Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups
Herein, we report a novel type of symmetrical trithiocarbonate chain transfer agent (CTA) based diphenylmethyl as R groups. The utilization of this CTA in the Reversible Addition-Fragmentation chain Transfer (RAFT) process reveals an efficient control in the polymerization of methacrylic monomers an...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-07-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/15/4618 |
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| author | Alvaro Leonel Robles Grana Hortensia Maldonado-Textle José Román Torres-Lubián Claude St Thomas Ramón Díaz de León José Luis Olivares-Romero Luis Valencia Francisco Javier Enríquez-Medrano |
| author_facet | Alvaro Leonel Robles Grana Hortensia Maldonado-Textle José Román Torres-Lubián Claude St Thomas Ramón Díaz de León José Luis Olivares-Romero Luis Valencia Francisco Javier Enríquez-Medrano |
| author_sort | Alvaro Leonel Robles Grana |
| collection | DOAJ |
| description | Herein, we report a novel type of symmetrical trithiocarbonate chain transfer agent (CTA) based diphenylmethyl as R groups. The utilization of this CTA in the Reversible Addition-Fragmentation chain Transfer (RAFT) process reveals an efficient control in the polymerization of methacrylic monomers and the preparation of block copolymers. The latter are obtained by the (co)polymerization of styrene or butyl acrylate using a functionalized macro-CTA polymethyl methacrylate (PMMA) previously synthesized. Data show low molecular weight dispersity values (Đ < 1.5) particularly in the polymerization of methacrylic monomers. Considering a typical RAFT mechanism, the leaving groups (R) from the fragmentation of CTA should be able to re-initiate the polymerization (formation of growth chains) allowing an efficient control of the process. Nevertheless, in the case of the polymerization of MMA in the presence of this symmetrical CTA, the polymerization process displays an atypical behavior that requires high [initiator]/[CTA] molar ratios for accessing predictable molecular weights without affecting the Đ. Some evidence suggests that this does not completely behave as a common RAFT agent as it is not completely consumed during the polymerization reaction, and it needs atypical high molar ratios [initiator]/[CTA] to be closer to the predicted molecular weight without affecting the Đ. This work demonstrates that MMA and other methacrylic monomers can be polymerized in a controlled way, and with “living” characteristics, using certain symmetrical trithiocarbonates. |
| first_indexed | 2024-03-10T09:10:50Z |
| format | Article |
| id | doaj.art-21c381fdc9ba4e4a94e0426f990112ad |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T09:10:50Z |
| publishDate | 2021-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-21c381fdc9ba4e4a94e0426f990112ad2023-11-22T06:00:46ZengMDPI AGMolecules1420-30492021-07-012615461810.3390/molecules26154618Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl GroupsAlvaro Leonel Robles Grana0Hortensia Maldonado-Textle1José Román Torres-Lubián2Claude St Thomas3Ramón Díaz de León4José Luis Olivares-Romero5Luis Valencia6Francisco Javier Enríquez-Medrano7Centro de Investigación en Química Aplicada, Enrique Reyna Hermosillo, No. 140, Col. San José de los Cerritos, Saltillo 25294, MexicoCentro de Investigación en Química Aplicada, Enrique Reyna Hermosillo, No. 140, Col. San José de los Cerritos, Saltillo 25294, MexicoCentro de Investigación en Química Aplicada, Enrique Reyna Hermosillo, No. 140, Col. San José de los Cerritos, Saltillo 25294, MexicoCONACyT-Centro de Investigación en Química Aplicada, Enrique Reyna Hermosillo, No. 140, Col. San José de los Cerritos, Saltillo 25294, MexicoCentro de Investigación en Química Aplicada, Enrique Reyna Hermosillo, No. 140, Col. San José de los Cerritos, Saltillo 25294, MexicoRed de Estudios Moleculares Avanzados, Clúster Científico y Tecnológico BioMimic, Campus III, Instituto de Ecología, Xalapa 91073, MexicoBiofiber Tech Sweden AB, Norrsken Hourse, Birger Jarlsgatan 57 C, SE-113 56 Stockholm, SwedenCentro de Investigación en Química Aplicada, Enrique Reyna Hermosillo, No. 140, Col. San José de los Cerritos, Saltillo 25294, MexicoHerein, we report a novel type of symmetrical trithiocarbonate chain transfer agent (CTA) based diphenylmethyl as R groups. The utilization of this CTA in the Reversible Addition-Fragmentation chain Transfer (RAFT) process reveals an efficient control in the polymerization of methacrylic monomers and the preparation of block copolymers. The latter are obtained by the (co)polymerization of styrene or butyl acrylate using a functionalized macro-CTA polymethyl methacrylate (PMMA) previously synthesized. Data show low molecular weight dispersity values (Đ < 1.5) particularly in the polymerization of methacrylic monomers. Considering a typical RAFT mechanism, the leaving groups (R) from the fragmentation of CTA should be able to re-initiate the polymerization (formation of growth chains) allowing an efficient control of the process. Nevertheless, in the case of the polymerization of MMA in the presence of this symmetrical CTA, the polymerization process displays an atypical behavior that requires high [initiator]/[CTA] molar ratios for accessing predictable molecular weights without affecting the Đ. Some evidence suggests that this does not completely behave as a common RAFT agent as it is not completely consumed during the polymerization reaction, and it needs atypical high molar ratios [initiator]/[CTA] to be closer to the predicted molecular weight without affecting the Đ. This work demonstrates that MMA and other methacrylic monomers can be polymerized in a controlled way, and with “living” characteristics, using certain symmetrical trithiocarbonates.https://www.mdpi.com/1420-3049/26/15/4618RAFT polymerizationmethacrylatesblock copolymers |
| spellingShingle | Alvaro Leonel Robles Grana Hortensia Maldonado-Textle José Román Torres-Lubián Claude St Thomas Ramón Díaz de León José Luis Olivares-Romero Luis Valencia Francisco Javier Enríquez-Medrano Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups Molecules RAFT polymerization methacrylates block copolymers |
| title | Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups |
| title_full | Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups |
| title_fullStr | Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups |
| title_full_unstemmed | Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups |
| title_short | Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups |
| title_sort | controlled co polymerization of methacrylates using a novel symmetrical trithiocarbonate raft agent bearing diphenylmethyl groups |
| topic | RAFT polymerization methacrylates block copolymers |
| url | https://www.mdpi.com/1420-3049/26/15/4618 |
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