Renewability is not Enough: Recent Advances in the Sustainable Synthesis of Biomass‐Derived Monomers and Polymers

Llevot, Audrey; Dannecker, Patrick‐Kurt; Czapiewski, Marc von; Over, Lena Charlotte; Söyler, Zafer; Meier, Michael A. R.

doi:10.1002/chem.201602068

Cited by 227 publications

(186 citation statements)

References 179 publications

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“…The production of industrial chemical intermediates from renewable resources is an alternative to petrochemicals, often offering energy savings and contributing to sustainable development . Among these intermediates, renewable polymer building blocks are especially attractive, as many of them are oxygenates (as is biomass), and they are used in very large quantities . Purified terephthalic acid (PTA), a building block of polyethylene terephthalate (PET), is a very high‐demand, commodity chemical.…”

Section: Introductionmentioning

confidence: 99%

Bioderived Muconates by Cross‐Metathesis and Their Conversion into Terephthalates

et al. 2018

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Polyethylene terephthalate that is 100 % bioderived is in high demand in the market guided by the ever-more exigent sustainability regulations with the challenge of producing renewable terephthalic acid remaining. Renewable terephthalic acid or its precursors can be obtained by Diels-Alder cycloaddition and further dehydrogenation of biomass-derived muconic acid. The cis,cis isomer of the dicarboxylic acid is typically synthesized by fermentation with genetically modified microorganisms, a process that requires complex separations to obtain a high yield of the pure product. Furthermore, the cis isomer has to be transformed into the trans,trans form and has to be esterified before it is suitable for terephthalate synthesis. To overcome these challenges, we investigated the synthesis of dialkyl muconates by cross-metathesis. The Ru-catalyzed cross-coupling of sorbates with acrylates, which can be bioderived, proceeded selectively to yield diester muconates in up to 41 % yield by using very low catalyst amounts (0.5-3.0 mol %) and no solvent. In the optimized procedure, the muconate precipitated as a solid and was easily recovered from the reaction medium. Analysis by GC-MS and NMR spectroscopy showed that this method delivered exclusively the trans,trans isomer of dimethyl muconate. The Diels-Alder reaction of dimethyl muconate with ethylene was studied in various solvents to obtain 1,4-bis(carbomethoxy)cyclohexene. The cycloaddition proceeded with very high conversions (77-100 %) and yields (70-98 %) in all of the solvents investigated, and methanol and tetrahydrofuran were the best choices. Next, the aromatization of 1,4-bis(carbomethoxy)cyclohexene to dimethyl terephthalate over a Pd/C catalyst resulted in up to 70 % yield in tetrahydrofuran under an air atmosphere. Owing to the high yield of the reaction of dimethyl muconate to 1,4-bis(carbomethoxy)cyclohexene, no separation step was needed before the aromatization. This is the first time that cross-metathesis is used to produce bioderived trans,trans-muconates as precursors to renewable terephthalates, important building blocks in the polymer industry.

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Section: Introductionmentioning

confidence: 99%

Bioderived Muconates by Cross‐Metathesis and Their Conversion into Terephthalates

et al. 2018

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“…Decreasing fossil feedstocks and simultaneously growing global population, accompanied with an increasing demand for energy and resources, stimulate the development of materials from renewable resources. As the polymer sector accounts for a large portion of the chemical industry, the search for sustainable alternatives for polymeric materials is of high interest . Lignin is one of the most abundant biopolymers on earth and the largest natural resource for aromatic compounds .…”

Section: Introductionmentioning

confidence: 99%

“…The development of sustainable pathways to lignin‐based polymers is one of the main challenges in lignin chemistry, as conventional methods are still dominating this field . Besides the utilization in blends, lignin was shown to be a suitable reagent for copolymers such as polyurethanes, epoxy resins, and phenolic resins …”

Section: Introductionmentioning

confidence: 99%

Metathesis Curing of Allylated Lignin and Different Plant Oils for the Preparation of Thermosetting Polymer Films with Tunable Mechanical Properties

Over

Hergert

Meier

2017

Macromol. Chem. Phys.

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Lignin and plant oils—two highly available renewable feedstocks—are cured via olefin metathesis to produce thermosetting polymer films with tunable mechanical properties. Therefore, an organosolv lignin, allylated in a recently described sustainable approach, is used. For the first time, unmodified plant oils are reacted with a lignin derivative. An increasing lignin content as well as an increasing amount of polyunsaturated fatty acids in the plant oil structure lead to higher Young's moduli and higher cross‐linking density. Stress–strain measurements reveal ductile behavior of the prepared films. Only a lignin content over 70% leads to brittle materials. To improve the overall sustainability of this approach, dimethyl carbonate is investigated as sustainable solvent for film formation, leading to materials with similar Young's moduli and tensile strength, but lower degree of cross‐linking if compared to the more volatile solvent dichloromethane.

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“…These have been widely used in various engineering and commodity applications . Plant oil is one of the most interesting environmental resources for the synthesis of monomers or polymers, because of the aliphatic chain and functional groups contribute as a primary element to the backbone of polymer . It has received much attention as a renewable resource to replace petroleum resource for preparing chemicals and polymers .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and curing performance of a novel bio‐based epoxy monomer from soybean oil

Yang

Zhang

et al. 2017

Euro J Lipid Sci & Tech

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A novel bio‐based epoxy monomer (EP) was obtained from the reaction of modify soybean oil and epichlorohydrin (ECH). And EP blended with bisphenol‐A epoxy oligomer (DGEBA) to form the epoxy networks using triethylene tetramine as curing agent. The weight fraction of EP affects the performance of epoxy networks have been studied. The structures of the monomers and networks were studied by Fourier transformation infrared spectrometer (FTIR), and were consistent with the theoretical structures. Thermo‐gravimetric analysis (TG) and differential scanning calorimetry analysis (DSC) were used to determine the thermal properties of the epoxy networks, indicating that glass transition temperature (Tg) and thermal stability decreased with increasing EP content. Mechanical properties analysis showed that the elongation at break and impact strength of the epoxy networks increased with the increasing EP content, while the tensile strength decreased. Dynamic non‐isothermal curing test and scanning electron microscope (SEM) analysis revealed that there was no obvious phase separation and formed homogeneous crosslinking network structure. The properties of the epoxy networks were hard and brittle in low EP content, and presented strong flexible or soft flexible in high EP content. Practical applications: Soybean oil is one of the most interesting environmental resources for the synthesis of monomers, because of the aliphatic chain and functional groups contribute as a primary element to the backbone of polymer. It has received much attention as a renewable resource to replace petroleum resource for preparing chemicals and polymers, due to its environmental advantages, renewable and economic. The bio‐based epoxy resin can be used to modify the commercial bisphenol‐A epoxy resin to overcome the weaknesses of brittleness of the cured networks. As a novel epoxy monomer, it can be used in many fields which the traditional epoxy resins were used, such as paint, coatings, adhesives, electronic materials, and structural materials. Also, it can be used as a modifier to modify other industrial epoxy resins, due to the flexible aliphatic chain structure and low viscosity property. The bio‐based may degrade after discarding and come into environmental cycle. Soybean oil has received much attention as a renewable resource to replace petroleum resource for preparing chemicals and polymers, due to its environmental advantages, renewable and economic. In this paper, a novel polyols is derived from soybean oil and used for the preparation of aliphatic epoxy monomer. And then the bio‐based epoxy monomer is used to modify the commercial bisphenol‐A epoxy oligomer to overcome the weaknesses of brittleness of the cured networks. The epoxy monomer and epoxy networks prepared from soybean oil are environmentally friendly materials. It may degrade after discarding and come into environmental cycle.

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Renewability is not Enough: Recent Advances in the Sustainable Synthesis of Biomass‐Derived Monomers and Polymers

Cited by 227 publications

References 179 publications

Bioderived Muconates by Cross‐Metathesis and Their Conversion into Terephthalates

Bioderived Muconates by Cross‐Metathesis and Their Conversion into Terephthalates

Metathesis Curing of Allylated Lignin and Different Plant Oils for the Preparation of Thermosetting Polymer Films with Tunable Mechanical Properties

Synthesis and curing performance of a novel bio‐based epoxy monomer from soybean oil

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