Pulsed-laser and quantum mechanics study of n-butyl cyanoacrylate and methyl methacrylate free-radical copolymerization
The free-radical polymerization (FRP) kinetics for n -butyl cyanoacrylate (BCA) and methyl methacrylate (MMA) copolymerization are studied in bulk at 30–70 °C using both a pulsed-laser polymerization technique and Quantum Mechanics (QM). Through the addition of 1 v% dichloroacetic acid, the notoriou...
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| Veröffentlicht in: | Polymer chemistry 2015-01, Vol.6 (9), p.1594-1603 |
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| creator | Rooney, Thomas R. Mavroudakis, Evangelos Lacík, Igor Hutchinson, Robin A. Moscatelli, Davide |
| description | The free-radical polymerization (FRP) kinetics for
n
-butyl cyanoacrylate (BCA) and methyl methacrylate (MMA) copolymerization are studied in bulk at 30–70 °C using both a pulsed-laser polymerization technique and Quantum Mechanics (QM). Through the addition of 1 v% dichloroacetic acid, the notoriously rapid anionic polymerization of alkyl-cyanoacrylates (ACA) is successfully suppressed without affecting the FRP process. A strongly alternating copolymer sequence distribution is confirmed by reactivity ratio estimates determined using
1
H-NMR composition analysis (
r
BCA
= 0.236 ± 0.042 and
r
MMA
= 0.057 ± 0.008), in excellent agreement with QM predictions (
r
BCA
= 0.272 and
r
MMA
= 0.057) made at 50 °C. For MMA-rich monomer mixtures (0.50 ≤
f
MMA
≤ 0.97), overall propagation rate coefficients (
k
p,cop
) greater than twice the value for MMA homopolymerization (
k
p,MMA
) are facilitated by the strongly alternating copolymerization kinetics, whereas the BCA propagation rate coefficient (
k
p,BCA
) is estimated to be only 336 ± 20 L mol
−1
s
−1
at 50 °C, approximately half the value of
k
p,MMA
. These detailed results renew our understanding of the FRP kinetics for this class of monomer, important to adhesive and biomedical applications, and illustrate that an extensive and otherwise inaccessible (
via
anionic polymerization) level of control can be achieved over poly(ACA) final properties. |
| doi_str_mv | 10.1039/C4PY01423E |
| format | Article |
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n
-butyl cyanoacrylate (BCA) and methyl methacrylate (MMA) copolymerization are studied in bulk at 30–70 °C using both a pulsed-laser polymerization technique and Quantum Mechanics (QM). Through the addition of 1 v% dichloroacetic acid, the notoriously rapid anionic polymerization of alkyl-cyanoacrylates (ACA) is successfully suppressed without affecting the FRP process. A strongly alternating copolymer sequence distribution is confirmed by reactivity ratio estimates determined using
1
H-NMR composition analysis (
r
BCA
= 0.236 ± 0.042 and
r
MMA
= 0.057 ± 0.008), in excellent agreement with QM predictions (
r
BCA
= 0.272 and
r
MMA
= 0.057) made at 50 °C. For MMA-rich monomer mixtures (0.50 ≤
f
MMA
≤ 0.97), overall propagation rate coefficients (
k
p,cop
) greater than twice the value for MMA homopolymerization (
k
p,MMA
) are facilitated by the strongly alternating copolymerization kinetics, whereas the BCA propagation rate coefficient (
k
p,BCA
) is estimated to be only 336 ± 20 L mol
−1
s
−1
at 50 °C, approximately half the value of
k
p,MMA
. These detailed results renew our understanding of the FRP kinetics for this class of monomer, important to adhesive and biomedical applications, and illustrate that an extensive and otherwise inaccessible (
via
anionic polymerization) level of control can be achieved over poly(ACA) final properties.</description><identifier>ISSN: 1759-9954</identifier><identifier>EISSN: 1759-9962</identifier><identifier>DOI: 10.1039/C4PY01423E</identifier><language>eng</language><subject>Copolymerization ; Copolymers ; Cyanoacrylates ; Fiber reinforced plastics ; Monomers ; Polymerization ; Polymethyl methacrylates ; Quantum mechanics</subject><ispartof>Polymer chemistry, 2015-01, Vol.6 (9), p.1594-1603</ispartof><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c300t-232ca8ecca91413ff9e57fe26f88a8f0aa92b1cb49c4e6b31a71e45729824b1e3</citedby><cites>FETCH-LOGICAL-c300t-232ca8ecca91413ff9e57fe26f88a8f0aa92b1cb49c4e6b31a71e45729824b1e3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Rooney, Thomas R.</creatorcontrib><creatorcontrib>Mavroudakis, Evangelos</creatorcontrib><creatorcontrib>Lacík, Igor</creatorcontrib><creatorcontrib>Hutchinson, Robin A.</creatorcontrib><creatorcontrib>Moscatelli, Davide</creatorcontrib><title>Pulsed-laser and quantum mechanics study of n-butyl cyanoacrylate and methyl methacrylate free-radical copolymerization</title><title>Polymer chemistry</title><description>The free-radical polymerization (FRP) kinetics for
n
-butyl cyanoacrylate (BCA) and methyl methacrylate (MMA) copolymerization are studied in bulk at 30–70 °C using both a pulsed-laser polymerization technique and Quantum Mechanics (QM). Through the addition of 1 v% dichloroacetic acid, the notoriously rapid anionic polymerization of alkyl-cyanoacrylates (ACA) is successfully suppressed without affecting the FRP process. A strongly alternating copolymer sequence distribution is confirmed by reactivity ratio estimates determined using
1
H-NMR composition analysis (
r
BCA
= 0.236 ± 0.042 and
r
MMA
= 0.057 ± 0.008), in excellent agreement with QM predictions (
r
BCA
= 0.272 and
r
MMA
= 0.057) made at 50 °C. For MMA-rich monomer mixtures (0.50 ≤
f
MMA
≤ 0.97), overall propagation rate coefficients (
k
p,cop
) greater than twice the value for MMA homopolymerization (
k
p,MMA
) are facilitated by the strongly alternating copolymerization kinetics, whereas the BCA propagation rate coefficient (
k
p,BCA
) is estimated to be only 336 ± 20 L mol
−1
s
−1
at 50 °C, approximately half the value of
k
p,MMA
. These detailed results renew our understanding of the FRP kinetics for this class of monomer, important to adhesive and biomedical applications, and illustrate that an extensive and otherwise inaccessible (
via
anionic polymerization) level of control can be achieved over poly(ACA) final properties.</description><subject>Copolymerization</subject><subject>Copolymers</subject><subject>Cyanoacrylates</subject><subject>Fiber reinforced plastics</subject><subject>Monomers</subject><subject>Polymerization</subject><subject>Polymethyl methacrylates</subject><subject>Quantum mechanics</subject><issn>1759-9954</issn><issn>1759-9962</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNpFkE1Lw0AQhhdRsNRe_AV7FCG6X_nYo5T6AQV70IOnMNnM0kiSbXc3SPz1plbqXN5h5nln4CXkmrM7zqS-X6rNB-NKyNUZmfE81YnWmTg_9am6JIsQPtlU8sBlM_K1GdqAddJCQE-hr-l-gD4OHe3QbKFvTKAhDvVInaV9Ug1xbKkZoXdg_NhCxF9Th3E7LQ5ymluPmHioGwOTxe1cO3bom2-IjeuvyIWF6fPiT-fk_XH1tnxO1q9PL8uHdWIkYzERUhgo0BjQXHFprcY0tygyWxRQWAagRcVNpbRRmFWSQ85RpbnQhVAVRzknN8e7O-_2A4ZYdk0w2LbQoxtCybM8L7TWvJjQ2yNqvAvBoy13vunAjyVn5SHg8j9g-QOK7HCa</recordid><startdate>20150101</startdate><enddate>20150101</enddate><creator>Rooney, Thomas R.</creator><creator>Mavroudakis, Evangelos</creator><creator>Lacík, Igor</creator><creator>Hutchinson, Robin A.</creator><creator>Moscatelli, Davide</creator><scope>AAYXX</scope><scope>CITATION</scope><scope>7SP</scope><scope>7SR</scope><scope>7U5</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20150101</creationdate><title>Pulsed-laser and quantum mechanics study of n-butyl cyanoacrylate and methyl methacrylate free-radical copolymerization</title><author>Rooney, Thomas R. ; Mavroudakis, Evangelos ; Lacík, Igor ; Hutchinson, Robin A. ; Moscatelli, Davide</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c300t-232ca8ecca91413ff9e57fe26f88a8f0aa92b1cb49c4e6b31a71e45729824b1e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Copolymerization</topic><topic>Copolymers</topic><topic>Cyanoacrylates</topic><topic>Fiber reinforced plastics</topic><topic>Monomers</topic><topic>Polymerization</topic><topic>Polymethyl methacrylates</topic><topic>Quantum mechanics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Rooney, Thomas R.</creatorcontrib><creatorcontrib>Mavroudakis, Evangelos</creatorcontrib><creatorcontrib>Lacík, Igor</creatorcontrib><creatorcontrib>Hutchinson, Robin A.</creatorcontrib><creatorcontrib>Moscatelli, Davide</creatorcontrib><collection>CrossRef</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Polymer chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Rooney, Thomas R.</au><au>Mavroudakis, Evangelos</au><au>Lacík, Igor</au><au>Hutchinson, Robin A.</au><au>Moscatelli, Davide</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Pulsed-laser and quantum mechanics study of n-butyl cyanoacrylate and methyl methacrylate free-radical copolymerization</atitle><jtitle>Polymer chemistry</jtitle><date>2015-01-01</date><risdate>2015</risdate><volume>6</volume><issue>9</issue><spage>1594</spage><epage>1603</epage><pages>1594-1603</pages><issn>1759-9954</issn><eissn>1759-9962</eissn><abstract>The free-radical polymerization (FRP) kinetics for
n
-butyl cyanoacrylate (BCA) and methyl methacrylate (MMA) copolymerization are studied in bulk at 30–70 °C using both a pulsed-laser polymerization technique and Quantum Mechanics (QM). Through the addition of 1 v% dichloroacetic acid, the notoriously rapid anionic polymerization of alkyl-cyanoacrylates (ACA) is successfully suppressed without affecting the FRP process. A strongly alternating copolymer sequence distribution is confirmed by reactivity ratio estimates determined using
1
H-NMR composition analysis (
r
BCA
= 0.236 ± 0.042 and
r
MMA
= 0.057 ± 0.008), in excellent agreement with QM predictions (
r
BCA
= 0.272 and
r
MMA
= 0.057) made at 50 °C. For MMA-rich monomer mixtures (0.50 ≤
f
MMA
≤ 0.97), overall propagation rate coefficients (
k
p,cop
) greater than twice the value for MMA homopolymerization (
k
p,MMA
) are facilitated by the strongly alternating copolymerization kinetics, whereas the BCA propagation rate coefficient (
k
p,BCA
) is estimated to be only 336 ± 20 L mol
−1
s
−1
at 50 °C, approximately half the value of
k
p,MMA
. These detailed results renew our understanding of the FRP kinetics for this class of monomer, important to adhesive and biomedical applications, and illustrate that an extensive and otherwise inaccessible (
via
anionic polymerization) level of control can be achieved over poly(ACA) final properties.</abstract><doi>10.1039/C4PY01423E</doi><tpages>10</tpages><oa>free_for_read</oa></addata></record> |
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| language | eng |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Copolymerization Copolymers Cyanoacrylates Fiber reinforced plastics Monomers Polymerization Polymethyl methacrylates Quantum mechanics |
| title | Pulsed-laser and quantum mechanics study of n-butyl cyanoacrylate and methyl methacrylate free-radical copolymerization |
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