Challenges and recent advances in bio-based isocyanate production

Niesiobędzka, Joanna; Datta, Janusz

doi:10.1039/d2gc04644j

Cited by 54 publications

(43 citation statements)

References 82 publications

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“…Nuclear Magnetic Resonance. 1 H nuclear magnetic resonance (NMR) and 13 C NMR spectra were recorded on JEOL 400 MHz ( 1 H) and JEOL 500 MHz ( 1 H) machines.…”

Section: Methodsmentioning

confidence: 99%

“…For example, 1 H NMR of TPU-4 (made from SaAzaPDO2000 polyester-polyol, 1,3-PDO, and TMDI) shows a clear signal of a urethane linkage (−NH) at around 7.03 ppm, confirming the PU reaction (Figure 4). Whereas 13 C NMR showed a chemical shift at 156.6 ppm and 172−173−4 ppm, corresponding to urethane and ester linkages in TPU-4, respectively (Figure 5). Similarly, TPU-5 to TPU-8 displayed characteristic chemical shifts based on the structure of TPUs (ESI Figures S40−S49).…”

Section: Synthesis Of Tpusmentioning

confidence: 99%

“…9 Diisocyanates are among the most commonly produced industrial chemicals in the world, owing to the industry's reliance on their unique reactivity. 13 The diisocyanate global market can be roughly classified by volume into three major groups: methylene diphenyl diisocyanate (MDI), toluene diphenyl diisocyanate (TDI), and aliphatic diisocyanates. Aliphatic diisocyanates are specialty intermediate materials used primarily to make CASEs in far smaller volumes than MDI and TDI.…”

Section: Introductionmentioning

confidence: 99%

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Variation of Aliphatic Diisocyanates in Bio-Based TPUs

Rajput,

Forman,

Halloran

et al. 2023

Macromolecules

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The utilization of bio-based materials for polymer production poses a challenge to both the industrial and academic sectors due to the availability and production costs of the necessary raw materials. Diisocyanates necessary for polyurethane synthesis have posed a particular challenge, given the paucity of natural diamine precursors for traditional phosgenation. We recently developed a phosgene-free flow chemistry methodology that allows for the safe, efficient, and scalable preparation of diisocyanates from naturally produced diacids. This chemistry broadens the potential for the development of renewable diisocyanates for a broad variety of applications. Here, we expand upon this work by demonstrating the scaled production of a panel of bio-based linear, aliphatic diisocyanates, with chain lengths ranging from four to eight carbons in good yields of 57–81% and high purity (∼97%). These are applied to the synthesis of thermoplastic polyurethanes (TPUs) containing up to a 100% renewable carbon content. TPUs formulated using shorter carbon-chained diisocyanates displayed a higher tensile strength compared to those formulated using longer chains. Ready access to diisocyanates of varying chain length affords the ability to tailor TPU properties through careful selection of the diisocyanate, polyol, and chain extender, offering hard and soft TPUs for multiple end-use applications.

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“…Nuclear Magnetic Resonance. 1 H nuclear magnetic resonance (NMR) and 13 C NMR spectra were recorded on JEOL 400 MHz ( 1 H) and JEOL 500 MHz ( 1 H) machines.…”

Section: Methodsmentioning

confidence: 99%

Section: Synthesis Of Tpusmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Variation of Aliphatic Diisocyanates in Bio-Based TPUs

Rajput,

Forman,

Halloran

et al. 2023

Macromolecules

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“…The level of anisotropy varies with the density of the foam, where denser foams are often manufactured in high-pressure molds. This pressure tends to shape the cells into spheres, thus decreasing the anisotropy of the material [ 12 , 13 , 14 ]. There are many works regarding polyurethanes’ main properties, applications and reinforcements, but the amount of information regarding bio-based PUF properties is still incomparable to the one for oil-based PUF.…”

Section: Introductionmentioning

confidence: 99%

Accelerated Aging on the Compression Properties of a Green Polyurethane Foam: Experimental and Numerical Analysis

Silva

Barros²,

Vieira

et al. 2023

Polymers

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The aim of this work is to evaluate the changes in compression properties of a bio-based polyurethane foam after exposure to 90 °C for different periods of time, and to propose a method to extrapolate these results and use a numerical approach to predict the compression behaviour after degradation for untested conditions at different degradation times and temperatures. Bio-based polymers are an important sustainable alternative to oil-based materials. This is explained by the foaming process and the density along the material as it was possible to see in a digital image correlation analysis. After 60 days, stiffness was approximately decreased by half in both directions. The decrease in yield stress due to thermo-oxidative degradation had a minor effect in the foaming directions, changing from 352 kPa to 220 kPa after 60 days, and the transverse property was harshly impacted changing from 530 kPa to 265 kPa. The energy absorption efficiency was slightly affected by degradation. The simulation of the compression stress-strain curves were in accordance to the experimental data and made it possible to predict the changes in mechanical properties for intermediate periods of degradation time. The plateau stress for the unaged foam transverse to the foaming direction presented experimental and numerical values of 450 kPa and 470 kPa, respectively. In addition, the plateau stresses in specimens degraded for 40 days present very similar experimental and numerical results in the same direction, at 310 kPa and 300 kPa, respectively. Therefore, this paper presents important information regarding the life-span and degradation of a green PUF. It provides insights into how compression properties vary along degradation time as function of material operation temperature, according to the Arrhenius degradation equation.

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“…[ 1 ] The worldwide production of PUs, the sixth‐most significant polymer, exceeded 24.7 million metric tonnes in 2021, and it is projected to reach 29.2 million metric tonnes by 2029. [ 2,3 ] Due to the worldwide PUs growing market having $95.13 billion in 2019 and is projected to increase at a compound annual growth rate of 12%, [ 4 ] PUs provides various advantages in terms of overall performance including foams, footwear, coatings, medical equipment, adhesives, and elastomers. [ 5–8 ] However, the majority of PUs produced today are created through the polyaddition reaction between polyols and isocyanates, and the isocyanates consumed for this purpose are extremely toxic and dangerous for both the environment and human health.…”

Section: Introductionmentioning

confidence: 99%

Innovations in applications and prospects of non‐isocyanate polyurethane bioplastics

Mangal,

H.,

Bose

et al. 2023

Biopolymers

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Currently, conventional plastics are necessary for a variety of aspects of modern daily life, including applications in the fields of healthcare, technology, and construction. However, they could also contain potentially hazardous compounds like isocyanates, whose degradation has a negative impact on both the environment and human health. Therefore, researchers are exploring alternatives to plastic which is sustainable and environmentally friendly without compromising its mechanical and physical features. This review study highlights the production of highly eco‐friendly bioplastic as an efficient alternative to non‐biodegradable conventional plastic. Bioplastics are produced from various renewable biomass sources such as plant debris, fatty acids, and oils. Poly‐addition of di‐isocyanates and polyols is a technique employed over decades to produce polyurethanes (PUs) bioplastics from renewable biomass feedstock. The toxicity of isocyanates is a major concern with the above‐mentioned approach. Novel green synthetic approaches for polyurethanes without using isocyanates have been attracting greater interest in recent years to overcome the toxicity of isocyanate‐containing raw materials. The polyaddition of cyclic carbonates (CCs) and polyfunctional amines appears to be the most promising method to obtain non‐isocyanate polyurethanes (NIPUs). This method results in the creation of polymeric materials with distinctive and adaptable features with the elimination of harmful compounds. Consequently, non‐isocyanate polyurethanes represent a new class of green polymeric materials. In this review study, we have discussed the possibility of creating novel NIPUs from renewable feedstocks in the context of the growing demand for efficient and ecologically friendly plastic products.

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Challenges and recent advances in bio-based isocyanate production

Abstract: Polyurethanes (PU) are key players in plastic industry. According to the Global Polyurethane Market (2019-2023), their value on the global market reached 95.13 billion $ in 2019, and is estimated...

Cited by 54 publications

References 82 publications

Variation of Aliphatic Diisocyanates in Bio-Based TPUs

Variation of Aliphatic Diisocyanates in Bio-Based TPUs

Accelerated Aging on the Compression Properties of a Green Polyurethane Foam: Experimental and Numerical Analysis

Innovations in applications and prospects of non‐isocyanate polyurethane bioplastics

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