scholarly journals Solvent-free bulk polymerization of lignin-polycaprolactone (PCL) copolymer and its thermoplastic characteristics

2019 ◽  
Vol 9 (1) ◽  
Author(s):  
In-Kyung Park ◽  
Hanna Sun ◽  
Sung-Hoon Kim ◽  
Youngjun Kim ◽  
Go Eun Kim ◽  
...  
Keyword(s):  
Bulk Polymerization ◽  
Kraft Lignin ◽  
Degree Of Polymerization ◽  
Hydroxyl Groups ◽  
Reaction Conditions ◽  
Oh Groups ◽  
Grafted Copolymer ◽  
Subsequent Activation ◽  
Chain Lengths ◽  
Lignin Polymerization

Abstract The pristine lignin molecules contain multiple reactive hydroxyl [OH] groups, some of which undergo limited polymerization depending on their configuration (aromatic or aliphatic) or conformation. The key issue in lignin-polymerization is to quantify the number of hydroxyl groups in the pristine molecules for subsequent activation to specific lignin-polymer chain lengths or degree of grafting. In this study, using ε-caprolactone (CL) as a reactive solvent, we successfully polymerized CL on the [OH] sites in the kraft lignin macromonomers (LM, Mw = 1,520 g mol−1), which resulted in a thermoplastic lignin-polycaprolactone (PCL) grafted copolymer. We found that the average number of [OH] groups in the LM was 15.3 groups mol−1, and further detected 40–71% of the [OH] groups in the CL bulk polymerization. The degree of polymerization of PCL grown on each [OH] site ranged between 7 and 26 depending on the reaction conditions ([CL]/[OH] and reaction-time) corresponding to 4,780 and 32,600 g mol−1 of PCL chains per a LM. The thermoplastic characteristics of the synthesized lignin-PCL copolymers were established by the melt viscosity exhibiting a shear-thinning behavior, e.g., 921 Pa.s at 180 °C. The thermal stability was remarkable providing a Tid (2% of weight loss) of 230 °C of the copolymers, compared with 69 °C for the pristine lignin.

Effect of different catalysts on the oxyalkylation of eucalyptus Lignoboost® kraft lignin

Holzforschung ◽  
2020 ◽  
Vol 74 (6) ◽  
pp. 567-576 ◽  
Author(s):  
Fernanda R. Vieira ◽  
Ana Barros-Timmons ◽  
Dmitry V. Evtuguin ◽  
Paula C. R. Pinto
Keyword(s):  
High Performance ◽  
Black Liquor ◽  
Kraft Lignin ◽  
Degree Of Polymerization ◽  
Kraft Pulping ◽  
Size Exclusion ◽  
Safe Procedure ◽  
Oh Groups ◽  
Exclusion Chromatography ◽  
A Minor

AbstractLignin obtained by Lignoboost® procedure from black liquor after kraft pulping of Eucalyptus globulus wood was characterized and converted into liquid polyols via an innovative and safe procedure using base catalyzed oxyalkylation with propylene carbonate (PC). The effect of four catalysts, Potassium carbonate (K2CO3), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), dicyanodiamide (DICY), and 1,4-diazabicyclo [2.2.2] octane (DABCO) was evaluated in terms of lignin polyol yield and weight gain. The ensuing polyols were also characterized by fourier transform infrared (FTIR), 1H NMR, 13C NMR, and size exclusion chromatography (SEC) to determine the degree of the substitution (DS), degree of polymerization (DP), and the molecular weight, respectively. Only a minor proportion of PC (ca. 3–15%) was converted to propylene glycol/homooligomers as revealed by high performance liquid chromatography (HPLC). All catalysts promoted preferential derivatization of lignin phenolic OH groups by oxypropyl moieties. The maximum average DP of propylene oxide chains in oxyalkylated Lignoboost® kraft lignin (oKL) was 1.85 per one phenylpropane unit (PPU) using DBU. Conversely, the DP of oKL using DICY was very low (0.27/PPU). DICY’s catalytic activity seems to be jeopardized due to the formation of unreactive adducts with lignin. The oKL obtained using DBU, DABCO, and K2CO3 have potential to be used as polyols in the production of polyurethanes as the corresponding hydroxyl number (IOH) is in the range of 198–410 mg KOH g−1.

Bleaching ability of pre-hydrolyzed pulps in the context of a biorefinery mill

TAPPI Journal ◽  
2013 ◽  
Vol 12 (11) ◽  
pp. 49-53 ◽  
Author(s):  
CHRISTINE CHIRAT ◽  
LUCIE BOIRON ◽  
DOMINIQUE LACHENAL
Keyword(s):  
Carbon Content ◽  
Acid Hydrolysis ◽  
13C Nmr ◽  
Kraft Lignin ◽  
Kappa Number ◽  
Hydroxyl Groups ◽  
Kraft Pulps ◽  
Quaternary Carbon ◽  
Oxygen Delignification

Autohydrolysis and acid hydrolysis treatments were applied on mixed softwood chips. The cooking ability was studied by varying the alkali and duration of the cook. Pulps with kappa numbers varying from 30 to 70 were obtained. The bleaching ability of these pulps was studied and compared to control kraft pulps. The prehydrolyzed pulps were shown to be more efficiently delignified by oxygen than the control kraft pulps starting from the same kappa number. Furthermore, the final bleaching was also easier for these pulps. It was also shown that extensive oxygen delignification applied on high-kappa pre-hydrolyzed pulps could be a way to improve the overall yield, which is a prerequisite for the development of such biorefinery concepts. Lignin was isolated from the control kraft and the two pre-hydrolyzed kraft pulps and analyzed by 13C NMR. Lignins from pre-hydrolyzed kraft pulps had similar free phenolic groups content to the control kraft lignin, but their aliphatic hydroxyl groups and β-O-4 content were lower than for the control lignin. The quaternary carbon content was the same for all the samples.

Properties and Applications of Modified Bacterial Cellulose-Based Materials

2020 ◽  
Vol 16 ◽  
Author(s):  
Munair Badshah ◽  
Hanif Ullah ◽  
Fazli Wahid ◽  
Taous Khan
Keyword(s):  
Surface Modification ◽  
Bacterial Cellulose ◽  
Degree Of Polymerization ◽  
Biomedical Science ◽  
Hydroxyl Groups ◽  
Market Demand ◽  
Ideal Candidate ◽  
Fibrous Network ◽  
Potential Applications ◽  
Surface Modification Techniques

Background: Bacterial cellulose (BC) is purest form of cellulose as it is free from pactin, lignin, hemicellulose and other active constituents associated with cellulose derived from plant sources. High biocompatibility and easy molding into desired shape make BC an ideal candidate for applications in biomedical field such as tissue engineering, wound healing and bone regeneration. In addition to this, BC has been widely studied for applications in the delivery of proteins and drugs in various forms via different routes. However, BC lacks therapeutic properties and resistance to free movement of small molecules i.e., gases and solvents. Therefore, modification of BC is required to meet the research ad market demand. Methods: We have searched the updated data relevant to as-synthesized and modified BC, properties and applications in various fields using Web of science, Science direct, Google and PubMed. Results: As-synthesized BC possesses properties such as high crystallinity, well organized fibrous network, higher degree of polymerization, and ability of being produced in swollen form. The large surface area with abundance of free accessible hydroxyl groups makes BC an ideal candidate for carrying out surface functionalization to enhance its features. The various reported surface modification techniques including, but not limited to, are amination, methylation and acetylation. Conclusion: In this review, we have highlighted various approaches made for BC surface modification. We have also reported enhancement in the properties of modified BC and potential applications in different fields ranging from biomedical science to drug delivery and paper-making to various electronic devices.

scholarly journals Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2131
Author(s):  
Leonardo Dalseno Antonino ◽  
Júlia Rocha Gouveia ◽  
Rogério Ramos de Sousa Júnior ◽  
Guilherme Elias Saltarelli Garcia ◽  
Luara Carneiro Gobbo ◽  
...  
Keyword(s):  
Experimental Work ◽  
Chemical Structure ◽  
31P Nmr ◽  
Kraft Lignin ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Diphenylmethane Diisocyanate ◽  
Complex Chemical ◽  
Heterogeneous Reactivity ◽  
Phenolic Hydroxyl Groups

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. 31P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.

scholarly journals Development of Highly Efficient, Glassy Carbon Foam Supported, Palladium Catalysts for Hydrogenation of Nitrobenzene

Nanomaterials ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 1172
Author(s):  
Ádám Prekob ◽  
Mahitha Udayakumar ◽  
Gábor Karacs ◽  
Ferenc Kristály ◽  
Gábor Muránszky ◽  
...  
Keyword(s):  
Zeta Potential ◽  
Glassy Carbon ◽  
Palladium Nanoparticles ◽  
Palladium Catalysts ◽  
Sucrose Solution ◽  
Supported Catalyst ◽  
Carbon Foam ◽  
Hydroxyl Groups ◽  
Polyurethane Elastomers ◽  
Oh Groups

Glassy carbon foam (GCF) catalyst supports were synthesized from waste polyurethane elastomers by impregnating them in sucrose solution followed by pyrolysis and activation (AC) using N2 and CO2 gas. The palladium nanoparticles were formed from Pd(NO3)2. The formed palladium nanoparticles are highly dispersive because the mean diameters are 8.0 ± 4.3 (Pd/GCF), 7.6 ± 4.2 (Pd/GCF-AC1) and 4.4 ± 1.6 nm (Pd/GCF-AC2). Oxidative post-treatment by CO2 of the supports resulted in the formation of hydroxyl groups on the GCF surfaces, leading to a decrease in zeta potential. The decreased zeta potential increased the wettability of the GCF supports. This, and the interactions between –OH groups and Pd ions, decreased the particle size of palladium. The catalysts were tested in the hydrogenation of nitrobenzene. The non-treated, glassy-carbon-supported catalyst (Pd/GCF) resulted in a 99.2% aniline yield at 293 K and 50 bar hydrogen pressure, but the reaction was slightly slower than other catalysts. The catalysts on the post-treated (activated) supports showed higher catalytic activity and the rate of hydrogenation was higher. The maximum attained aniline selectivities were 99.0% (Pd/GCF-AC1) at 293 K and 98.0% (Pd/GCF-AC2) at 323 K.

Adsorption of Benzene from Aqueous Solution Using Base Modified Expanded Perlite

2012 ◽  
Vol 622-623 ◽  
pp. 1779-1783
Author(s):  
Richard Appiah-Ntiamoah ◽  
Xuan Thang Mai ◽  
Francis W.Y. Momade ◽  
Hern Kim
Keyword(s):  
Zeta Potential ◽  
Adsorption Capacity ◽  
Linear Regression Analysis ◽  
Basic Medium ◽  
Maximum Adsorption Capacity ◽  
Hydroxyl Groups ◽  
Expanded Perlite ◽  
Oh Groups ◽  
Base Solution ◽  
Ph Range

In this study, the adsorption capacity of expanded perlite (EP) for benzene at low concentrations in water was investigated after EP was treated with sodium hydroxide (NaOH). IR spectra used to characterize the modified EP showed that there was no bonding between NaOH and the hydroxyl groups on the surface of EP. However, the NaOH provided a basic medium for negatively charged surface oxide ions (-SO-) to form on EP. This fact was corroborated by pH readings of the modification solution. This reduced in pH from 10 to 9 at the end of the reaction which indicated that the hydroxyl OH- groups on the EP underwent deprotonation and hence releases H+ into the solution, and also positive sites on EP adsorbed OH- ions from the base solution. Mahir et al. in their paper Zeta potential of unexpanded and expanded perlite samples in various electrolyte media confirmed that EP has no isoelectric point and exhibits negative zeta potential in the pH range of 2-11. The surface oxides (-SO-) were believed to have given EP it adsorptive potential. Adsorption isotherm values correlated reasonably well with the Langmuir isotherm model and it parameters (qo and K) were obtained using linear regression analysis. A maximum adsorption capacity (qo) value of 19.42 mg/g was achieved.

scholarly journals Controlled Depolymerization of Cellulose Fibres Isolated from Lignocellulosic Biomass Wastes

2018 ◽  
Vol 2018 ◽  
pp. 1-11
Author(s):  
Suh Cem Pang ◽  
Lee Ken Voon ◽  
Suk Fun Chin
Keyword(s):  
Lignocellulosic Biomass ◽  
Acid Catalyst ◽  
Degree Of Polymerization ◽  
Second Order ◽  
Water Soluble ◽  
Cellulose Fibres ◽  
Amberlyst 15 ◽  
Pseudo Second Order ◽  
Chain Lengths ◽  
Optimized Conditions

Various types of lignocellulosic biomass wastes (LBW) had been successfully converted into cello-oligomers with different chain lengths via a controlled depolymerization process. Cellulose fibres isolated from LBW samples were dissolved with room temperature ionic liquid (RTIL) in the presence of an acid catalyst, Amberlyst 15 DRY. The effects of reaction time on the degree of polymerization and yields of water-insoluble cello-oligomers formed were studied. Besides, the yields of water-soluble cello-oligomers such as glucose and xylose were also determined. The depolymerization of cellulose fibres isolated from LBW was observed to follow both second-order and pseudo-second order kinetics under specific conditions. As such, cello-oligomers of controllable chain lengths could be obtained by adjusting the duration of depolymerization process under optimized conditions.

Proton spin–spin coupling constants and intramolecular hydrogen bonding in bromine derivatives of 1,3-dihydroxybenzene

1976 ◽  
Vol 54 (14) ◽  
pp. 2228-2230 ◽  
Author(s):  
Ted Schaefer ◽  
J. Brian Rowbotham
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Proton Spin ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Hydroxyl Groups ◽  
Oh Groups ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Derivatives Of

The conformational preferences in CCl4 solution at 32 °C of the hydroxyl groups in bromine derivatives of 1,3-dihydroxybenzene are deduced from the long-range spin–spin coupling constants between hydroxyl protons and ring protons over five bonds. Two hydroxyl groups hydrogen bond to the same bromine substituent in 2-bromo-1,3-dihydroxybenzene but prefer to hydrogen bond to different bromine substituents when available, as in 2,4-dibromo-1,3-dihydroxybenzene. When the OH groups can each choose between two ortho bromine atoms, as in 2,4,6-tribromoresorcinol, they apparently do so in a very nearly statistical manner except that they avoid hydrogen bonding to the common bromine atom.

scholarly journals The Role of Carboxyl and Hydroxyl Groups of Humic Acid in Removing AuCl4- from Aqueous Solution

2017 ◽  
Vol 17 (1) ◽  
pp. 95 ◽  
Author(s):  
Sri Sudiono ◽  
Mustika Yuniarti ◽  
Dwi Siswanta ◽  
Eko Sri Kunarti ◽  
Triyono Triyono ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Humic Acid ◽  
Peat Soil ◽  
Sharp Decrease ◽  
Hydroxyl Groups ◽  
Mixed Solution ◽  
Oh Groups ◽  
Characterization Result ◽  
Ft Ir

Humic acid (HA) extracted from peat soil according to the recommended procedure of the International Humic Substances Society (IHSS) has been tested to remove AuCl4- from aqueous solution. The removal was optimum at pH 2.0 and it was mainly dictated by attachment through hydrogen bonding to unionized carboxyl (–COOH) groups and reduction by the action of the hydroxyl (–OH) groups to gold (Au) metal. The removal of AuCl4- improved after HA was purified through repeated immersion and shaking in a mixed solution containing 0.1 M HCl and 0.3 M HF. When the purification led to the sharp decrease in ash content from 39.34 to 0.85% (w/w) and significant increase in both the –COOH and –OH contents from 3240 to 3487 mmol/kg and from 4260 to 4620 mmol/kg, respectively; the removal of AuCl4- improved from 0.105 to 0.133 mmol/g. This improvement of AuCl4- removal by the purified HA was accompanied by higher ability in reduction to Au metal. The attached AuCl4- on –COOH groups of both crude and purified HAs was qualitatively observed by the characterization result of FT-IR spectroscopy, while the presence of Au metal on the surface of those HAs was verified by the characterization result of XRD.

Cell adhesion to hydroxyl groups of a monolayer film

1988 ◽  
Vol 91 (2) ◽  
pp. 269-279
Author(s):  
N.F. Owens ◽  
D. Gingell ◽  
A. Trommler
Keyword(s):  
Cell Adhesion ◽  
Flow Chamber ◽  
Cell Contact ◽  
Hydroxyl Groups ◽  
Adjacent Area ◽  
Oh Groups ◽  
Monomolecular Films ◽  
Langmuir Blodgett Films ◽  
Long Chain Alcohol ◽  
Minimal Measure

We have studied cells on chemically defined monomolecular films of the long-chain alcohol docosanol. Langmuir-Blodgett films of the alcohol were deposited on glass coverslips, previously made hydrophobic with octadecyl groups. This gives films in which the alcohol headgroups face outwards to the water. Molecular orientation and film integrity were shown by a fluorescence adsorption test. Cell contacts on the films were observed in media without proteins by interference reflection microscopy (IRM) and the mechanics of detachment were examined by hydrodynamic shearing in a flow chamber. Cell contact with docosanol was compared with that on an adjacent area of octadecyl glass without a monolayer. Dictyostelium amoebae settled and spread on both docosanol and octadecyl glass, but little or no locomotion was seen on docosanol. On octadecyl glass the amoebae moved actively, forming ultrathin cytoplasmic lamellae, which look dark under IRM, and left distinctive trails of membranous debris. Hydrodynamic shearing showed that the amoebae stuck strongly to both surfaces and could not be removed from either at the maximum attainable wall shear stress of 6Nm-2. Red blood cells also adhered to both surfaces and removal from both occurred between 1 and 3Nm-2. IRM and scanning electron microscopy (SEM) studies indicated that this force leads to a minimal measure of red cell adhesion, since removal often involved the breakage of cytoplasmic tethers. Our results show that alcoholic -OH groups, in a two-dimensional array, provide a surface that is strongly adhesive for cells. No other method has made it possible to demonstrate cell adhesion purely to -OH groups, in a known orientation and density, and in the absence of any other functional groups on the interface.

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