Kinetics and Chemorheological Analysis of Cross-Linking Reactions in Humins

Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-iso...

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Veröffentlicht in:	Polymers Jg. 11; H. 11; S. 1804
Hauptverfasser:	Sangregorio, Anna, Guigo, Nathanaël, Jong, Ed de, Sbirrazzuoli, Nicolas
Format:	Journal Article
Sprache:	Englisch
Veröffentlicht:	Switzerland MDPI AG 02.11.2019 MDPI
Schriftenreihe:	Special issue: Sustainable Bio-Based Polymers: Towards a Circular Bioeconomy
Schlagworte:	Acids Chemical reactions Chemical Sciences Conversion Crosslinking Curing Energy Experiments Heat Initiators Kinetics Lignocellulose Material chemistry Mathematical functions Rheology Temperature Temperature effects Viscosity isoconversional method biobased thermoset kinetics humins lignocellulosic biomass valorization
ISSN:	2073-4360, 2073-4360
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Abstract	Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy (Eα-dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower Eα. The shift from chemical to diffusion control was also estimated.
AbstractList	Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy (Eα-dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower Eα. The shift from chemical to diffusion control was also estimated. Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy ( -dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower . The shift from chemical to diffusion control was also estimated. Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy (Eα-dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower Eα. The shift from chemical to diffusion control was also estimated.Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy (Eα-dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower Eα. The shift from chemical to diffusion control was also estimated. Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy (E-alpha-dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower E-alpha. The shift from chemical to diffusion control was also estimated.
Author	Sbirrazzuoli, Nicolas Sangregorio, Anna Jong, Ed de Guigo, Nathanaël
AuthorAffiliation	1 Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV Amsterdam, The Netherlands; anna.sangregorio@avantium.com (A.S.); ed.dejong@avantium.com (E.d.J.) 2 Institut de Chimie de Nice, Université Côte d’Azur, CNRS, UMR 7272, 06108 Nice, France; nathanael.guigo@univ-cotedazur.fr
AuthorAffiliation_xml	– name: 2 Institut de Chimie de Nice, Université Côte d’Azur, CNRS, UMR 7272, 06108 Nice, France; nathanael.guigo@univ-cotedazur.fr – name: 1 Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV Amsterdam, The Netherlands; anna.sangregorio@avantium.com (A.S.); ed.dejong@avantium.com (E.d.J.)
Author_xml	– sequence: 1 givenname: Anna surname: Sangregorio fullname: Sangregorio, Anna – sequence: 2 givenname: Nathanaël surname: Guigo fullname: Guigo, Nathanaël – sequence: 3 givenname: Ed de orcidid: 0000-0001-5300-4230 surname: Jong fullname: Jong, Ed de – sequence: 4 givenname: Nicolas orcidid: 0000-0002-6031-5448 surname: Sbirrazzuoli fullname: Sbirrazzuoli, Nicolas
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Keywords	isoconversional method biobased thermoset kinetics humins lignocellulosic biomass valorization
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Snippet	Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a...
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SubjectTerms	Acids Chemical reactions Chemical Sciences Conversion Crosslinking Curing Energy Experiments Heat Initiators Kinetics Lignocellulose Material chemistry Mathematical functions Rheology Temperature Temperature effects Viscosity
Title	Kinetics and Chemorheological Analysis of Cross-Linking Reactions in Humins
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