Special Issue "Bio-Based Resins and Crosslinked Polymers from Renewable Resources"

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: 30 September 2018

Special Issue Editors

Guest Editor
Dr. Naozumi Teramoto

Department of Life and Environmental Sciences, Faculty of Engineering, Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba 275-0016, Japan
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Fax: +81 47 478 0406
Interests: biomaterial; bio-based polymer; bioplastics; biodegradable polymer; biopolymer; composite material comprising a polymer matrix
Guest Editor
Professor Mitsuhiro Shibata

Department of Applied Chemistry, Faculty of Engineering, Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba 275-0016, Japan
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Special Issue Information

Dear Colleagues,

Most synthetic polymers developed in the 20th century are derived from fossil resources, and we have often faced some problems relating to an excessive dependence on fossil resources. The economic issue currently faced is the price fluctuation of crude oil, which has repeated ups and downs, reflecting governmental issues and anxiety of supply shortage. Additionally, there are concerns over global warming caused by carbon dioxide emissions and the depletion of fossil resources in the near future. As the solution to these problems, polymers derived from renewable resources have been developed over the span of a few decades. Among these polymers, crosslinked polymers and resins are attractive due to the diversity of choices for resources, compared to linear thermoplastics. Research and development on bio-based resins and crosslinked polymers from renewable resources are steady and continuous, and there are still possibilities for us to encounter novel materials.

This Special Issue covers preparation, characterization, properties and applications of bio-based resins and crosslinked polymers from renewable resources, as well as their hybrids or composites with other materials. The methods for crosslinking are not limited to simple thermal curing methods, and can be extended to photocuring, non-covalent crosslinking and topological crosslinking methods. The aim of this Special Issue is to update recent knowledge and broaden our perspective of bio-based resins and crosslinked polymers from renewable resources for environmentally-benign materials.

Dr. Naozumi Teramoto
Prof. Dr. Mitsuhiro Shibata
Guest Editors

Manuscript Submission Information

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Keywords

  • bio-based polymer
  • bio-based resin
  • crosslinked polymer
  • renewable resources
  • natural polymer
  • composite material
  • environmentally-benign material

Published Papers (8 papers)

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Research

Open AccessArticle Improve the Performance of Soy Protein-Based Adhesives by a Polyurethane Elastomer
Polymers 2018, 10(9), 1016; https://doi.org/10.3390/polym10091016
Received: 19 July 2018 / Revised: 9 September 2018 / Accepted: 11 September 2018 / Published: 13 September 2018
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Abstract
The purpose of this study was to improve the performance of soy protein isolate (SPI) adhesives using a polyurethane elastomer. Triglycidylamine (TGA), SPI, thermoplastic polyurethane elastomer (TPU), and γ-(2,3-epoxypropoxy) propyltrimethoxysilane (KH-560) were used to develop a novel SPI-based adhesive. The residual rate, functional
[...] Read more.
The purpose of this study was to improve the performance of soy protein isolate (SPI) adhesives using a polyurethane elastomer. Triglycidylamine (TGA), SPI, thermoplastic polyurethane elastomer (TPU), and γ-(2,3-epoxypropoxy) propyltrimethoxysilane (KH-560) were used to develop a novel SPI-based adhesive. The residual rate, functional groups, thermal stability, and fracture surface micrographs of the cured adhesives were characterized. Three-ply plywood was fabricated, and the dry/wet shear strength was determined. The experimental results suggested that introducing 2% TGA improved the residual rate of the SPI/TGA adhesive by 4.1% because of the chemical cross-linking reaction between epoxy groups and protein molecules. Incorporating 7% TPU into the SPI/TGA adhesive, the residual rate of the adhesive increased by 5.2% and the dry/wet shear strength of plywood bonded by SPI/TGA/TPU adhesive increased by 10.7%/67.7%, respectively, compared with that of SPI/TGA adhesive. When using KH-560 and TPU together, the residual rate of the adhesive improved by 0.9% compared with that of SPI/TGA/TPU adhesive. The dry and wet shear strength of the plywood bonded by the SPI/TGA/TPU/KG-560 adhesive further increased by 23.2% and 23.6% respectively when compared with that of SPI/TGA/TPU adhesive. TPU physically combined with the SPI/TGA adhesive to form a interpenetration network and KH-560 acted as a bridge to connect TPU and SPI/TGA to form a joined crosslinking network, which improved the thermo stability/toughness of the adhesive and created a uniform ductile fracture section of the adhesive. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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Open AccessArticle A One Pot Method for Preparing an Antibacterial Superabsorbent Hydrogel with a Semi-IPN Structure Based on Tara Gum and Polyquaternium-7
Polymers 2018, 10(7), 696; https://doi.org/10.3390/polym10070696
Received: 28 May 2018 / Revised: 20 June 2018 / Accepted: 21 June 2018 / Published: 22 June 2018
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Abstract
An antibacterial superabsorbent polymer was prepared by graft polymerization of acrylic acid onto tara gum polysaccharide, by adding N,N-dimethyl-N-2-propenyl-2-propen-1-aminium chloride and a polymer with 2-propenamide (polyquaternium-7, PQ7) as an antibacterial agent. The effects of the amount of PQ7
[...] Read more.
An antibacterial superabsorbent polymer was prepared by graft polymerization of acrylic acid onto tara gum polysaccharide, by adding N,N-dimethyl-N-2-propenyl-2-propen-1-aminium chloride and a polymer with 2-propenamide (polyquaternium-7, PQ7) as an antibacterial agent. The effects of the amount of PQ7 in the hydrogel on its swelling ratio were investigated and maximum swelling ratios of 712 g/g and 68 g/g, in distilled water and 0.9 wt % NaCl solution were attained with 0.5 g PQ7 per gram of tara gum. The superabsorbent hydrogel was characterized by using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and thermal gravimetric analysis. The results showed that poly (acrylic acid) was successfully grafted onto tara gum and a three-dimensional network structure formed with PQ7 chains penetrated in the networks. The antibacterial properties of these superabsorbent hydrogels against Staphylococcus aureus and Escherichia coli improved with increasing PQ7 content. This study demonstrates a method of preparing novel functional superabsorbent hydrogels. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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Open AccessArticle Effect of Selected Thiols on Cross-Linking of Acrylated Epoxidized Soybean Oil and Properties of Resulting Polymers
Polymers 2018, 10(4), 439; https://doi.org/10.3390/polym10040439
Received: 28 March 2018 / Revised: 10 April 2018 / Accepted: 12 April 2018 / Published: 14 April 2018
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Abstract
The effect of the chemical structure and functionality of three structurally different thiols on the cross-linking of acrylated epoxidized soybean oil and on the properties of the resulting polymers was investigated in this study. 1,3-Benzenedithiol, pentaerythritol tetra(3-mercaptopropionate), and an hexathiol synthesized from squalene
[...] Read more.
The effect of the chemical structure and functionality of three structurally different thiols on the cross-linking of acrylated epoxidized soybean oil and on the properties of the resulting polymers was investigated in this study. 1,3-Benzenedithiol, pentaerythritol tetra(3-mercaptopropionate), and an hexathiol synthesized from squalene were used in the cross-linking of acrylated epoxidized soybean oil by thiol–Michael addition reaction. The reactivity of thiols determined from calorimetric curves followed the order: 1,3-benzenedithiol > pentaerythritol tetra(3-mercaptopropionate) > hexathiolated squalene. Thermal and mechanical properties and the swelling in different solvents of the cross-linked polymers were studied. The cross-linked polymer obtained from 1,3-benzenedithiol showed the highest swelling values in chloroform and toluene. The cross-linked polymer with pentaerythritol tetra(3-mercaptopropionate) fragments showed the best mechanical performance (highest mechanical strength and Young’s modulus) and thermal stability. The cross-linked polymers from hexathiolated squalene showed the highest glass transition temperature. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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Open AccessArticle Synthesis and Characterization of Wooden Magnetic Activated Carbon Fibers with Hierarchical Pore Structures
Polymers 2018, 10(4), 435; https://doi.org/10.3390/polym10040435
Received: 16 March 2018 / Revised: 7 April 2018 / Accepted: 11 April 2018 / Published: 13 April 2018
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Abstract
Wooden magnetic activated carbon fibers (WMACFs) with hierarchical pore structures were obtained by adding magnetic iron oxide (Fe3O4) nanoparticles into the liquefied wood. The structures and properties of WMACFs were analyzed by scanning electronmicroscopy (SEM), X-ray diffraction (XRD), Fourier
[...] Read more.
Wooden magnetic activated carbon fibers (WMACFs) with hierarchical pore structures were obtained by adding magnetic iron oxide (Fe3O4) nanoparticles into the liquefied wood. The structures and properties of WMACFs were analyzed by scanning electronmicroscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N2 adsorption, and vibrating sample magnetometer (VSM). The results showed that WMACFs had high Brunauer-Emmett-Teller (BET) surface area (1578 m2/g) and total pore volume (0.929 cm3/g), of which 45% was the contribution of small mesopores of 2–3 nm. It is believed that Fe3O4 nanoparticles play an important role in the formation of hierarchical pores. With the Fe3O4 content increasing, the yield rate of WMACFs decreased, and the Fe3O4 crystal plane diffraction peaks and characteristic adsorption peaks were obviously observed. At the same time, it was also found that WMACFs had favorable magnetic properties when the Fe3O4 content was above 1.5%. As a result, WMACFs could be a promising candidate for high efficiency, low cost, and convenient separation for the magnetic field. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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Open AccessArticle Preparation and Characterization of Graphene Oxide-Modified Sapium sebiferum Oil-Based Polyurethane Composites with Improved Thermal and Mechanical Properties
Polymers 2018, 10(2), 133; https://doi.org/10.3390/polym10020133
Received: 30 December 2017 / Revised: 28 January 2018 / Accepted: 29 January 2018 / Published: 30 January 2018
Cited by 4 | PDF Full-text (4974 KB) | HTML Full-text | XML Full-text
Abstract
Bio-based polyurethane (PU) composites with superior thermal and mechanical properties have received wide attention. This is due to the recent rapid developments in the PU industry. In the work reported here, novel nano-composites with graphene oxide (GO)-modified Sapium sebiferum oil (SSO)-based PU has
[...] Read more.
Bio-based polyurethane (PU) composites with superior thermal and mechanical properties have received wide attention. This is due to the recent rapid developments in the PU industry. In the work reported here, novel nano-composites with graphene oxide (GO)-modified Sapium sebiferum oil (SSO)-based PU has been synthesized via in situ polymerization. GO, prepared using the improved Hummers method from natural graphene (NG), and SSO-based polyol with a hydroxyl value of 211 mg KOH/g, prepared by lipase hydrolysis, were used as raw materials. The microstructures and properties of GO and the nano-composites were both characterized using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and tensile tests. The results showed that GO with its nano-sheet structure possessed a significant number of oxygen-containing functional groups at the surface. The nano-composites containing 1 wt % GO in the PU matrix (PU1) exhibited excellent comprehensive properties. Compared with those for pure PU, the glass transition temperature (Tg) and initial decomposition temperature (IDT) of the PU1 were enhanced by 14.1 and 31.8 °C, respectively. In addition, the tensile strength and Young’s modulus of the PU1 were also improved by 126% and 102%, respectively, compared to the pure PU. The significant improvement in both the thermal stability and mechanical properties for PU/GO composites was attributed to the homogeneous dispersion and good compatibility of GO with the PU matrix. The improvement in the properties upon the addition of GO may be attributable to the strong interfacial interaction between the reinforcing agent and the PU matrix. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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Open AccessArticle Styrene-Assisted Maleic Anhydride Grafted Poly(lactic acid) as an Effective Compatibilizer for Wood Flour/Poly(lactic acid) Bio-Composites
Polymers 2017, 9(11), 623; https://doi.org/10.3390/polym9110623
Received: 13 October 2017 / Revised: 4 November 2017 / Accepted: 12 November 2017 / Published: 15 November 2017
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Abstract
This study aimed to evaluate the effect of styrene-assisted maleic anhydride-grafted poly(lactic acid) (PLA-g-St/MAH) on the interfacial properties of wood flour/poly(lactic acid) (PLA) bio-composites. PLA-g-St/MAH was synthesized by free-radical melt grafting using styrene as a comonomer and dicumyl peroxide
[...] Read more.
This study aimed to evaluate the effect of styrene-assisted maleic anhydride-grafted poly(lactic acid) (PLA-g-St/MAH) on the interfacial properties of wood flour/poly(lactic acid) (PLA) bio-composites. PLA-g-St/MAH was synthesized by free-radical melt grafting using styrene as a comonomer and dicumyl peroxide as an initiator. The structure of PLA-g-St/MAH was characterized by Fourier transform infrared spectroscopy. Wood flour/PLA composites were prepared by compression molding using PLA-g-St/MAH as a compatibilizer. The effects of PLA-g-St/MAH on the rheological and mechanical properties, as well as on the fractured surface morphology of the composites were investigated. Results indicated that storage modulus, complex viscosity, equilibrium torque, and shear heat were significantly increased. The mechanical properties of the wood flour/PLA composites were also significantly increased after the addition of PLA-g-St/MAH. The maximum values were achieved at the loading rate of 3 wt % because of the improved interfacial adhesion between the wood flour and the PLA matrix. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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Open AccessArticle Stereocomplexation, Thermal and Mechanical Properties of Conetworks Composed of Star-Shaped l-Lactide, d-Lactide and ε-Caprolactone Oligomers Utilizing Sugar Alcohols as Core Molecules
Polymers 2017, 9(11), 582; https://doi.org/10.3390/polym9110582
Received: 2 October 2017 / Revised: 30 October 2017 / Accepted: 1 November 2017 / Published: 6 November 2017
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Abstract
It is important to develop tailor-made biodegradable/biocompatible polymer networks usable for biomaterials whose thermal and mechanical properties are easily controlled by changing the composition. We synthesized sugar-alcohol-based polymer networks (SPN-mscLAO/3CLO, m = 4, 5 or 6) by the crosslinking reactions of
[...] Read more.
It is important to develop tailor-made biodegradable/biocompatible polymer networks usable for biomaterials whose thermal and mechanical properties are easily controlled by changing the composition. We synthesized sugar-alcohol-based polymer networks (SPN-mscLAO/3CLO, m = 4, 5 or 6) by the crosslinking reactions of erythritol, xylitol or sorbitol-based m-armed star-shaped l-lactide and d-lactide oligomers (HmSLLAO and HmSDLAO), a glycerol-based 3-armed star-shaped ε-caprolactone oligomer (H3SCLO) and hexamethylene diisocyanate (HDI) at the weight ratios of HmSLLAO/HmSDLAO = 1/1 and (HmSLLAO + HmSDLAO)/H3CLO = 100/0, 75/25, 50/50, 25/75 or 0/100). The influence of the arm number on the crystallization behavior, thermal and mechanical properties of SPN-mscLAO/3CLOs were systematically investigated by comparing with those of sugar-alcohol-based homochiral polymer network (SPN-mLLAO, m = 4, 5 or 6) prepared by the reaction of HmSLLAO and HDI. Stereocomplex (sc) crystallites are dominantly formed for SPN-mscLAO/3CLOs 100/0–25/75, whereas SPN-mLLAOs were amorphous. The higher order of melting temperature of sc-crystals for SPN-mscLAO/3CLOs 100/0–25/75 was m = 5 > m = 6 > m = 4. The sc-crystallinities of SPN-4scLAO/3CLOs 100/0–50/50 were significantly lower than those of SPN-mscLAO/3CLOs 100/0–50/50 (m = 5 and 6). The larger order of the sc-spherulite size at crystallization temperature of 110 °C was m = 5 > m = 6 > m = 4 for SPN-mscLAO/3CLO 100/0. The size and number of sc-spherulites decreased with increasing crystallization temperature over the range of 110–140 °C and with increasing CLO fraction. Among all the networks, SPN-5scLAO/3CLOs 75/25 and 50/50 exhibited the highest and second highest tensile toughnesses (21.4 and 20.3 MJ·m−3), respectively. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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Open AccessArticle Fast Curing Bio-Based Phenolic Resins via Lignin Demethylated under Mild Reaction Condition
Polymers 2017, 9(9), 428; https://doi.org/10.3390/polym9090428
Received: 5 August 2017 / Revised: 2 September 2017 / Accepted: 5 September 2017 / Published: 7 September 2017
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Abstract
Demethylation technique has been used to enhance lignin reactivity for preparation of phenolic resins. However, the demethylation efficiency and the demethylated lignin (DL) reactivity were still unsatisfactory. To improve the demethylation efficiency, alkali lignin was demethylated under different mild conditions using sodium sulfite
[...] Read more.
Demethylation technique has been used to enhance lignin reactivity for preparation of phenolic resins. However, the demethylation efficiency and the demethylated lignin (DL) reactivity were still unsatisfactory. To improve the demethylation efficiency, alkali lignin was demethylated under different mild conditions using sodium sulfite as a catalyst. Lignin and DL were characterized by 1H-NMR (nuclear magnetic resonance) and Fourier transform infrared (FT-IR) spectroscopy to determine the demethylation mechanism. With the demethylation of lignin, the methoxyl group content decreased from 1.93 m mol/g to 1.09 m mol/g, and the phenolic hydroxyl group content increased from 0.56 m mol/g to 0.82 m mol/g. These results revealed that methoxyl groups were attacked by SO32, and some methoxyl groups were converted to phenolic hydroxyl groups by a nucleophilic substitution reaction, generating DL with high reactivity. The chemical properties of lignin-based phenolic resins were studied by 13C-NMR and FT-IR spectroscopy, and their physical properties were also investigated. The results indicated that lignin-based phenolic resins exhibited faster curing rate and shorter gel time. In addition, the bonding strength increased from 0.92 MPa to 1.07 MPa, and the formaldehyde emission decreased from 0.58 mg/L to 0.22 mg/L after lignin demethylated at the optimum condition. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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