Crosslinking during radical polymerization of dodecyl methacrylate

Dibutyl Itaconate and Lauryl Methacrylate Copolymers by Emulsion Polymerization for Development of Sustainable Pressure-Sensitive Adhesives

“…The emulsion polymerization process can occur chain branching and gel formation, without a cross-linking agent, due to the propagation of terminal double bond or via intermolecular chain transfer to polymer [ 37 , 38 ]. Furthermore, it has been reported that the polymerization of LMA by the mechanism free radical polymerization forms cross-linked networks at high conversion and temperatures up to 90 °C as a consequence of chain transfer to the polymer through the attack of the alkyl side-group [ 39 , 40 ]. In this research, the conversion from monomer to copolymer is above 97% for all samples.…”

Dibutyl Itaconate and Lauryl Methacrylate Copolymers by Emulsion Polymerization for Development of Sustainable Pressure-Sensitive Adhesives

“…The emulsion polymerization process can occur chain branching and gel formation, without a cross-linking agent, due to the propagation of terminal double bond or via intermolecular chain transfer to polymer [ 37 , 38 ]. Furthermore, it has been reported that the polymerization of LMA by the mechanism free radical polymerization forms cross-linked networks at high conversion and temperatures up to 90 °C as a consequence of chain transfer to the polymer through the attack of the alkyl side-group [ 39 , 40 ]. In this research, the conversion from monomer to copolymer is above 97% for all samples.…”

Dodecyl Methacrylate Polymerization under Nanoconfinement: Reactivity and Resulting Properties

“…The latter is consistent with the literature and attributed to chain transfer to polymer. 12,13 For reactions carried out under nanoconfinement, mass-average molar masses are lower than for bulk reactions at temperatures of 170 °C and above, suggesting that the nanoconfined termination reaction is faster relative to propagation under nanoconfinement at high temperatures. The result differs from our previous work on MMA, 4 where molar mass was found to increase in nanoconfined polymerization due to earlier autoacceleration.…”

“…The effect of synthesis under nanoconfinement on the molar mass for longer n -alkyl methacrylate monomers is not as straightforward, however. In the particular case of n -dodecyl methacrylate, chain transfer to the polymer during the bulk polymerization leads to branching and cross-linked products, − and if such products are suppressed under nanoconfinement, as is the case for vinyl esters in metallic organic frameworks and for ε-caprolactone in aluminum oxide membranes, one might expect a decrease in molar mass for polymer synthesized under nanoconfinement. In addition to promoting chain transfer to polymer, the long alkyl side chain in the dodecyl methacrylate monomer leads to a suppression of autoacceleration, , an increase in the propagation rate constant, − a decrease in the rate of termination, and a propensity of the dodecyl groups in the polymer to crystallize…”

“…In the particular case of n -dodecyl methacrylate, chain transfer to the polymer during the bulk polymerization leads to branching and cross-linked products, − and if such products are suppressed under nanoconfinement, as is the case for vinyl esters in metallic organic frameworks and for ε-caprolactone in aluminum oxide membranes, one might expect a decrease in molar mass for polymer synthesized under nanoconfinement. In addition to promoting chain transfer to polymer, the long alkyl side chain in the dodecyl methacrylate monomer leads to a suppression of autoacceleration, , an increase in the propagation rate constant, − a decrease in the rate of termination, and a propensity of the dodecyl groups in the polymer to crystallize…”

Covalent Adaptable Networks Made by Reactive Processing of Highly Entangled Polymer: Synthesis-Structure-Thermomechanical Property-Reprocessing Relationship in Covalent Adaptable Networks

“…It occurs to a much lesser extent in low-density PE (LDPE); chain transfer and branching are the predominant mechanisms with LDPE. − CH 2 units in branches off the LDPE backbone also serve as sites for radical formation and cross-linking. − Similarly, radicals may form on CH 2 units in the side chains of other polymers and, thus, cause further branching, cross-linking, and chain scission . This phenomenon has been observed in ethylene-vinyl acetate copolymer (EVA), , poly­(vinyl ethers), − polyacrylates, − and polymethacrylates. − In these polymers, cross-linking efficiency (moles of generated cross-links per mole of decomposed initiator) and the proportion of cross-linking to chain scission after radical formation have been studied as functions of side-chain length, isomerism, and average molecular weight. − …”

Dibutyl Itaconate and Lauryl Methacrylate Copolymers by Emulsion Polymerization for Development of Sustainable Pressure-Sensitive Adhesives

“…The emulsion polymerization process can occur chain branching and gel formation, without a cross-linking agent, due to the propagation of terminal double bond or via intermolecular chain transfer to polymer [ 37 , 38 ]. Furthermore, it has been reported that the polymerization of LMA by the mechanism free radical polymerization forms cross-linked networks at high conversion and temperatures up to 90 °C as a consequence of chain transfer to the polymer through the attack of the alkyl side-group [ 39 , 40 ]. In this research, the conversion from monomer to copolymer is above 97% for all samples.…”

Dodecyl Methacrylate Polymerization under Nanoconfinement: Reactivity and Resulting Properties

“…The latter is consistent with the literature and attributed to chain transfer to polymer. 12,13 For reactions carried out under nanoconfinement, mass-average molar masses are lower than for bulk reactions at temperatures of 170 °C and above, suggesting that the nanoconfined termination reaction is faster relative to propagation under nanoconfinement at high temperatures. The result differs from our previous work on MMA, 4 where molar mass was found to increase in nanoconfined polymerization due to earlier autoacceleration.…”

“…The effect of synthesis under nanoconfinement on the molar mass for longer n -alkyl methacrylate monomers is not as straightforward, however. In the particular case of n -dodecyl methacrylate, chain transfer to the polymer during the bulk polymerization leads to branching and cross-linked products, − and if such products are suppressed under nanoconfinement, as is the case for vinyl esters in metallic organic frameworks and for ε-caprolactone in aluminum oxide membranes, one might expect a decrease in molar mass for polymer synthesized under nanoconfinement. In addition to promoting chain transfer to polymer, the long alkyl side chain in the dodecyl methacrylate monomer leads to a suppression of autoacceleration, , an increase in the propagation rate constant, − a decrease in the rate of termination, and a propensity of the dodecyl groups in the polymer to crystallize…”

“…In the particular case of n -dodecyl methacrylate, chain transfer to the polymer during the bulk polymerization leads to branching and cross-linked products, − and if such products are suppressed under nanoconfinement, as is the case for vinyl esters in metallic organic frameworks and for ε-caprolactone in aluminum oxide membranes, one might expect a decrease in molar mass for polymer synthesized under nanoconfinement. In addition to promoting chain transfer to polymer, the long alkyl side chain in the dodecyl methacrylate monomer leads to a suppression of autoacceleration, , an increase in the propagation rate constant, − a decrease in the rate of termination, and a propensity of the dodecyl groups in the polymer to crystallize…”

Covalent Adaptable Networks Made by Reactive Processing of Highly Entangled Polymer: Synthesis-Structure-Thermomechanical Property-Reprocessing Relationship in Covalent Adaptable Networks

“…It occurs to a much lesser extent in low-density PE (LDPE); chain transfer and branching are the predominant mechanisms with LDPE. − CH 2 units in branches off the LDPE backbone also serve as sites for radical formation and cross-linking. − Similarly, radicals may form on CH 2 units in the side chains of other polymers and, thus, cause further branching, cross-linking, and chain scission . This phenomenon has been observed in ethylene-vinyl acetate copolymer (EVA), , poly­(vinyl ethers), − polyacrylates, − and polymethacrylates. − In these polymers, cross-linking efficiency (moles of generated cross-links per mole of decomposed initiator) and the proportion of cross-linking to chain scission after radical formation have been studied as functions of side-chain length, isomerism, and average molecular weight. − …”

Dibutyl Itaconate and Lauryl Methacrylate Copolymers by Emulsion Polymerization for Development of Sustainable Pressure-Sensitive Adhesives

“…The emulsion polymerization process can occur chain branching and gel formation, without a cross-linking agent, due to the propagation of terminal double bond or via intermolecular chain transfer to polymer [ 37 , 38 ]. Furthermore, it has been reported that the polymerization of LMA by the mechanism free radical polymerization forms cross-linked networks at high conversion and temperatures up to 90 °C as a consequence of chain transfer to the polymer through the attack of the alkyl side-group [ 39 , 40 ]. In this research, the conversion from monomer to copolymer is above 97% for all samples.…”

Dodecyl Methacrylate Polymerization under Nanoconfinement: Reactivity and Resulting Properties

“…The latter is consistent with the literature and attributed to chain transfer to polymer. 12,13 For reactions carried out under nanoconfinement, mass-average molar masses are lower than for bulk reactions at temperatures of 170 °C and above, suggesting that the nanoconfined termination reaction is faster relative to propagation under nanoconfinement at high temperatures. The result differs from our previous work on MMA, 4 where molar mass was found to increase in nanoconfined polymerization due to earlier autoacceleration.…”

“…The effect of synthesis under nanoconfinement on the molar mass for longer n -alkyl methacrylate monomers is not as straightforward, however. In the particular case of n -dodecyl methacrylate, chain transfer to the polymer during the bulk polymerization leads to branching and cross-linked products, − and if such products are suppressed under nanoconfinement, as is the case for vinyl esters in metallic organic frameworks and for ε-caprolactone in aluminum oxide membranes, one might expect a decrease in molar mass for polymer synthesized under nanoconfinement. In addition to promoting chain transfer to polymer, the long alkyl side chain in the dodecyl methacrylate monomer leads to a suppression of autoacceleration, , an increase in the propagation rate constant, − a decrease in the rate of termination, and a propensity of the dodecyl groups in the polymer to crystallize…”

“…In the particular case of n -dodecyl methacrylate, chain transfer to the polymer during the bulk polymerization leads to branching and cross-linked products, − and if such products are suppressed under nanoconfinement, as is the case for vinyl esters in metallic organic frameworks and for ε-caprolactone in aluminum oxide membranes, one might expect a decrease in molar mass for polymer synthesized under nanoconfinement. In addition to promoting chain transfer to polymer, the long alkyl side chain in the dodecyl methacrylate monomer leads to a suppression of autoacceleration, , an increase in the propagation rate constant, − a decrease in the rate of termination, and a propensity of the dodecyl groups in the polymer to crystallize…”

Covalent Adaptable Networks Made by Reactive Processing of Highly Entangled Polymer: Synthesis-Structure-Thermomechanical Property-Reprocessing Relationship in Covalent Adaptable Networks

“…It occurs to a much lesser extent in low-density PE (LDPE); chain transfer and branching are the predominant mechanisms with LDPE. − CH 2 units in branches off the LDPE backbone also serve as sites for radical formation and cross-linking. − Similarly, radicals may form on CH 2 units in the side chains of other polymers and, thus, cause further branching, cross-linking, and chain scission . This phenomenon has been observed in ethylene-vinyl acetate copolymer (EVA), , poly­(vinyl ethers), − polyacrylates, − and polymethacrylates. − In these polymers, cross-linking efficiency (moles of generated cross-links per mole of decomposed initiator) and the proportion of cross-linking to chain scission after radical formation have been studied as functions of side-chain length, isomerism, and average molecular weight. − …”