| 1. |
- Bonjour, Olivier, et al.
(författare)
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Lignin-Inspired Polymers with High Glass Transition Temperature and Solvent Resistance from 4-Hydroxybenzonitrile, Vanillonitrile, and Syringonitrile Methacrylates
- 2021
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Ingår i: ACS Sustainable Chemistry & Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 9:50, s. 16874-16880
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Tidskriftsartikel (refereegranskat)abstract
- We here report on the synthesis and polymerization of nitrile-containing methacrylate monomers, prepared via straightforward nitrilation of the corresponding lignin-inspired aldehyde. The polymethacrylates reached exceptionally high glass transition temperatures (Tg values), i.e., 150, 164, and 238 °C for the 4-hydroxybenzonitrile, vanillonitrile, and syringonitrile derivatives, respectively, and were thermally stable up to above 300 °C. Copolymerizations of the nitrile monomers with styrene and methyl methacrylate, respectively, gave potentially melt processable materials with tunable Tg values and enhanced solvent resistance. The use of lignin-derived nitrile-containing monomers represents an efficient strategy toward well-defined biobased high Tg polymer materials.
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| 2. |
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| 3. |
- Bonjour, Olivier, et al.
(författare)
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Rigid biobased polycarbonates with good processability based on a spirocyclic diol derived from citric acid
- 2020
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Ingår i: Green Chemistry. - 1463-9270. ; 22:12, s. 3940-3951
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Tidskriftsartikel (refereegranskat)abstract
- Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bicyclic diketone (cis-bicyclo[3.3.0]octane-3,7-dione, obtained from citric acid) using trimethylolpropane. This spiro-diol monomer has two reactive primary hydroxyl groups and the synthesis from inexpensive biobased starting materials is straightforward and readily upscalable, involving no chromatographic purification. In order to explore the usefulness of the new monomer, it was employed in melt polycondensations with diphenylcarbonate at up to 280 °C to form rigid fully amorphous polycarbonates (PCs). Molecular weights (MWs) up to Mn = 28 kg mol-1 were achieved, and thermal and dynamic mechanical measurements showed glass transitions up to Tg = 100 °C, with no thermal decomposition until Td ~ 350 °C. Solvent cast films had excellent mechanical flexibility and strength, as well as a high transparency with only slight coloration. Results by dynamic melt rheology implied that the high-MW PCs had a good processability at 170 °C, with a stable shear modulus over time, but started to degrade via chain scission reactions when the temperature approached 200 °C. In conclusion, the present work demonstrates the straightforward preparation of the citric acid-based spiro-diol, and indicates that it is an efficient building block for the preparation of rigid biobased PCs and other condensation polymers.
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| 4. |
- Gathergood, Nicholas
(creator_code:cre_t)
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Synthesis and polymerization of isosorbide-based monomethacrylates
- 2019
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Patent (övrigt vetenskapligt/konstnärligt)abstract
- Isosorbide-5-methacrylate was obtained by enzymatic catalysis with Lipozyme RM IM in a highly regioselective manner in up to 87% yield. The process uses readily available acyl donors (methacrylic anydride or vinyl methacrylate), is easily scalable and chromatography free. Simple extractive workup followed by decoloration and filtration affords the monomer with up to > 99% purity. In addition, the developed enzymatic strategy was applied for the synthesis of a series of isosorbide 5- and 2-methacrylate derivatives. All the sythesized isosorbide monomethacrylates were radically polymerized with AIBN. The properties of these polymers with different side groups in either endo or exo configuration in the isosorbide structure was examined. The methacrylic isosorbide derivatives with OH-group were found to have very high glass transition temperature (Tg = 167 °C) and good thermal stability (at 5% weight loss under N2, Td,95 = 240 °C). The highest molecular weight (Mn = 80.6 kg/mol) was determined for the polymethacrylate with Ac-substitute.
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| 5. |
- Ismagilova, Alina, et al.
(författare)
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Ecotoxicity of isosorbide acrylate and methacrylate monomers and corresponding polymers
- 2023
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Ingår i: Green Chemistry. - 1463-9270. ; 25:4, s. 1626-1634
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Tidskriftsartikel (refereegranskat)abstract
- Isosorbide is a well-investigated and accessible biomass-derived compound that has found wide use in medicine, cosmetics, and material sciences. The efforts to employ this rigid bicyclic diol as a sustainable building block in high-performance biobased plastics for, e.g., the engineering, coating, and packaging sectors have grown sharply in recent years. Due to the biomass origin, there is an implicit assumption of a low toxicity and an environmentally benign nature of isosorbide-derived plastics. In the present work, the ecotoxicity of isosorbide acrylate and methacrylate monomers and the corresponding poly(meth)acrylates, as well as industrially produced latexes from these monomers, were evaluated towards bacteria (Escherichia coli, Aliivibrio fischeri), vascular plants (Spirodela polyrhiza) and invertebrates (Thamnocephalus platyurus) using widely acknowledged test assays. The measured half maximal effective concentration (EC50) values indicate that the chemically reactive isosorbide acrylate monomers are toxic towards higher multicellular organisms (S. polyrhiza and T. platyurus, EC50 ~9 mg L-1) and moderately toxic towards bacteria (E. coli), whereas the corresponding methacrylate monomers can be considered as practically harmless or harmless on the same test assays. Corresponding isosorbide polyacrylate and polymethacrylate polymers are harmless towards the tested organisms (EC50 > 1000 mg L-1), except towards E. coli, where two polymers are classified as practically harmless (EC50 = 374 and 514 mg L-1). Moreover, industrially produced isosorbide methacrylate derived latexes can be classified as harmless based on this study.
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| 6. |
- Laanesoo, Siim, et al.
(författare)
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Combining isosorbide and lignin-related benzoic acids for high-Tg polymethacrylates
- 2024
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Ingår i: European Polymer Journal. - 0014-3057. ; 202
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Tidskriftsartikel (refereegranskat)abstract
- The insertion of rigid aliphatic or aromatic building blocks in polymer structures is an efficient synthetic strategy towards high-Tg polymer materials. In the present work, we have functionalized isosorbide 5-methacrylate with various aromatic lignin-inspired esters to yield a series of isosorbide-2-aryl carboxylate-5-methacrylate monomers (ArIMAs) as single regioisomers. The selection of phenyl carboxylate side groups included benzoate, p-cyanobenzoate, meta/para-methoxybenzoates, and different vanillic acid esters. This afforded a range of seven bio-based monomers with different size, polarity, and substitutions. Polymerizations were carried out by conventional free radical initiation to obtain the corresponding high molecular-weight poly(aryl carboxylate isosorbide methacrylate)s (PArIMAs). The polymerizations were evaluated in different solvents, including toluene, EtOAc, γ-valerolactone, 2-MeTHF, and DMSO to identify the most suitable conditions. The polymers exhibited high glass transition temperatures (Tgs) in a broad range, from 80 to 168 °C, and were thermally stable up to 268 °C. Furthermore, dynamic rheology experiments indicated that the polymers were sufficiently stable for melt processing. The availability of the building blocks combined with the high stability of the polymers make these materials attractive for use as high-performance plastics and coatings.
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| 7. |
- Laanesoo, Siim, et al.
(författare)
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Poly(alkanoyl isosorbide methacrylate)s: from amorphous to semi-crystalline and liquid crystalline biobased materials
- 2021
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Ingår i: Biomacromolecules. - : American Chemical Society (ACS). - 1526-4602 .- 1525-7797. ; 22:2, s. 640-648
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Tidskriftsartikel (refereegranskat)abstract
- We have prepared a series of twelve D-isosorbide-2-alkanoate-5-methacrylate monomers as single regioisomers with different pendant linear C2 to C20 alkanoyl chains by using biocatalytic and chemical acylations. By conventional radical polymerization, these monomers afforded high-molecular weight biobased poly(alkanoyl isosorbide methacrylate)s (PAIMAs). Samples with C2-C12 alkanoyl chains were amorphous with glass transition temperatures from 107 to 54 °C, while C14-C20 chains gave semi-crystalline materials with melting points up to 59 °C. Moreover, PAIMAs with C13-C20 chains formed liquid crystalline mesophases with transition temperatures up to 93 °C. The mesophases were studied by polarized optical microscopy, and rheology showed stepwise changes of the viscosity at the transition temperature. Unexpectedly, a PAIMA prepared from a regioisomeric monomer (C18) showed semi-crystallinity but no liquid crystallinity. Consequently, the properties of the PAIMAs were readily tunable by controlling the phase structure and transitions through the alkanoyl chain length and the regiochemistry to form fully amorphous, semi-crystalline or semi-/liquid crystalline materials.
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