RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

Sean T. Hemp; Adam E. Smith; W. Clayton Bunyard; Michael H. Rubinstein; Timothy E. Long

doi:10.1016/j.polymer.2014.03.062

RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

Sean T. Hemp, Adam E. Smith, W. Clayton Bunyard, Michael H. Rubinstein, Timothy E. Long

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

Abstract

Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG₉₅TMA₅) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG₉₈TMA ₂-b-OEG-b-DEG₉₈TMA₂) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.

Original language	English (US)
Pages (from-to)	2325-2331
Number of pages	7
Journal	Polymer
Volume	55
Issue number	10
DOIs	https://doi.org/10.1016/j.polymer.2014.03.062
State	Published - May 13 2014
Externally published	Yes

Keywords

Hydrogels
RAFT polymerization
Stimuli-responsive

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Materials Chemistry

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10.1016/j.polymer.2014.03.062

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title = "RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels",

abstract = "Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG95TMA5) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG98TMA 2-b-OEG-b-DEG98TMA2) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.",

keywords = "Hydrogels, RAFT polymerization, Stimuli-responsive",

author = "Hemp, {Sean T.} and Smith, {Adam E.} and Bunyard, {W. Clayton} and Rubinstein, {Michael H.} and Long, {Timothy E.}",

note = "Funding Information: The authors gratefully thank Kimberly-Clark Corporation for financial and material support. This material is based upon work supported in part by the Army Research Office under grant number W911NF-07-1-0452 Ionic Liquids in Electro-Active Devices (ILEAD) MURI. This material is based upon work supported in part by the U.S. Army Research Laboratory and the Army Research Office under the Army Materials Center of Excellence Program, contract W911NF-06-2-0014 . This material is based upon work supported by the Army Research Office (ARO) under Award No. W911NF-10-1-0307 (DURIP). Dr. Michael H. Rubinstein would like to acknowledge financial support from the National Science Foundation under grants DMR-1309892 , DMR-1121107 , and DMR-1122483 , the National Institutes of Health under 1-P50-HL107168 , 1-P01-HL108808-01A1 , and the Cystic Fibrosis Foundation .",

year = "2014",

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doi = "10.1016/j.polymer.2014.03.062",

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volume = "55",

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T1 - RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

AU - Hemp, Sean T.

AU - Smith, Adam E.

AU - Bunyard, W. Clayton

AU - Rubinstein, Michael H.

AU - Long, Timothy E.

N1 - Funding Information: The authors gratefully thank Kimberly-Clark Corporation for financial and material support. This material is based upon work supported in part by the Army Research Office under grant number W911NF-07-1-0452 Ionic Liquids in Electro-Active Devices (ILEAD) MURI. This material is based upon work supported in part by the U.S. Army Research Laboratory and the Army Research Office under the Army Materials Center of Excellence Program, contract W911NF-06-2-0014 . This material is based upon work supported by the Army Research Office (ARO) under Award No. W911NF-10-1-0307 (DURIP). Dr. Michael H. Rubinstein would like to acknowledge financial support from the National Science Foundation under grants DMR-1309892 , DMR-1121107 , and DMR-1122483 , the National Institutes of Health under 1-P50-HL107168 , 1-P01-HL108808-01A1 , and the Cystic Fibrosis Foundation .

PY - 2014/5/13

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N2 - Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG95TMA5) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG98TMA 2-b-OEG-b-DEG98TMA2) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.

AB - Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG95TMA5) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG98TMA 2-b-OEG-b-DEG98TMA2) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.

KW - Hydrogels

KW - RAFT polymerization

KW - Stimuli-responsive

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RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

Abstract

Keywords

ASJC Scopus subject areas

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