Insertion of ester bonds in three terpolymerization systems

Jean Baptiste Lena; Balamurugan Ramalingam; Wendy Rusli; Lohitha Rao Chennamaneni; Praveen Thoniyot; Alexander M. Van Herk

doi:10.1016/j.eurpolymj.2022.111627

Insertion of ester bonds in three terpolymerization systems

Jean Baptiste Lena
, Balamurugan Ramalingam
, Wendy Rusli
, Lohitha Rao Chennamaneni
, Praveen Thoniyot (Corresponding author)
, Alexander M. Van Herk (Corresponding author)

Building Materials

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

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Abstract

Nonbiodegradable (co)polymers with all-carbon backbone produced via radical polymerization are used in various applications. For some applications, like for example in skincare and haircare, these polymers are nonrecoverable and therefore would be preferably made biodegradable. Therefore, inserting ester bonds in the backbone via radical ring opening terpolymerization of acrylates and 2-methylene-1,3 dioxepane (MDO) could be a suitable approach to obtain biodegradable terpolymers. This report investigates the influence of batch versus semibatch process on the polymerization of three terpolymerization systems viz. (i) methacrylamide (MAAM)/n-butyl acrylate (nBA)/BMDO (5,6-Benzo-2-Methylene-1,3-Dioxepane), (ii) MAAM/nBA/MDO, and (iii) methyl methacrylate (MMA)/VAc (vinyl acetate) /MDO. We demonstrate the improvement in number of ester groups inserted and the homogeneity of insertion via semibatch polymerization processes. The process is guided via optimal monomer addition feeding profiles generated using the reactivity ratios of comonomers. Such improved insertion was demonstrated by the molecular weight distribution of fragments after alkali degradation in the investigated systems.

Original language	English
Article number	111627
Number of pages	12
Journal	European Polymer Journal
Volume	181
DOIs	https://doi.org/10.1016/j.eurpolymj.2022.111627
Publication status	Published - 5 Dec 2022

Funding

Farhan Aidil (A*STAR, ISCE2) is acknowledged for the synthesis of MDO and BMDO monomers. Anueshree Rajendran and Don Lim Chen Chuan (A*STAR, ICES) are acknowledged for successfully running TGA and DSC analyses. Li Li Ong (A*STAR, ISCE2). Is acknowledged for the technical assistance with the NMR spectroscopy. Zhao Wenguang (A*STAR, ICES) is acknowledged for having run the GPC analyses. Fiona Liausvia (A*STAR, IHPC) for modifying and writing the code for MAP using Python. Alexander William Jackson (A*STAR, ISCE2) and Vivek Arjunan Vasantha (A*STAR, ICES) are acknowledged for their continuous help in the lab. A*STAR is acknowledged through Grant in Specialty Chemicals AME IAF-PP Programme with grant ID A1786a0030. Farhan Aidil (A*STAR, ISCE2) is acknowledged for the synthesis of MDO and BMDO monomers. Anueshree Rajendran and Don Lim Chen Chuan (A*STAR, ICES) are acknowledged for successfully running TGA and DSC analyses. Li Li Ong (A*STAR, ISCE2). Is acknowledged for the technical assistance with the NMR spectroscopy. Zhao Wenguang (A*STAR, ICES) is acknowledged for having run the GPC analyses. Fiona Liausvia (A*STAR, IHPC) for modifying and writing the code for MAP using Python. Alexander William Jackson (A*STAR, ISCE2) and Vivek Arjunan Vasantha (A*STAR, ICES) are acknowledged for their continuous help in the lab. A*STAR is acknowledged through Grant in Specialty Chemicals AME IAF-PP Programme with grant ID A1786a0030.

Keywords

Biodegradable
Chemical composition distribution
Optimal feeding profile
Semibatch
Terpolymers

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10.1016/j.eurpolymj.2022.111627

1-s2.0-S0014305722006310-mainFinal published version, 5.18 MBLicence: TAVERNE

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title = "Insertion of ester bonds in three terpolymerization systems",

abstract = "Nonbiodegradable (co)polymers with all-carbon backbone produced via radical polymerization are used in various applications. For some applications, like for example in skincare and haircare, these polymers are nonrecoverable and therefore would be preferably made biodegradable. Therefore, inserting ester bonds in the backbone via radical ring opening terpolymerization of acrylates and 2-methylene-1,3 dioxepane (MDO) could be a suitable approach to obtain biodegradable terpolymers. This report investigates the influence of batch versus semibatch process on the polymerization of three terpolymerization systems viz. (i) methacrylamide (MAAM)/n-butyl acrylate (nBA)/BMDO (5,6-Benzo-2-Methylene-1,3-Dioxepane), (ii) MAAM/nBA/MDO, and (iii) methyl methacrylate (MMA)/VAc (vinyl acetate) /MDO. We demonstrate the improvement in number of ester groups inserted and the homogeneity of insertion via semibatch polymerization processes. The process is guided via optimal monomer addition feeding profiles generated using the reactivity ratios of comonomers. Such improved insertion was demonstrated by the molecular weight distribution of fragments after alkali degradation in the investigated systems.",

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AU - Lena, Jean Baptiste

AU - Ramalingam, Balamurugan

AU - Rusli, Wendy

AU - Rao Chennamaneni, Lohitha

AU - Thoniyot, Praveen

AU - Van Herk, Alexander M.

PY - 2022/12/5

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N2 - Nonbiodegradable (co)polymers with all-carbon backbone produced via radical polymerization are used in various applications. For some applications, like for example in skincare and haircare, these polymers are nonrecoverable and therefore would be preferably made biodegradable. Therefore, inserting ester bonds in the backbone via radical ring opening terpolymerization of acrylates and 2-methylene-1,3 dioxepane (MDO) could be a suitable approach to obtain biodegradable terpolymers. This report investigates the influence of batch versus semibatch process on the polymerization of three terpolymerization systems viz. (i) methacrylamide (MAAM)/n-butyl acrylate (nBA)/BMDO (5,6-Benzo-2-Methylene-1,3-Dioxepane), (ii) MAAM/nBA/MDO, and (iii) methyl methacrylate (MMA)/VAc (vinyl acetate) /MDO. We demonstrate the improvement in number of ester groups inserted and the homogeneity of insertion via semibatch polymerization processes. The process is guided via optimal monomer addition feeding profiles generated using the reactivity ratios of comonomers. Such improved insertion was demonstrated by the molecular weight distribution of fragments after alkali degradation in the investigated systems.

AB - Nonbiodegradable (co)polymers with all-carbon backbone produced via radical polymerization are used in various applications. For some applications, like for example in skincare and haircare, these polymers are nonrecoverable and therefore would be preferably made biodegradable. Therefore, inserting ester bonds in the backbone via radical ring opening terpolymerization of acrylates and 2-methylene-1,3 dioxepane (MDO) could be a suitable approach to obtain biodegradable terpolymers. This report investigates the influence of batch versus semibatch process on the polymerization of three terpolymerization systems viz. (i) methacrylamide (MAAM)/n-butyl acrylate (nBA)/BMDO (5,6-Benzo-2-Methylene-1,3-Dioxepane), (ii) MAAM/nBA/MDO, and (iii) methyl methacrylate (MMA)/VAc (vinyl acetate) /MDO. We demonstrate the improvement in number of ester groups inserted and the homogeneity of insertion via semibatch polymerization processes. The process is guided via optimal monomer addition feeding profiles generated using the reactivity ratios of comonomers. Such improved insertion was demonstrated by the molecular weight distribution of fragments after alkali degradation in the investigated systems.

KW - Biodegradable

KW - Chemical composition distribution

KW - Optimal feeding profile

KW - Semibatch

KW - Terpolymers

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VL - 181

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Insertion of ester bonds in three terpolymerization systems

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