Synthesis Of Phenolic Resins Research Articles

Synthesis of phenolic resins with cyclotriphosphazene for enhancement of ablation and char yields

A novel phenolic resin with combined hydroxymethyl-substituted phosphazene unit as a part of cured network was prepared which exhibited excellent thermal properties and ablation resistance. The novel phenolic resin was synthesized via copolymerizing from hexa (4-hydroxymethylphenoxy) cyclotriphosphazene (CHPP), phenol and paraformaldehyde. The CHPP contains abundant –CH2OH groups, which can be a part of phenolic resin network through condensation reactions between the –CH2OH groups and active hydrogens on benzene rings of phenolic resins. The optimal curing temperature for the modified phenolic resins was determined using the non-isothermal DSC method. The ablation resistance was investigated using the oxyacetylene flame method. The char yield and linear ablation rate of the modified phenolic resins are 71.3 % and 0.0020 mm/s, respectively. The ablation resistance of the novel resin is significantly improved, compared with other phenolic resin composites. The modification method for the phenolic resin provides a novel pathway to improve the application prospects of phenolic resins in the field of thermal protective materials.

Characterization and properties of phenolic resin doped modified lignin

Phenolic resins occupy an important position in industrial applications, but phenol, one of the raw materials for synthesis, is a non-renewable resource. Lignin, as a natural polymer containing phenolic hydroxyl groups, alcohol hydroxyl groups and other reactive groups, can replace some of the phenol in the synthesis of phenolic resins, which can reduce the amount of phenol, thus reducing the cost of phenolic resins, while effectively promoting the high value-added use of renewable biomass resources. Due to its low reactivity, alkaline lignin is usually discharged as production waste, unaware that lignin macromolecules can be modified. In this paper, the phenolic monomers were obtained by acid-catalyzed depolymerization of DES (choline chloride/p-toluenesulfonic acid or choline chloride/lactic acid) from waste alkaline lignin, and the recovery rate of the DES solution during the catalytic treatment was more than 85 %, in which the main monomer was 2-methoxy-4-(1-propyl) phenol. The degradation of alkaline lignin is still favorable after five times of DES solvent recovery. The depolymerized lignin monomer replaced phenol by 50 wt% and then ternary co-polymerized with phenol and formaldehyde to form a biomass phenol-based phenolic resin, providing a green route for phenolic resin production. The cost of resin preparation was economically calculated, and it was found that the cost of resin after accumulating 4 cycles of DES treatment was only 51.1 % of that of pure phenolic resin. The density functional theory (DFT) was used to simulate the possible radical reactions in the intermediate process of phenolic resin reaction, to explore the microscopic mechanism and competition, to provide theoretical reference for further experimental realization of resin structure control and optimization, and to improve the theoretical system of resin synthesis.

Synthesis of a water‐soluble high hydroxymethyl content phenolic resin crosslinker and the associated polyacrylamide weak gel property investigation

AbstractAs an in‐depth profile control agent, water‐soluble phenolic resin crosslinking polyacrylamide weak gel has been widely used in the middle and high water cut stage of water flooding reservoir. In this study, the phenolic resin was synthesized by two‐step alkali catalysis. Factors influencing the synthesis of phenolic resin, including the molar ratio of phenol and formaldehyde, catalyst types, reaction time, were investigated with hydroxylmethyl and aldehyde content as the criterion. When the molar ratio of phenolic resin was 1:2 and NaOH was catalyst, at 80°C for 4 h, the phenolic resin had the highest hydroxymethyl content (49.37%) and the lowest free aldehyde content (2.95%). Weak gel was formed by the reaction of LT002‐polyacrylamide with phenolic resin. Taking the gelation time and strength as criteria, the factors influencing the crosslinking property, including hydroxymethyl content, crosslinker addition, and polyacrylamide concentration were investigated respectively. Under optimal formulation, the property investigation shows that the hydroxymethyl group in the phenolic resin can be crosslinked with the amide group in polyacrylamide, the gelation time is long (50–60 h), and the gelation strength is larger than 5 × 104 mPa s, which is conductive to the plugging of deep oil layers. When the permeability was 5061 × 10−3 μm2, the plugging rate was 72.73%.

Phenol and formaldehyde alternatives for novel synthetic phenolic resins: state of the art

Since their appearance and commercialization, phenolic resins have been widely used and adopted in many sectors of activity. Produced from phenol and formaldehyde, these thermosetting materials are now being singled out because of the dangerousness of their precursors as well as the fossil raw material from which they are produced. To address and deal with the current general issue on the reduction of the impact of human activity on the environment, this review details and evaluates current studies on alternative molecules that can be used instead of phenol and formaldehyde in the synthesis of phenolic resins. After a contextualizing introduction and a quick review of what phenolic resins are and how these materials are obtained, two main parts are devoted to the platform molecules likely to replace phenol, first, and formaldehyde, second. Finally, the author gives his opinion on the future potential of research concerning the substitution of these molecules and the future of phenolic resins.

Preparation and Characterization of Date Palm Bio-Oil Modified Phenolic Foam.

In this work, the potential of biomass-derived date palm bio-oil as a partial substitute for phenol in the phenolic resin was evaluated. Date palm bio-oils derived from date palm were used for the partial substitution of phenol in the preparation of phenolic foam (PF) insulation materials. Date palm waste material was processed using pyrolysis at 525 °C to produce bio-oil rich in phenolic compounds. The bio-oil was used to partially replace phenol in the synthesis of phenolic resin, which was subsequently used to prepare foams. The resulting changes in the physical, mechanical, and thermal properties of the foams were studied. The substituted foams exhibited 93%, 181%, and 40% improvement in compressive strength with 10%, 15%, and 20% bio-oil substitution, respectively. Due to the incorporation of biomass waste material, the partial reduction in phenol uses, and the favorable properties, the date palm bio-oil substituted phenolic foams are considered more environmentally benign alternatives to traditional phenolic foams.

Lignin phenolation by graft copolymerization to boost its reactivity

Lignin is the most abundant phenolic biopolymer and a renewable resource of aromatics. It can be used as a phenol substitute in the synthesis of phenolic resins. However, lignin is not as reactive as phenol, so phenolation is generally carried out to improve lignin reactivity. In this work, we suggest a solution to circumvent the limitations of traditional phenolation (e.g., high temperature, strong acids/bases, limited reactivity, and phenol toxicity). We first attempt new lignin phenolation by graft copolymerization in which polymeric phenol, instead of toxic phenol, is introduced to lignin. Organosolv lignin from hardwood was modified with 2-bromoisobutyryl bromide to act as a lignin macroinitiator (L-Br). A protected phenolic monomer, 4-acetoxystyrene, was graft copolymerized onto L-Br using CuBr2/tris[2-(dimethylamino)ethyl]amine as a catalyst/ligand, after which the resultant lignin copolymer was deacetylated to produce lignin grafted with poly(4-hydroxystyrene). This poly-phenolation process was conducted at room temperature without the strong acids/bases and toxic phenol required in conventional phenolation. The poly-phenolated lignin was analyzed using 1H-, 13C-, and 31P NMR spectroscopy and gel permeation chromatography. This novel phenolation process enhanced the reactive sites of lignin more than tenfold. It also reduced the dark color of technical lignins significantly, thereby overcoming a serious obstacle to their applicability.

Production of pyrolytic lignin for the phenolic resin synthesis via fast pyrolysis

Recycling of waste wood into resol type phenol-formaldehyde (PF) resins via fast pyrolysis was demonstrated. Waste wood collected from the building demolition site in Finland was pyrolyzed with 20 kg/h circulating fluidized bed pyrolysis pilot unit. Pilot was operated with high organic liquid yield (60 wt% on average) and the produced fast pyrolysis bio-oil was fractionated by water addition into aqueous phase and water insoluble phase. The obtained fractions were characterized, and the water-insoluble viscous lignin fraction was used in the synthesis of PF-resins. Commercial phenol was successfully replaced by pyrolytic lignin fraction at 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% producing resins of low in free formaldehyde content, but resins with high replacement ratio exhibited higher viscosities. The use of H2O/n-butanol mixture as solvent at a ratio 70:30 wt/wt% proved capable to prolong the storage time of the resin and helped to maintain the viscosity at acceptable values for at least 2 weeks before their use in the targeted application. Finally, the gluing performance of the resins was evaluated by measuring the tensile shear strength of lap joints formed by gluing 5 mm thick beech wood veneers. All the produced resins fulfilled a dry strength limit of ≥ 10 N/mm2. Wet strength limit ≥ 7 N/mm2 was fulfilled by the resins with the replacement ratio up 40 wt%, but resins with replacement ratio of 50 wt% had somewhat reduced wet strength. These results confirm a promising protentional application of pyrolysis derived lignin fraction in phenolic wood adhesives, at least in dry conditions.

Selection of kraft lignin fractions as a partial substitute for phenol in synthesis of phenolic resins: Structure-property correlation

In this work, a strategy was proposed aiming to describe an efficient kraft lignin (KL) fractionation method to extract large amounts of low molar mass lignin to partially replace non-renewable phenol with the KL fractions in the synthesis of phenolic resins. KL from Eucalyptus urograndis wood was refined by a fractionation process in ethyl acetate (EtAc). The lignin-phenol-formaldehyde (LPF) resins were formulated by replacing 25% and 50% of phenol with the fractionated lignin. The lignin employed were KL, fraction of KL insoluble in EtAc (LFIns) and fraction of KL soluble in EtAc (LFSol). The LFSol and LFIns fractions were analyzed for composition, functional group content, and thermal properties. Gel Permeation Chromatography (GPC) results indicated that the lower molar mass lignin fractions (LFSol) showed higher solubility in EtAc. The total hydroxyl groups content (by 31 P NMR) of the soluble EtAc fraction increased to 4.73 mmol.g −1 after fractionation. The phenolic resin based on monomers derived from LFSol showed adhesion strength, glass transition temperature and thermal stability with values close to commercial phenolic resins. The better homogeneity of the LPF resin produced from LFSol at 25% phenol substitution resulted in adhesion properties similar to the control resin. On the other hand, LFSol could successfully directly replace 15% of the commercial PF resin (corresponding to > 30% phenol replacement) showing the performance similar to the commercial PF control and significantly higher than the LFIns and non-fractionated KL. • Extraction method of low molar mass kraft lignin. • Structure-performance correlation of selection of kraft lignin fractions. • Partial replacement of non-renewable phenol by lignin fractions. • Improved performance of the soluble lignin fraction as an adhesive.

Synthesis of phenolic resins by substituting phenol with modified spruce kraft lignin

Synthesis of phenolic resins by substituting phenol with modified spruce kraft lignin

Microwave co-pyrolysis for simultaneous disposal of environmentally hazardous hospital plastic waste, lignocellulosic, and triglyceride biowaste

Microwave co-pyrolysis was examined as an approach for simultaneous reduction and treatment of environmentally hazardous hospital plastic waste (HPW), lignocellulosic (palm kernel shell, PKS) and triglycerides (waste vegetable oil, WVO) biowaste as co-feedstock. The co-pyrolysis demonstrated faster heating rate (16–43 °C/min) compared to microwave pyrolysis of single feedstock (9–17 °C/min). Microwave co-pyrolysis of HPW/WVO performed at 1:1 ratio produced a higher yield (80.5 wt%) of hydrocarbon liquid fuel compared to HPW/PKS (78.2 wt%). The liquid oil possessed a low nitrogen content (< 4 wt%) and free of sulfur that could reduce the release of hazardous pollutants during its use as fuel in combustion. In particular, the liquid oil obtained from co-pyrolysis of HPW/WVO has low oxygenated compounds (< 16%) leading to reduction in generation of potentially hazardous sludge or problematic acidic tar during oil storage. Insignificant amount of benzene derivatives (< 1%) was also found in the liquid oil, indicating the desirable feature of this pyrolysis approach to suppress the formation of toxic polycyclic aromatic hydrocarbons (PAHs). Microwave co-pyrolysis of HPW/WVO improved the yield and properties of liquid oil for potential use as a cleaner fuel, whereas the liquid oil from co-pyrolysis of HPW/PKS is applicable in the synthesis of phenolic resin.

Synthesis and Thermal Degradation Study of Polyhedral Oligomeric Silsesquioxane (POSS) Modified Phenolic Resin.

In this paper, a new polyhedral oligomeric silsesquioxane containing a phenol group (POSS-Phenol) is prepared through the Michael addition reaction, which is added to the synthesis of phenolic resin as a functional monomer. Infrared spectroscopy (IR) is used to demonstrate the chemistry structure of the synthesized POSS modified phenolic resin. After introducing POSS into the resole, a comprehensive study is conducted to reveal the effects of POSS on the thermal degradation of phenolic resin. First, thermal degradation behaviors of neat phenolic resin and modified phenolic resin are carried out by thermogravimetric analysis (TGA). Then, the gas volatiles from thermal degradation are investigated by thermogravimetric mass spectrometry (TG-MS). Finally, the residues after thermal degradation are characterized by X-ray diffraction (XRD). The research indicates that POSS modified phenolic resin shows a better thermal stability than neat phenolic resin, especially at high temperatures under air atmosphere. On the one hand, the introduction of the POSS group can effectively improve the release temperature of oxygen containing volatiles. On the other hand, the POSS group forms silica at high temperatures under air, which can effectively inhibit the thermal oxidation of phenolic resin and make phenolic resin show a better high-temperature oxidation resistance.

Novel lignin-based phenolic nanosphere supported palladium nanoparticles with highly efficient catalytic performance and good reusability

Lignin, the most abundant aromatic biopolymer, has great potential as a sustainable phenol replacement in phenolic resin synthesis, which has been considered as one of the most promising options for lignin valorization. In this work, kraft lignin from bamboo was used as a phenol substitute for the fabrication of novel lignin-based phenolic resin (LPR) nanosphere using a facile hydrothermal process. The as-prepared LPR nanosphere was then used as a reducing agent and a stabilizing support for synthesis of Pd nanoparticles (NPs). It was found that 40 % replacement of phenol by lignin led to a significant decrease of the nanosphere size and enhancement of the nanosphere surface roughness, which eventually increased the specific surface area of LPR nanosphere. Owing to the enhanced specific surface area and the excellent reducing activity of lignin, the as-prepared LPR nanosphere had considerably higher Pd NPs loading amount compared with the lignin-free PR support. Therefore, the as-prepared Pd@LPR nanocomposites demonstrated highly efficient catalytic ability for the reduction of toxic Cr(VI) and two typical dyes. Moreover, the Pd@LPR nanocomposites exhibited excellent reusability owing to the stable loading of Pd NPs on the lignin-based support. Consequently, the lignin-based nanosphere, prepared by a facile hydrothermal process, is used as a reducing agent and a support for Pd NPs synthesis, which presents a novel approach to develop lignin-functionalized catalyst materials.

A haem-peroxidase from the seeds of Araujia sericifera: Characterization and use as bio-tool to remove phenol from aqueous solutions

Abstract Plants seeds are an important source of enzymes with biotechnological interest. In particular, plant peroxidases, because of their enzymatic activity and stability, are used for the synthesis of phenolic resins, in the treatment of waste waters, or as labelling enzymes and in food industry. Thus, these enzymes can give a potential substitute of other polluting industrial catalysts to the conservation of the environment. In the present work, a novel plant peroxidase (named As-sP) was purified and characterised from seeds of Araujia sericifera. This enzyme (∼40 kDa) exhibits a maximum activity at pH 5.0 and is a haem-peroxidase, basing on both the spectroscopic properties and amino acid composition. As-sP activity increased by Ca2+, Cu2+, Mg2+; while in presence of EDTA, it is lost. On the other hand, As-sP activity is stable in a range of 40–60 °C, while decreased at higher temperature (70–80 °C). Furthermore, the activity has been tested in presence of natural (chlorogenic acid, pyrogallol and guaiacol) or synthetic (ABTS) substrates, finding that chlorogenic acid (Km 38.6 ± 2.4 μM and Vmax 92.6 ± 3.9 μM min−1) was the most suitable. Finally, this enzyme was able to remove phenol from water solutions, and this capacity increases in presence of Ca2+ and polyethylene glycol. This novel peroxidase, due to its enzymatic properties and heat stability, is a novel tool for bioremediation and can be used as a beneficial candidate for industrial applications, such as in decontamination of phenol-polluted waters.

Bio-Crude by Acidic Phenolation and Carbamation for the Preparation of Phenolic Thermosetting Resin and Its Application in Thermoresistant Laminates

Abstract Fir sawdust was liquefied in phenol solvent under acidic catalyst at 135, 150 and 165 °C, respectively; after neutralization, bio-crude was obtained where contained oil-like liquid and tiny powder-like residue. The bio-crude was chemically modified with urea at high temperature (e. g. &gt; 130 °C) to form carbamate so as to improve chemical reactivity of bio-crude in phenolic resin synthesis. The carbamate-containing bio-crude was condensed with paraformaldehyde into thermosetting phenolic resin. Finally, this biomass-derived phenolic resin matrixed silica fabric laminates were processed. The uncured and thermally cured bio-based resins were characterized by the techniques of Differential Scanning Calorimetry (DSC), Fourier Transform Infrared spectrum (FT-IR), rheology and Thermogravimetric Analysis (TGA), and the laminates’ structure and mechanical performances were studied using the methods of Scanning Electron Microscopy (SEM), three point bending mechanical test and Dynamic Mechanical Analysis (DMA). The results showed: (1) the chemical reactivity of bio-crude was highly improved by carbamation; (2) biomass-derived thermosetting phenolic resin was thermally curable at 150–250 °C (with two exothermic peaks at 185 °C and 220 °C); (3) the char yield was about 47 %, which was not in apparent relationship with sawdust liquefaction temperatures; (4) flexural strength of silica fabric laminates at room temperature was around 357 MPa (similar with that of conventional phenolic laminate); (5) glass transition temperature of silica fabric laminate was above 270 °C (much higher than Tg of conventional phenolic resin laminate, which is normally at 215 °C). The biomass-derived phenolic resin is expected to be widely used as cost-effective and environment-friendly thermosetting resin in the application of high-performance composites.

Lignin Phenol Formaldehyde Resoles Using Base-Catalysed Depolymerized Kraft Lignin.

Lignin phenol formaldehyde (LPF) resols were produced using depolymerized lignin fractions at various levels of phenol substitution (50 to 70 wt %). To produce monomeric-rich (BCD-oil) and oligomeric (BCD-oligomers) bio-based phenolic compounds, softwood kraft lignin was base-catalysed degraded. These base-catalysed depolymerized (BCD) building blocks were further used to substitute phenol in the synthesis of phenolic resins and were characterized in detail (such as viscosity, free formaldehyde and phenol content, chemical composition, curing and bonding behaviour). The adhesive properties were compared to a phenol formaldehyde (PF) reference resin and a LPF with untreated kraft lignin. The resins synthesized with the two depolymerized lignin types differ significantly from each other with increasing phenol substitution. While with LPF-BCD-oligomers the viscosity increases and the bonding strength is not effected by increasing lignin content in the resin, a reduction of these properties could be observed with LPF-BCD-oil. Furthermore, LPF-BCD-oil showed similar curing behaviour and ultimate strength as the reference LPF. Adhesive bonds made using LPF-BCD-oligomers exhibited similar strength to those made using PF. Compared to the reference resins, it has been demonstrated that modified renewable lignin based phenolic components can be an equally performing alternative to phenol even for high degrees of substitution of 70%.

SYNTHESIS AND MECHANICAL PROPERTIES OF LAMINATES BASED ON PHENOLIC RESINS MODIFIED WITH SODIUM LIGNOSULFONATE

The reduction of phenol and/or formaldehyde consumption during phenolic resin synthesis is of great technological and scientific interest because of its economic and environmental implications. In this work, the addition of sodium lignosulfonate as partial replacement of phenol in the phenolic resol base resins used for decorative laminates production is experimentally studied. The work involves: i) the characterization and reactivation of lignosulfonate, ii) the industrial synthesis of traditional and modified resols by replacement of 10%w/w of phenol, iii) the industrial impregnation of Kraft-type papers with the produced resins, iv) the production of laminates at laboratory and industrial scale, and, v) the measurement of their final properties. Tensile, bending and impact strength were evaluated. Modified laminates exhibited mechanical properties statistically comparable with those of traditional laminates. Industrial tests were carried out at Centro S.A, San Francisco, Córdoba.

Preparation and Characterization of Lignin from Malaysian Coconut Coir Husk (CCH) as a Potential Precursor in Phenol-Formaldehyde (Phenolic) Resins for the Plastics Industry

Coconut coir husk (CCH) was chosen to extract it lignin due to high lignin content comparable with other natural fibre. The lignin was extracted and its utilization in production of phenolic resin was investigated. The percentage extracted lignin obtained in this studied was 38.1% which indicated the high yield of lignin. Two phenolic resins were prepared, which are phenol-formaldehyde resin and lignin-formaldehyde resin. The functional group present in the lignin and both phenolic resins were further analyzed using the Fourier Transform Infrared Spectroscopy (FTIR). The findings from the infrared spectra of the lignin-formaldehyde resin were similar to the phenol-formaldehyde resin. These indicate that lignin can be partially used as phenol in phenolic resin synthesis.

Analysis of Synthesis of General-Purpose Phenolic Resin and Its Curing Mechanism

Based on analysis of existing problems related to general-purpose phenolic resin and extensive laboratory experimental studies, a synthetic method for general-purpose phenolic resin was determined. Its curing mechanism and the influencing factors of curing rate were investigated. Commonly used curing agents and corresponding dosage for phenolic resin synthesis were also identified. This paper provides a reference for research on phenolic resin modification.

Production of bio-based phenolic resin and activated carbon from bio-oil and biochar derived from fast pyrolysis of palm kernel shells

A fraction of palm kernel shells (PKS) was pyrolyzed in a fluidized bed reactor. The experiments were performed in a temperature range of 479–555°C to produce bio-oil, biochar, and gas. All the bio-oils were analyzed quantitatively and qualitatively by GC-FID and GC–MS. The maximum content of phenolic compounds in the bio-oil was 24.8wt.% at ∼500°C. The maximum phenol content in the bio-oil, as determined by the external standard method, was 8.1wt.%. A bio-oil derived from the pyrolysis of PKS was used in the synthesis of phenolic resin, showing that the bio-oil could substitute for fossil phenol up to 25wt.%. The biochar was activated using CO2 at a final activation temperature of 900°C with different activation time (1–3h) to produce activated carbon. Activated carbons produced were microporous, and the maximum surface area of the activated carbons produced was 807m2/g.

Bark extractives-based phenol–formaldehyde resins from beetle-infested lodgepole pine

In this study, phenol–formaldehyde (PF) resins derived from the bark extractives were synthesized and characterized. Bark of lodgepole pine (Pinus contorta Dougl.) infested by mountain pine beetle (Dendroctonus ponderosae Hopkins) was first extracted with 1% NaOH. The bark extractives with and without acid-neutralization were then dried to the solid state. The neutralized and non-neutralized extractives were used to partially replace petroleum-based phenol for synthesizing the bark extractives-PF resins. In comparison with a commercial PF resin and a laboratory made PF resin (Lab PF), the bark extractive-PF resins were found to have higher molecular weights, higher viscosities, and shorter gel times. Acid neutralization of the bark extractives increased the molecular weight of the extractives and modified the performance and curing behavior of the resulting bark extractive-PF resins. Bark extractive-PF resins (BEPF) showed a similar level of post-cured thermal stability to that of the lab PF at higher temperatures, but they differed significantly from that of the commercial PF resin. The bark extractive-PF resins made from both neutralized and non-neutralized extractives at 30% replacement of phenol (by weight) exhibited similar dry and wet bond strengths to the commercial PF resin. At 50% substitution level, BEPF had dry and wet bond strengths similar to the lab PF resin. Our findings suggest that alkaline extractives from mountain pine beetle-infested lodgepole pine bark are suitable for partially substituting phenol in the synthesis of phenolic resin for use in wood adhesives.