Controlled Polymerization of Next-Generation Renewable Monomers and Beyond

Abstract

Natural molecular biomass plays an important role in the field of renewable polymers, as they can be directly used or derivatized as monomers for controlled polymerization, in a way similar to many petroleum-derived monomers. We deliver this perspective primarily based on a monomer approach. Biomass-derived monomers are separated into four major categories according to their natural resource origins: (1) oxygen-rich monomers including carboxylic acids (lactic acid, succinic acid, itaconic acid, and levulinic acid) and furan; (2) hydrocarbon-rich monomers including vegetable oils, fatty acids, terpenes, terpenoids and resin acids; (3) hydrocarbon monomers (bio-olefins); and (4) non-hydrocarbon monomers (carbon dioxide). A variety of emerging synthetic tools (controlled polymerization and click chemistry) are particularly summarized. An overview on future opportunities and challenges, which are critical to promote biorefinery in the production of renewable chemicals and polymers, is given.

A highly rigid diamine monomer derived from naturally occurringmyo-inositol and its use for polyamide synthesis

“…However, polyamide 6b was less soluble than 6c , and thus, its C‐NMR spectrum was measured in the solid state by CPMAS. In addition, polyamide 6d was scarcely soluble in DMSO and, thus, was analyzed with solid state C‐NMR (also CPMAS). The NMR spectra of polyamides 6b , 6c , and 6d are shown in Supporting Information Figures S7–S9, respectively.…”

“…All signals in the 1 H‐NMR spectrum are attributable to the expected components, and their intensities agreed with those expected from the molecular structure of 5a . In the C‐NMR spectrum of 5a , signals arising from the carbonyl carbon atoms in the amide moieties and those attributable to the quaternary carbons in the cyclohexylidene moieties were observed. In addition, the IR spectrum of 5a contains strong absorption peaks at 1649 and 1540 cm −1 , confirming the presence of amide bonds.…”

“…1 H‐NMR (in DMSO‐ d 6 , at rt, δ ): 7.74 (br, 1H), 7.44 (br, d, J = 8.3 Hz, 1H), 5.11 − 4.01 (br, 6H), 3.74 (br, 1H), 3.67 (br, 1H), 3.56 (br, 2H), 2.14 (br, 4H), 1.48 (br, 4H), 1.24 (br, 8H); C‐NMR (in DMSO‐ d 6 at rt, δ ): 172.66, 171.92, 73.91, 71.29, 68.41, 47.58, 46.35, 35.63, 35.31, 28.87, 28.83, 28.75, 28.72, 25.46; IR (KBr): ν = 3328, 2925, 1633, 1539, 1091 cm −1 .…”

A highly rigid diamine monomer derived from naturally occurringmyo-inositol and its use for polyamide synthesis

“…However, polyamide 6b was less soluble than 6c , and thus, its C‐NMR spectrum was measured in the solid state by CPMAS. In addition, polyamide 6d was scarcely soluble in DMSO and, thus, was analyzed with solid state C‐NMR (also CPMAS). The NMR spectra of polyamides 6b , 6c , and 6d are shown in Supporting Information Figures S7–S9, respectively.…”

“…All signals in the 1 H‐NMR spectrum are attributable to the expected components, and their intensities agreed with those expected from the molecular structure of 5a . In the C‐NMR spectrum of 5a , signals arising from the carbonyl carbon atoms in the amide moieties and those attributable to the quaternary carbons in the cyclohexylidene moieties were observed. In addition, the IR spectrum of 5a contains strong absorption peaks at 1649 and 1540 cm −1 , confirming the presence of amide bonds.…”

“…1 H‐NMR (in DMSO‐ d 6 , at rt, δ ): 7.74 (br, 1H), 7.44 (br, d, J = 8.3 Hz, 1H), 5.11 − 4.01 (br, 6H), 3.74 (br, 1H), 3.67 (br, 1H), 3.56 (br, 2H), 2.14 (br, 4H), 1.48 (br, 4H), 1.24 (br, 8H); C‐NMR (in DMSO‐ d 6 at rt, δ ): 172.66, 171.92, 73.91, 71.29, 68.41, 47.58, 46.35, 35.63, 35.31, 28.87, 28.83, 28.75, 28.72, 25.46; IR (KBr): ν = 3328, 2925, 1633, 1539, 1091 cm −1 .…”

Ethylene Copolymerization with Limonene and β-Pinene: New Bio-Based Polyolefins Prepared by Coordination Polymerization

“…66 In contrast, the Cp* analogue (5) gave a polymer with bimodal molecular weight distribution (run 11), 66 and the Cp analogue (1) gave a low-molecularweight polymer possessing two T m values in the DSC thermogram (run 1, Figure S3-1, Supporting Information). 66 As reported previously, 47 introduction of SiMe 3 (6) and SiEt 3 (7) groups into the phenoxide ligand improved the activity (and the stability) affording polymers with unimodal molecular weight distributions, and their compositions are uniform as confirmed by DSC thermograms (Figures S3-6 and S3-7, Supporting Information). 66 Both the t BuC 5 H 4 (2) and the indenyl (4) analogues gave rather high-molecular-weight (co)polymers with unimodal molecular weight distributions, and the T m values decreased upon increasing the initial Lim concentration charged (runs 2 and 3 and runs 8−10).…”

Green chain-shattering polymers based on a self-immolative azobenzene motif

“…31 Upon treatment with 1 equivalent of the reducing agent in phosphate-buffered saline (PBS, pH 7.4), 32 the reaction was incubated at 37 °C for several hours. 1 H NMR analysis of the final reaction mixture showed far different results than expected, i.e. no degradation.…”

A highly rigid diamine monomer derived from naturally occurringmyo-inositol and its use for polyamide synthesis

“…However, polyamide 6b was less soluble than 6c , and thus, its C‐NMR spectrum was measured in the solid state by CPMAS. In addition, polyamide 6d was scarcely soluble in DMSO and, thus, was analyzed with solid state C‐NMR (also CPMAS). The NMR spectra of polyamides 6b , 6c , and 6d are shown in Supporting Information Figures S7–S9, respectively.…”

“…All signals in the 1 H‐NMR spectrum are attributable to the expected components, and their intensities agreed with those expected from the molecular structure of 5a . In the C‐NMR spectrum of 5a , signals arising from the carbonyl carbon atoms in the amide moieties and those attributable to the quaternary carbons in the cyclohexylidene moieties were observed. In addition, the IR spectrum of 5a contains strong absorption peaks at 1649 and 1540 cm −1 , confirming the presence of amide bonds.…”

“…1 H‐NMR (in DMSO‐ d 6 , at rt, δ ): 7.74 (br, 1H), 7.44 (br, d, J = 8.3 Hz, 1H), 5.11 − 4.01 (br, 6H), 3.74 (br, 1H), 3.67 (br, 1H), 3.56 (br, 2H), 2.14 (br, 4H), 1.48 (br, 4H), 1.24 (br, 8H); C‐NMR (in DMSO‐ d 6 at rt, δ ): 172.66, 171.92, 73.91, 71.29, 68.41, 47.58, 46.35, 35.63, 35.31, 28.87, 28.83, 28.75, 28.72, 25.46; IR (KBr): ν = 3328, 2925, 1633, 1539, 1091 cm −1 .…”

Ethylene Copolymerization with Limonene and β-Pinene: New Bio-Based Polyolefins Prepared by Coordination Polymerization

“…66 In contrast, the Cp* analogue (5) gave a polymer with bimodal molecular weight distribution (run 11), 66 and the Cp analogue (1) gave a low-molecularweight polymer possessing two T m values in the DSC thermogram (run 1, Figure S3-1, Supporting Information). 66 As reported previously, 47 introduction of SiMe 3 (6) and SiEt 3 (7) groups into the phenoxide ligand improved the activity (and the stability) affording polymers with unimodal molecular weight distributions, and their compositions are uniform as confirmed by DSC thermograms (Figures S3-6 and S3-7, Supporting Information). 66 Both the t BuC 5 H 4 (2) and the indenyl (4) analogues gave rather high-molecular-weight (co)polymers with unimodal molecular weight distributions, and the T m values decreased upon increasing the initial Lim concentration charged (runs 2 and 3 and runs 8−10).…”

Green chain-shattering polymers based on a self-immolative azobenzene motif

“…31 Upon treatment with 1 equivalent of the reducing agent in phosphate-buffered saline (PBS, pH 7.4), 32 the reaction was incubated at 37 °C for several hours. 1 H NMR analysis of the final reaction mixture showed far different results than expected, i.e. no degradation.…”

A highly rigid diamine monomer derived from naturally occurringmyo-inositol and its use for polyamide synthesis

“…However, polyamide 6b was less soluble than 6c , and thus, its C‐NMR spectrum was measured in the solid state by CPMAS. In addition, polyamide 6d was scarcely soluble in DMSO and, thus, was analyzed with solid state C‐NMR (also CPMAS). The NMR spectra of polyamides 6b , 6c , and 6d are shown in Supporting Information Figures S7–S9, respectively.…”

“…All signals in the 1 H‐NMR spectrum are attributable to the expected components, and their intensities agreed with those expected from the molecular structure of 5a . In the C‐NMR spectrum of 5a , signals arising from the carbonyl carbon atoms in the amide moieties and those attributable to the quaternary carbons in the cyclohexylidene moieties were observed. In addition, the IR spectrum of 5a contains strong absorption peaks at 1649 and 1540 cm −1 , confirming the presence of amide bonds.…”

“…1 H‐NMR (in DMSO‐ d 6 , at rt, δ ): 7.74 (br, 1H), 7.44 (br, d, J = 8.3 Hz, 1H), 5.11 − 4.01 (br, 6H), 3.74 (br, 1H), 3.67 (br, 1H), 3.56 (br, 2H), 2.14 (br, 4H), 1.48 (br, 4H), 1.24 (br, 8H); C‐NMR (in DMSO‐ d 6 at rt, δ ): 172.66, 171.92, 73.91, 71.29, 68.41, 47.58, 46.35, 35.63, 35.31, 28.87, 28.83, 28.75, 28.72, 25.46; IR (KBr): ν = 3328, 2925, 1633, 1539, 1091 cm −1 .…”

Ethylene Copolymerization with Limonene and β-Pinene: New Bio-Based Polyolefins Prepared by Coordination Polymerization

“…66 In contrast, the Cp* analogue (5) gave a polymer with bimodal molecular weight distribution (run 11), 66 and the Cp analogue (1) gave a low-molecularweight polymer possessing two T m values in the DSC thermogram (run 1, Figure S3-1, Supporting Information). 66 As reported previously, 47 introduction of SiMe 3 (6) and SiEt 3 (7) groups into the phenoxide ligand improved the activity (and the stability) affording polymers with unimodal molecular weight distributions, and their compositions are uniform as confirmed by DSC thermograms (Figures S3-6 and S3-7, Supporting Information). 66 Both the t BuC 5 H 4 (2) and the indenyl (4) analogues gave rather high-molecular-weight (co)polymers with unimodal molecular weight distributions, and the T m values decreased upon increasing the initial Lim concentration charged (runs 2 and 3 and runs 8−10).…”

Green chain-shattering polymers based on a self-immolative azobenzene motif

“…31 Upon treatment with 1 equivalent of the reducing agent in phosphate-buffered saline (PBS, pH 7.4), 32 the reaction was incubated at 37 °C for several hours. 1 H NMR analysis of the final reaction mixture showed far different results than expected, i.e. no degradation.…”