress crosslinking. For some potential applications of branched polymers soln. polymn. would not be cost-effective. We have therefore carried out high conversion aq. emulsion copolymns. of Me methacrylate (MMA) and divinylbenzene (DVB) using sodium dodecyl sulfate as the emulsifier, potassium persulfate as the initiator and benzylthiol as the chain transfer agent. No org. solvent is employed and complete suppression of crosslinking is achieved for MMA/DVB feed mole ratios up to 5/1. 'H NMR spectroscopic and MALS/SEC analyses confirm the highly branched nature of the PMMA products which is far higher than we have been able to achieve under bulk or aq. suspension polymn. conditions. In addn. the molar mass distributions are significantly lower than those of similar materials prepd. in soln. polymns. To date we not been able to rationalise all of these exptl. findings. Early in our branching studies we realized that use of controlled polymns. might yield less broad mol. wt. distributions. We also speculated that crosslinking might be avoided, even at high conversion and without the use of a chain regulating agent, by employing a mole ratio of difunctional comonomer/initiator of ∼ 1/1, to favor statistically one branch per primary polymer chain. This proved to be so exptl. and we have now synthesized densely branched poly(Me methacrylate)s with high conversions via soln. ATR copolymn. of MMA and EGDMA. Also by employing an ATRP initiator with a discrete signature in its 'H NMR spectrum, coupled with MALS/SEC anal., very detailed evaluation of mol. structure and backbone architecture is possible. [on SciFinder(R)]

Conference

Conference235th American Chemical Society National Meeting
CountryUnited States
CityNew Orleans
Period7/04/08 → …

Fingerprint

divinyl benzene
Methacrylates
Polymers
Crosslinking
Monomers
Nuclear magnetic resonance
Molar mass
Atom transfer radical polymerization
Polymethyl Methacrylate
Emulsions
Sodium Dodecyl Sulfate
Free Radicals
Suspensions
Costs

Keywords

  • vinyl polymers
  • monovinyl monomer
  • polymerization

Cite this

Sherrington, D. C., Bouhier, M-H., Cormack, P. A. G., & Graham, S. (2008). Exploitation of the Strathclyde methodology in synthesizing branched vinyl polymers. Abstract from 235th American Chemical Society National Meeting, New Orleans, United States.
Sherrington, David C. ; Bouhier, Marc-Henri ; Cormack, Peter A. G. ; Graham, Susan. / Exploitation of the Strathclyde methodology in synthesizing branched vinyl polymers. Abstract from 235th American Chemical Society National Meeting, New Orleans, United States.
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abstract = "The 'Strathclyde Route' to branched vinyl polymers involves the conventional free radical soln. polymn. of a monovinyl monomer with a multi-functional monomer in the presence of an appropriate level of a chain transfer agent to suppress crosslinking. For some potential applications of branched polymers soln. polymn. would not be cost-effective. We have therefore carried out high conversion aq. emulsion copolymns. of Me methacrylate (MMA) and divinylbenzene (DVB) using sodium dodecyl sulfate as the emulsifier, potassium persulfate as the initiator and benzylthiol as the chain transfer agent. No org. solvent is employed and complete suppression of crosslinking is achieved for MMA/DVB feed mole ratios up to 5/1. 'H NMR spectroscopic and MALS/SEC analyses confirm the highly branched nature of the PMMA products which is far higher than we have been able to achieve under bulk or aq. suspension polymn. conditions. In addn. the molar mass distributions are significantly lower than those of similar materials prepd. in soln. polymns. To date we not been able to rationalise all of these exptl. findings. Early in our branching studies we realized that use of controlled polymns. might yield less broad mol. wt. distributions. We also speculated that crosslinking might be avoided, even at high conversion and without the use of a chain regulating agent, by employing a mole ratio of difunctional comonomer/initiator of ∼ 1/1, to favor statistically one branch per primary polymer chain. This proved to be so exptl. and we have now synthesized densely branched poly(Me methacrylate)s with high conversions via soln. ATR copolymn. of MMA and EGDMA. Also by employing an ATRP initiator with a discrete signature in its 'H NMR spectrum, coupled with MALS/SEC anal., very detailed evaluation of mol. structure and backbone architecture is possible. [on SciFinder(R)]",
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author = "Sherrington, {David C.} and Marc-Henri Bouhier and Cormack, {Peter A. G.} and Susan. Graham",
year = "2008",
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note = "235th American Chemical Society National Meeting ; Conference date: 07-04-2008",

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Sherrington, DC, Bouhier, M-H, Cormack, PAG & Graham, S 2008, 'Exploitation of the Strathclyde methodology in synthesizing branched vinyl polymers' 235th American Chemical Society National Meeting, New Orleans, United States, 7/04/08, .

Exploitation of the Strathclyde methodology in synthesizing branched vinyl polymers. / Sherrington, David C.; Bouhier, Marc-Henri; Cormack, Peter A. G.; Graham, Susan.

2008. Abstract from 235th American Chemical Society National Meeting, New Orleans, United States.

Research output: Contribution to conferenceAbstract

TY - CONF

T1 - Exploitation of the Strathclyde methodology in synthesizing branched vinyl polymers

AU - Sherrington, David C.

AU - Bouhier, Marc-Henri

AU - Cormack, Peter A. G.

AU - Graham, Susan.

PY - 2008/4/7

Y1 - 2008/4/7

N2 - The 'Strathclyde Route' to branched vinyl polymers involves the conventional free radical soln. polymn. of a monovinyl monomer with a multi-functional monomer in the presence of an appropriate level of a chain transfer agent to suppress crosslinking. For some potential applications of branched polymers soln. polymn. would not be cost-effective. We have therefore carried out high conversion aq. emulsion copolymns. of Me methacrylate (MMA) and divinylbenzene (DVB) using sodium dodecyl sulfate as the emulsifier, potassium persulfate as the initiator and benzylthiol as the chain transfer agent. No org. solvent is employed and complete suppression of crosslinking is achieved for MMA/DVB feed mole ratios up to 5/1. 'H NMR spectroscopic and MALS/SEC analyses confirm the highly branched nature of the PMMA products which is far higher than we have been able to achieve under bulk or aq. suspension polymn. conditions. In addn. the molar mass distributions are significantly lower than those of similar materials prepd. in soln. polymns. To date we not been able to rationalise all of these exptl. findings. Early in our branching studies we realized that use of controlled polymns. might yield less broad mol. wt. distributions. We also speculated that crosslinking might be avoided, even at high conversion and without the use of a chain regulating agent, by employing a mole ratio of difunctional comonomer/initiator of ∼ 1/1, to favor statistically one branch per primary polymer chain. This proved to be so exptl. and we have now synthesized densely branched poly(Me methacrylate)s with high conversions via soln. ATR copolymn. of MMA and EGDMA. Also by employing an ATRP initiator with a discrete signature in its 'H NMR spectrum, coupled with MALS/SEC anal., very detailed evaluation of mol. structure and backbone architecture is possible. [on SciFinder(R)]

AB - The 'Strathclyde Route' to branched vinyl polymers involves the conventional free radical soln. polymn. of a monovinyl monomer with a multi-functional monomer in the presence of an appropriate level of a chain transfer agent to suppress crosslinking. For some potential applications of branched polymers soln. polymn. would not be cost-effective. We have therefore carried out high conversion aq. emulsion copolymns. of Me methacrylate (MMA) and divinylbenzene (DVB) using sodium dodecyl sulfate as the emulsifier, potassium persulfate as the initiator and benzylthiol as the chain transfer agent. No org. solvent is employed and complete suppression of crosslinking is achieved for MMA/DVB feed mole ratios up to 5/1. 'H NMR spectroscopic and MALS/SEC analyses confirm the highly branched nature of the PMMA products which is far higher than we have been able to achieve under bulk or aq. suspension polymn. conditions. In addn. the molar mass distributions are significantly lower than those of similar materials prepd. in soln. polymns. To date we not been able to rationalise all of these exptl. findings. Early in our branching studies we realized that use of controlled polymns. might yield less broad mol. wt. distributions. We also speculated that crosslinking might be avoided, even at high conversion and without the use of a chain regulating agent, by employing a mole ratio of difunctional comonomer/initiator of ∼ 1/1, to favor statistically one branch per primary polymer chain. This proved to be so exptl. and we have now synthesized densely branched poly(Me methacrylate)s with high conversions via soln. ATR copolymn. of MMA and EGDMA. Also by employing an ATRP initiator with a discrete signature in its 'H NMR spectrum, coupled with MALS/SEC anal., very detailed evaluation of mol. structure and backbone architecture is possible. [on SciFinder(R)]

KW - vinyl polymers

KW - monovinyl monomer

KW - polymerization

UR - http://oasys2.confex.com/acs/235nm/techprogram/P1123338.HTM

M3 - Abstract

ER -

Sherrington DC, Bouhier M-H, Cormack PAG, Graham S. Exploitation of the Strathclyde methodology in synthesizing branched vinyl polymers. 2008. Abstract from 235th American Chemical Society National Meeting, New Orleans, United States.