Effect of the Z‐ and Macro‐R‐Group on the Thermal Desulfurization of Polymers Synthesized with Acid/Base “Switchable” Dithiocarbamate RAFT Agents

Thermolysis is examined as a method for complete desulfurization of reversible addition‐fragmentation chain transfer (RAFT)‐synthesized polymers prepared with acid/base “switchable” N‐methyl‐N‐pyridyldithiocarbamates [RS2CZ or RS2CZH+]. Macro‐RAFT agents from more activated monomers (MAMs) (i.e.,...

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Published in:Macromolecular rapid communications. 2018-10, Vol.39 (19), p.e1800228-n/a
Main Authors: Stace, Sarah J., Fellows, Christopher M., Moad, Graeme, Keddie, Daniel J.
Format: Article
Language:English
Subjects:
Acetic acid
Addition polymerization
Chain transfer
Chemical synthesis
Degradation
Desulfurization
Desulfurizing
dithiocarbamate
end groups
Isopropylacrylamide
Models, Chemical
Monomers
Polymerization
Polymers
Polymers - chemical synthesis
Polymers - chemistry
Polymethyl methacrylate
RAFT
Styrene
Thermogravimetric analysis
thermogravimetric analysis (TGA)
thermolysis
Vinyl acetate
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Fellows, Christopher M.
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Keddie, Daniel J.
description Thermolysis is examined as a method for complete desulfurization of reversible addition‐fragmentation chain transfer (RAFT)‐synthesized polymers prepared with acid/base “switchable” N‐methyl‐N‐pyridyldithiocarbamates [RS2CZ or RS2CZH+]. Macro‐RAFT agents from more activated monomers (MAMs) (i.e., styrene (St), N‐isopropylacrylamide (NIPAm), and methyl methacrylate (MMA)) with RS2CZH+ and less activated monomers (LAMs) (i.e., vinyl acetate (VAc) and N‐vinylpyrolidone (NVP)) with RS2CZ are prepared by RAFT polymerization and analyzed by thermogravimetric analysis. In all cases, a mass loss consistent with loss of the end group (ZCS2H) is observed at temperatures lower than, and largely discrete from, that required for further degradation of the polymer. The temperatures for end group loss and the new end groups formed are strongly dependent on the identity of the R(P)n and the state of the pyridyl Z group; increasing in the series poly(MMA) < poly(St) ∼ poly(NIPAm)
doi_str_mv 10.1002/marc.201800228
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Macro‐RAFT agents from more activated monomers (MAMs) (i.e., styrene (St), N‐isopropylacrylamide (NIPAm), and methyl methacrylate (MMA)) with RS2CZH+ and less activated monomers (LAMs) (i.e., vinyl acetate (VAc) and N‐vinylpyrolidone (NVP)) with RS2CZ are prepared by RAFT polymerization and analyzed by thermogravimetric analysis. In all cases, a mass loss consistent with loss of the end group (ZCS2H) is observed at temperatures lower than, and largely discrete from, that required for further degradation of the polymer. The temperatures for end group loss and the new end groups formed are strongly dependent on the identity of the R(P)n and the state of the pyridyl Z group; increasing in the series poly(MMA) &lt; poly(St) ∼ poly(NIPAm) &lt;&lt; poly(VAc) ∼ poly(NVP) for S2CZ and poly(MMA) &lt; poly(St) ∼ poly(NIPAm) for S2CZH+. Clean end group removal is possible for poly(St) and poly(NVP). For poly(NIPAm), the thiocarbonyl chain end is removed, but the end group identity is less certain. For poly(MMA) and poly(VAc), some degradation of the polymer accompanies end group loss under the conditions used and further refinement of the process is required. Thermolysis is shown to be a simple and effective method for thiocarbonylthio end group removal from polymers prepared using acid/base “switchable” dithiocarbamate reversible addition‐fragmentation chain transfer (RAFT) agents. The onset temperature for end group loss is strongly dependent on the identity of the monomer‐derived macro‐R group and the charge state of the pyridyl Z group of the macro‐RAFT agent.</description><identifier>ISSN: 1022-1336</identifier><identifier>EISSN: 1521-3927</identifier><identifier>DOI: 10.1002/marc.201800228</identifier><identifier>PMID: 29748984</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Acetic acid ; Addition polymerization ; Chain transfer ; Chemical synthesis ; Degradation ; Desulfurization ; Desulfurizing ; dithiocarbamate ; end groups ; Isopropylacrylamide ; Models, Chemical ; Monomers ; Polymerization ; Polymers ; Polymers - chemical synthesis ; Polymers - chemistry ; Polymethyl methacrylate ; RAFT ; Styrene ; Thermogravimetric analysis ; thermogravimetric analysis (TGA) ; thermolysis ; Vinyl acetate</subject><ispartof>Macromolecular rapid communications., 2018-10, Vol.39 (19), p.e1800228-n/a</ispartof><rights>2018 WILEY‐VCH Verlag GmbH &amp; Co. 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Macro‐RAFT agents from more activated monomers (MAMs) (i.e., styrene (St), N‐isopropylacrylamide (NIPAm), and methyl methacrylate (MMA)) with RS2CZH+ and less activated monomers (LAMs) (i.e., vinyl acetate (VAc) and N‐vinylpyrolidone (NVP)) with RS2CZ are prepared by RAFT polymerization and analyzed by thermogravimetric analysis. In all cases, a mass loss consistent with loss of the end group (ZCS2H) is observed at temperatures lower than, and largely discrete from, that required for further degradation of the polymer. The temperatures for end group loss and the new end groups formed are strongly dependent on the identity of the R(P)n and the state of the pyridyl Z group; increasing in the series poly(MMA) &lt; poly(St) ∼ poly(NIPAm) &lt;&lt; poly(VAc) ∼ poly(NVP) for S2CZ and poly(MMA) &lt; poly(St) ∼ poly(NIPAm) for S2CZH+. Clean end group removal is possible for poly(St) and poly(NVP). For poly(NIPAm), the thiocarbonyl chain end is removed, but the end group identity is less certain. For poly(MMA) and poly(VAc), some degradation of the polymer accompanies end group loss under the conditions used and further refinement of the process is required. Thermolysis is shown to be a simple and effective method for thiocarbonylthio end group removal from polymers prepared using acid/base “switchable” dithiocarbamate reversible addition‐fragmentation chain transfer (RAFT) agents. The onset temperature for end group loss is strongly dependent on the identity of the monomer‐derived macro‐R group and the charge state of the pyridyl Z group of the macro‐RAFT agent.</description><subject>Acetic acid</subject><subject>Addition polymerization</subject><subject>Chain transfer</subject><subject>Chemical synthesis</subject><subject>Degradation</subject><subject>Desulfurization</subject><subject>Desulfurizing</subject><subject>dithiocarbamate</subject><subject>end groups</subject><subject>Isopropylacrylamide</subject><subject>Models, Chemical</subject><subject>Monomers</subject><subject>Polymerization</subject><subject>Polymers</subject><subject>Polymers - chemical synthesis</subject><subject>Polymers - chemistry</subject><subject>Polymethyl methacrylate</subject><subject>RAFT</subject><subject>Styrene</subject><subject>Thermogravimetric analysis</subject><subject>thermogravimetric analysis (TGA)</subject><subject>thermolysis</subject><subject>Vinyl acetate</subject><issn>1022-1336</issn><issn>1521-3927</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNqFkT1vFDEQhlcIREKgpUSWaGj24vF-2eVy-QApEehyNDSW1zvLOdqPw95VdKnuJ9ADf-5-CRMuBImGwhrPzONXnnmj6CXwGXAujjvj7UxwkJQI-Sg6hExAnChRPKY71WJIkvwgehbCNedcplw8jQ6EKlKpZHoYfT9tGrQjGxo2rpB93m2_MdPX7NJYP1CyoHPuh2nNhv43sVyh70zLTjBMbTN5d2tGRz0S-Di0mw59YFebntDgbrFmN25csdK6-vitCch22x9XVLIrU7W42_5kJ9R3gzW-Mp0ZkS3KsyUrv2A_hufRk8a0AV_cx6Po09npcv4uvvhw_n5eXsQ2zbiMK5tglislalVXQDMXwgAUDc8KBMBUNqlqUFSSK5tXVknI6xxyKbmBzIgqOYre7HXXfvg6YRh154LFtjU9DlPQgidS5AWkGaGv_0Gvh8n39DstAPI0pc3nRM32FO0wBI-NXntHTm00cH1nm76zTT_YRg9e3ctOVYf1A_7HJwLUHrhxLW7-I6cvy8X8r_gvugCopw</recordid><startdate>201810</startdate><enddate>201810</enddate><creator>Stace, Sarah J.</creator><creator>Fellows, Christopher M.</creator><creator>Moad, Graeme</creator><creator>Keddie, Daniel J.</creator><general>Wiley Subscription Services, Inc</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8FD</scope><scope>JG9</scope><scope>JQ2</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-8976-8651</orcidid><orcidid>https://orcid.org/0000-0003-3422-2034</orcidid><orcidid>https://orcid.org/0000-0002-4375-5580</orcidid></search><sort><creationdate>201810</creationdate><title>Effect of the Z‐ and Macro‐R‐Group on the Thermal Desulfurization of Polymers Synthesized with Acid/Base “Switchable” Dithiocarbamate RAFT Agents</title><author>Stace, Sarah J. ; 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Macro‐RAFT agents from more activated monomers (MAMs) (i.e., styrene (St), N‐isopropylacrylamide (NIPAm), and methyl methacrylate (MMA)) with RS2CZH+ and less activated monomers (LAMs) (i.e., vinyl acetate (VAc) and N‐vinylpyrolidone (NVP)) with RS2CZ are prepared by RAFT polymerization and analyzed by thermogravimetric analysis. In all cases, a mass loss consistent with loss of the end group (ZCS2H) is observed at temperatures lower than, and largely discrete from, that required for further degradation of the polymer. The temperatures for end group loss and the new end groups formed are strongly dependent on the identity of the R(P)n and the state of the pyridyl Z group; increasing in the series poly(MMA) &lt; poly(St) ∼ poly(NIPAm) &lt;&lt; poly(VAc) ∼ poly(NVP) for S2CZ and poly(MMA) &lt; poly(St) ∼ poly(NIPAm) for S2CZH+. Clean end group removal is possible for poly(St) and poly(NVP). For poly(NIPAm), the thiocarbonyl chain end is removed, but the end group identity is less certain. For poly(MMA) and poly(VAc), some degradation of the polymer accompanies end group loss under the conditions used and further refinement of the process is required. Thermolysis is shown to be a simple and effective method for thiocarbonylthio end group removal from polymers prepared using acid/base “switchable” dithiocarbamate reversible addition‐fragmentation chain transfer (RAFT) agents. The onset temperature for end group loss is strongly dependent on the identity of the monomer‐derived macro‐R group and the charge state of the pyridyl Z group of the macro‐RAFT agent.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>29748984</pmid><doi>10.1002/marc.201800228</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0002-8976-8651</orcidid><orcidid>https://orcid.org/0000-0003-3422-2034</orcidid><orcidid>https://orcid.org/0000-0002-4375-5580</orcidid><oa>free_for_read</oa></addata></record>
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source Wiley-Blackwell Read & Publish Collection
subjects Acetic acid
Addition polymerization
Chain transfer
Chemical synthesis
Degradation
Desulfurization
Desulfurizing
dithiocarbamate
end groups
Isopropylacrylamide
Models, Chemical
Monomers
Polymerization
Polymers
Polymers - chemical synthesis
Polymers - chemistry
Polymethyl methacrylate
RAFT
Styrene
Thermogravimetric analysis
thermogravimetric analysis (TGA)
thermolysis
Vinyl acetate
title Effect of the Z‐ and Macro‐R‐Group on the Thermal Desulfurization of Polymers Synthesized with Acid/Base “Switchable” Dithiocarbamate RAFT Agents
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