Engineering Plastics from Lignin. IX. Phenolic Resin Synthesis and Characterization

The performance of phenol-formaldehyde (PF) resins, formulated with lignin derivatives previously synthesized as phenolic resin prepolymers, was evaluated by thermal analysis of the curing process, and by a hard maple shear block test. At 54 and 60% phenol replacement levels, respectively, kraft (KL) and steam explosion lignin (SEL)-based resoles exhibited cure behavior very similar to a standard PF resin. Acid hydrolysis lignin gelled prematurely, and was found to be incompatible with the normal synthesis procedure. Differential scanning calorimetry (DSC) was used to compare kinetic parameters for the curing process of neat and lignin derived phenolic resins. Activation energies and cure rates determined by DSC showed no difference between adhesives. High lignin contents had no inhibitory effect on resin cure. Shear strength properties were evaluated in a compression test, and results illustrate that both lignin-based resins have acceptable strength properties, both in a dry and accelerated aging test. Of the lignins tested, kraft lignin consistently demonstrated superior performance as a pre-polymer in phenolic adhesives. This was attributed to differences in the chemical structure of the two lignins, which had been found to vary in terms of their reactivity with formaldehyde and phenol. KL had been noted to be more amenable to derivatization with formaldehyde and phenol, hence its ability to crosslink with a phenol-formaldehyde fraction during resin synthesis was increased. Positive structural features in KL are a high phenolic guaiacyl (3-methoxy, 4-hydroxy phenyl) content, low carbon-to-carbon bonding between aromatic rings, high solubility in alkali, and a higher number average molecular weight than SEL.     

Preparation and Characterization of Demethylated Lignin-Polyethylenimine Adhesives

Petrochemical-based adhesives such as urea-formaldehyde and phenol-formaldehyde resins are predominant wood adhesives. In this study, a new wood adhesive from lignin was developed and characterized. The new adhesive consisted of demethylated kraft lignin (DKL), a byproduct in the production of dimethyl sulfoxide from kraft lignin, and a polyethylenimine (PEI). Lap-shear specimens bonded with this new DKL-PEI adhesive system had very high shear strength and were very water-resistant. The effects of the preparation time, the curing conditions, the total solids content of the adhesive, the DKL/PEI weight ratio and the molecular weight of PEI on the shear strength and water-resistance of the resulting lap-shear specimens were studied in detail. Investigation on the curing chemistry of this new adhesive revealed that phenolic hydroxyl groups were oxidized to form quinones that further reacted with PEI. It was proposed that the curing mechanisms of this DKL-PEI adhesive were similar to the quinone-tanning processes in nature.     

Preparation and Characterization of Demethylated Lignin-Polyethylenimine Adhesives

Petrochemical-based adhesives such as urea-formaldehyde and phenol-formaldehyde resins are predominant wood adhesives. In this study, a new wood adhesive from lignin was developed and characterized. The new adhesive consisted of demethylated kraft lignin (DKL), a byproduct in the production of dimethyl sulfoxide from kraft lignin, and a polyethylenimine (PEI). Lap-shear specimens bonded with this new DKL-PEI adhesive system had very high shear strength and were very water-resistant. The effects of the preparation time, the curing conditions, the total solids content of the adhesive, the DKL/PEI weight ratio and the molecular weight of PEI on the shear strength and water-resistance of the resulting lap-shear specimens were studied in detail. Investigation on the curing chemistry of this new adhesive revealed that phenolic hydroxyl groups were oxidized to form quinones that further reacted with PEI. It was proposed that the curing mechanisms of this DKL-PEI adhesive were similar to the quinone-tanning processes in nature.     

Oxidation of Various Kraft Lignins with a Bacterial Laccase Enzyme

Modification of kraft lignin (KL), traditionally uses harsh and energy-demanding physical and chemical processes. In this study, the potential of the bacterial laccase CotA (spore coating protein A) for oxidation of KL under mild conditions was assessed. Thereby, the efficiency of CotA to oxidize both softwood and hardwood KL of varying purity at alkaline conditions was examined. For the respective type of wood, the highest oxidation activity by CotA was determined for the medium ash content softwood KL (MA_S) and the medium ash content hardwood KL (MA_H), respectively. By an up to 95% decrease in fluorescence and up to 65% in phenol content coupling of the structural lignin units was indicated. These results correlated with an increase in viscosity and molecular weight, which increased nearly 2 and 20-fold for MA_H and about 1.3 and 6.0-fold for MA_S, respectively. Thus, this study confirms that the CotA laccase can oxidize a variety of KL at alkaline conditions, while the origin and purity of KL were found to have a major impact on the efficiency of oxidation. Under the herein tested conditions, it was observed that the MA_H KL showed the highest susceptibility to CotA oxidation when compared to the other hardwood KLs and the softwood KLs. Therefore, this could be a viable method to produce sustainable resins and adhesives.     

Origin and Nature of Kraft Colour: 2 The Role of Bleaching in the Formation of the Extraction Stage Effluent Colour

Upon chlorination and extraction, high molecular weight (>1000D) kraft lignin (KL) is degraded to a material which is structurally similar to extraction stage effluent. During bleaching there is a significant decrease in the aromaticity of KL without a concomitant decrease in colour, which would be expected if aromatic residues are the kraft chromophores. Treatment of simple sugars under conditions similar to those of kraft pulping yielded polymeric products which, on treatment with chlorine and subsequential extraction (CE), gave products with similar spectral characteristics to extraction stage effluent. It is proposed that the chromophores responsible for kraft colour are keto-enols probably derived from the degradation of carbohydrates during the kraft cook.     

Kraft lignin in polyurethanes I. Mechanical properties of polyurethanes from a kraft lignin–polyether triol–polymeric MDI system

Polyurethanes with various NCO/OH ratios and kraft lignin contents were synthesized by polymerization of kraft lignin (free of the low and high molecular weight fractions), a propylene–oxide-based polyether triol and polymeric MDI in tetrahydrofuran solution. Films were made by solvent casting and tested with respect to swelling behavior and tensile properties. The main findings were: At low NCO/OH ratios, kraft lignin contributed effectively to the formation of the three dimensional network; under particular conditions of NCO/OH ratio and kraft lignin content, polyurethanes of considerable toughness were obtained; at high kraft lignin contents, the obtained polyurethanes were hard and brittle regardless of the NCO/OH ratio used.     

Ionic liquid modified lignin-phenol-glyoxal resin: a green alternative resin for production of particleboards

The aim of this research was to evaluate the properties of particleboard panels bonded with ionic liquid treated lignin- phenol- glyoxal (LPG) resin. For this purpose, soda bagasse lignin was modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid and then various contents of virgin and modified lignin (20, 30 and 40 wt% based on weight of phenol), phenol and glyoxal were used for synthesis of LPG resins. After resin synthesis, thermal and physicochemical properties of the synthesized resins such as curing behavior, gelation time, viscosity, solid content and density were measured. Finally, the resins so prepared were used for laboratory particleboard manufacturing. The panels physical (water absorption, thickness swelling) as well as mechanical (MOE, MOR and internal bond strength) properties were measured according to standard methods. The resins tests indicated that modification of lignin with ionic liquid not only can accelerate the gelation time and increase viscosity, density and solid content of LPG resins but also decrease the temperature required for curing the LPG resins. Based on the results of this work, the mechanical strength and dimensional stability of the particleboards bonded with a LPG resin can be improved by using modified lignin. The particleboards prepared with the LPG resin, using either modified or virgin lignin, presented higher water absorption as well as weaker mechanical strength than those prepared with the control PF resin. However, there does not appear to be any statistically significant difference between the some properties of the panels bonded with the control PF resin and those bonded with the LPG resin containing modified lignin.     

CONTRIBUTION OF CARBOHYDRATE-DERIVED CHROMOPHORES TO KRAFT PULPING LIQUOR COLOUR

Pine wood, holocellulose, glucose and milled wood lignin were kraft cooked and the acid-insoluble materials isolated. Based on the amounts of precipitates isolated and their absorbances, most, or all, of the absorbance of the acid-insoluble material in kraft spent liquor (kraft lignin, KL) could be ascribed to lignin-derived chromophores. The absorption spectrum of kraft-cooked glucose (KG) differed significantly from that of KL and kraft-cooked milled wood lignin (KMWL), with a higher absorbance in the visible region of the spectrum. It also responded differently on treatment with a number of chemicals, strongly suggesting that carbohydrate-derived chromophores could only contribute slightly to the absorbance of KL. The effect of sequential treatment with oxygen, chlorine dioxide and alkali on the absorption spectra of KL, KG and KMWL was also determined. This produced no evidence to suggest that carbohydrate-derived chromophores contribute significantly to chromophore changes during these bleaching stages.     

Influence of Resin Molecular Weight on Curing and Thermal Degradation of Plywood Made From Phenolic Prepreg Palm Veneers

The present work evaluates curing and the thermal behavior of different molecular weight phenol formaldehyde (PF) resins used to prepare PF prepreg oil palm stem veneers. The physical properties (solid contents, gelation time, pH, and viscosity) of PF resins were determined. The molecular weight of resins was characterized by gel permeation chromatography, whilst thermal properties were determined by differential scanning calorimetry and thermogravimetric analyses. The average molecular weight of PF resins were 526 g/mole (low), 1889 g/mole (medium), and 5178 g/mole (control - commercial). Among the resins, medium (MMwPF) gives better thermal stability with a retained weight of 48.9% at 300°C. High (Commercial PF) had a low decomposition temperature (109.3°C) which occurred within 11 min. Both low (LMwPF) and MMwPF started to melt at ≥120°C. Based on strength and shear values, phenolic prepreg palm veneers can be prepared using either low or medium molecular weight PF but with varying results. In all cases, the mechanical properties of palm plywood made from PF prepreg veneers were superior to those made from PF-bonded plywood using the commercial process.     

Epoxidation of Methanol-Soluble Kraft Lignin for Lignin-Derived Epoxy Resin and Its Usage in the Preparation of Biopolyester

Most commercial epoxy resins have been produced using toxic bisphenol A. Lignin can be utilized as green substitute for bisphenol A to produce bio-epoxy resins. Methanol-soluble kraft lignin was extracted by methanol fractionation for lignin epoxidation, and epoxidized into lignin-derived epoxy resin via two-step epoxidation consisting of epichlorohydrin addition and epoxide ring restructuring. Epoxidized lignin was selectively separated from non- or less-reacted lignin based on their solubility differences in organic solvents. The existence of epoxide groups in the lignin-derived epoxy resin was confirmed using FT-IR, ¹H-NMR, and TGA analyses. Epoxidized lignin was used as a reactive lignin macromonomer to prepare biopolyester. The characteristics of the synthesized biopolyester were analyzed using FT-IR, and the thermal properties were analyzed by TGA. The thermal decomposition temperature of 5% weight loss (T_d5) was determined to be 257.1°C, which is comparable to epoxy resins that are used in electronic applications.     

Origin and Nature of Kraft Colour: 1 Role of Aromatics

The chromophores responsible for kraft colour have been generally assumed to be derived from the aromatic portions of the lignin molecule. Analytical studies of the high molecular weight dissolved materials from kraft lignin, kraft cooked sugars, and extraction stage effluent by pyrolysis GC-MS, permanganate/periodate oxidation, and UV-visible spectroscopy showed that these materials had a wide variation in aromatic content but similar spectral properties. It is now proposed that carbohydrate degradation products produced by the kraft cooking of sugars are primarily responsible for the kraft colour.     

Engineering biomass into formaldehyde‐free phenolic resin for composite materials

The use of formaldehyde to prepare phenol‐formaldehyde (PF) resins is one of the primary challenges for the world‐wide PF industry with respect to both sustainability and human health. This study reports a novel one‐pot synthesis process for phenol‐5‐hydroxymethylfurfural (PHMF) resin as a formaldehyde‐free phenolic resin using phenol and glucose, and the curing of the phenolic resin with a green curing agent organosolv lignin (OL) or Kraft lignin (KL). Evidenced by ¹³C NMR, the curing mechanism involves alkylation reaction between the hydoxyalkyl groups of lignin and the ortho‐ and para‐carbon of PHMF phenolic hydroxyl group. The curing kinetics was studied using differential scanning calorimetry and the kinetic parameters were obtained. The OL/KL cured PHMF resins were tested in terms of thermal stability, and mechanical properties for their applications in fiberglass reinforced composite materials. The results obtained demonstrated that OL/KL can be promising curing agents for the PHMF resins. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1275–1283, 2015     

Rheology Study of Sugar Cane Bagasse Lignin-Added Phenol–Formaldehyde Adhesives

The rheological properties of sugar cane bagasse lignin–phenol formaldehyde (PF) (30% lignin – PF) resins were studied using oscillation tests. The bagasse lignin was introduced in the classic adhesive formulation in order to supply a part of PF. Rheological qualities of optimal lignin–PF (30% lignin – PF) resins and commercial PF resin were assessed by using a rotary rheometer (ARES). Dynamic rheological measurements, performed at low strain in the linear range, are useful to characterize the network properties of resins.

The results obtained showed that the time sweep indicates excellent structural stability of optimal lignin–PF (30% lignin–PF) resins and commercial PF resin. The elastic modulus is greater than the viscous one showing a remarkable elastic character of the resins, and the performed frequency sweeps show a typical spectrum of a “weak gels” structure. The time dependence at 125°C shows that the optimum cure time is 7.5 min.     

THE INFLUENCE OF COMPOSITION ON THE SWELLING OF KRAFT BLACK LIQUOR DURING PYROLYSIS

During the drying and pyrolysis phases of kraft black liquor combustion, significant swelling of individual liquor particles occurs. Swollen volumes can reach 20 to 30 times the original volume during combustion. The swelling process can affect the combustibility of black liquor and the amount of carryover in a recovery furnace.

The composition of black liquor was found to have a large influence on swelling. A combination of sugar acids and kraft lignin swelled to a larger extent than when either component was pyrolyzed separately. A 1:1 ratio of these two components resulted in maximum swelling for the various ratios tested. The molecular weight of kraft lignin had an effect on swollen volume with higher molecular weight fractions producing lower swelling chars.

Other components were found to reduce the swelling of black liquors. Extractives interfered with the swelling by appearing to change the deformable properties of the pyrolyzing material. Inorganic salts acted as a diluent.

Analysis of the surface characteristics of chars revealed that good swelling chars were composed of small bubbles 50 to 150 microns in diameter. Poor swelling liquors did not exhibit this phenomenon. The formation of bubbles was found to be initiated at 240°C, which closely corresponded to the thermal decomposition temperature of a sugar acid. Kraft lignin appeared to have a major influence on the fluid properties of the pyrolyzing particle. The composition of black liquor determines to a large extent surface forces present in black liquor; these forces are thought to be responsible for the extent to which kraft black liquors deform and swell during pyrolysis.     

Synthesis and characterization of lignin–poly(acrylamide)–poly(2‐methacryloyloxyethyl) trimethyl ammonium chloride copolymer

In this work, two monomers, acrylamide (AM) and [2‐(methacryloyloxy)ethyl]trimethylammonium chloride (DMC) were copolymerized from kraft lignin (KL) in an aqueous suspension initiated by free radical copolymerization in the presence of potassium persulfate. The impact of copolymerization conditions on the charge density and molecular weight of the copolymers was investigated. The molecular weight and mass balance analyses confirmed that the homopolymer [polyDMC (PDMC) and polyAM (PAM)] and undesired copolymer (AM–DMC) productions dominated as time, initiator, and DMC dosage increased more than the optimum values. The activation energy of the polymerization of KL and AM (43.02 kJ mol^?1), KL and DMC (21.99 kJ mol^?1), AM (14.54 kJ mol^?1), DMC (10.34 kJ mol^?1), and AM and DMC (18.13 kJ mol^?1) was determined. Proton nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, and elemental analysis confirmed the production of KL–AM–DMC copolymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46338.     

Characterization of four different lignins as a first step toward the identification of suitable end‐use applications

To determine the most appropriate use of lignin, surface, structural, and thermal characteristics of lignin was investigated in this work. It was observed that kraft lignin (KL), the lignin of prehydrolysis liquor (LPHL), lignosulfonate of NSSC process (LSL), and lignosulfonates (LSs) of sulfite pulping process had 0.67, 0.25, 0.90, and 1.52–2.25 meq/g anionic charge density, and 6.3, 2.1, 10.1, and 8.8–10.1 nm hydrodynamic diameter, respectively. These results suggested that LSL and LSs could be used more effectively than other lignin as filler modifiers, flocculants, and dispersants. The combustion studies of the lignin samples suggested that KL and LPHL combusted more efficiently than other samples, as they had high heating (calorific) values of 27.02 and 19.2 MJ/kg, the apparent activation energy of 126.64 and 99.14 kJ/mol based on Flynn–Wall–Ozawa method and 122.16 and 94.73 kJ/mol based on Kissinger–Akahira–Sunose and no ash, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42336.     

Novel applications of lignin in composite materials

Some exploratory work was done to look at novel applications, such as filler use and comonomers, for lignin in thermosetting unsaturated polyesters and vinyl esters. The solubility of different lignins (pine kraft, hardwood, ethoxylated, and maleinated) was determined in different resin systems (acrylated epoxidized soybean oil, hydroxylated soybean oil, soy oil monoglyceride, and a commercial vinyl ester) to give an idea of the compatibility of lignin with the resin systems that were used. Further, the use of lignin as a filler was studied. An increase in the glass‐transition temperature was noticed, and the modulus at 20°C decreased because of the plasticizing effect of lignin. The lignin was modified to improve its effect on the matrix properties by adding double bond functionality, thus making it possible to incorporate the lignin molecule in the resin through free‐radical polymerization. Modified lignin was introduced in several resins by a reaction with maleic anhydride and epoxidized soybean oil and was tested for its effect on the solubility, glass‐transition temperature, and modulus. This modification improved the solubility of lignin in styrene‐containing resins, as well as the chemical incorporation of lignin in the resin. Moreover, lignin was used to treat the surfaces of natural hemp fibers to utilize lignin's natural affinity for cellulosic fibers. The idea was to cure the surface defects on the natural fibers and increase the bonding strength between the resin and fiber. An optimum improvement was noticed that depended on the amount of lignin covering the fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 323–331, 2002     

Parameters Affecting the Cross-Flow Filtration of Dissolved LignoBoost Kraft Lignin

In the kraft pulping process, the lignin-containing by-product kraft black liquor is currently combusted as an energy source. LignoBoost is a technique that extracts lignin from kraft black liquor, resulting in a lignin-lean black liquor, which is returned to the process, and an extracted kraft lignin. To facilitate the use of the extracted kraft lignin in high-value applications, it can be refined via fractionation to produce a more homogeneous starting raw material. Hence, the aim of this study is to investigate the behavior of dissolved softwood kraft lignin during cross-flow filtration. The effects of the lignin concentration, pH, and ionic strength on the fractionation of the dissolved lignin during cross-flow filtration are investigated. The results indicate that large amounts of low-molecular-weight kraft lignin can be produced from solutions having a low lignin concentration. Furthermore, the effects of pH and ionic strength on the fractionation of low-molecular-weight lignin are identified within the studied ranges.     

Effect of irradiation on the composition and thermal properties of softwood kraft lignin and styrene grafted lignin

Lignin is an abundant, underutilized natural resource that has potential to be used as a biomaterial but is currently hampered in its use by not being uniform in structure and composition and is thermally unstable due to phenolic group. To address these issues and modify its thermal properties, softwood kraft lignin was modified using γ‐irradiation at low doses with and without styrene present and characterized. Irradiation of kraft lignin alone with γ‐radiation shows an initial decrease in molecular weight due to chain scission up to about 10 kGy followed by an increase in molecular weight due to crosslinking. NMR results indicate a decrease of about 15% in the OH content of the lignin with 30 kGy irradiation. Thermal properties such as T_g, free volume and ΔC_p follow accordingly. Irradiation at very low dosages was determined to facilitate the grafting of styrene monomer to lignin, decreasing the OH content by 23%. This effect increased the hydrophobicity of the material, depressed the value of T_g, increased the ΔC_p, increased the mobility in the liquid state, and made the material more thermally stable relative to the lignin alone, thus improving its processability at high temperatures. Both the irradiation of lignin alone and the grafting of styrene to lignin increased the yield of mass during pyrolysis and the activation energy for mass loss relative to untreated lignin alone. This work has demonstrated that the application of low dosages of γ‐irradiation is a promising method to attach functional molecules onto lignin for use in various applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39743.     

Tailoring the molecular and thermo–mechanical properties of kraft lignin by ultrafiltration

This study has shown that ultrafiltration allows the selective extraction from industrial black liquors of lignin fraction with specific thermo‐mechanical properties, which can be matched to the intended end uses. Ultrafiltration resulted in the efficient fractionation of kraft lignin according to its molecular weight, with an accumulation of sulfur‐containing compounds in the low‐molecular weight fractions. The obtained lignin samples had a varying quantities of functional groups, which correlated with their molecular weight with decreased molecular size, the lignin fractions had a higher amount of phenolic hydroxyl groups and fewer aliphatic hydroxyl groups. Depending on the molecular weight, glass‐transition temperatures (T_g) between 70 and 170°C were obtained for lignin samples isolated from the same batch of black liquor, a tendency confirmed by two independent methods, DSC, and dynamic rheology (DMA). The Fox–Flory equation adequately described the relationship between the number average molecular masses (M_n) and T_g's‐irrespective of the method applied. DMA showed that low‐molecular‐weight lignin exhibits a good flow behavior as well as high‐temperature crosslinking capability. Unfractionated and high molecular weight lignin (M_w >5 kDa), on the other hand, do not soften sufficiently and may require additional modifications for use in thermal processings where melt‐flow is required as the first step. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40799.