Curing of phenolic resins modified with chestnut tannin extract

Phenolic novolac resins have been modified with chestnut tannin for reduction of phenol content in resins. In this work, rheological and kinetic analysis of curing reactions of these resins with hexamethylenetetramine (hexamine) has been performed. Chemical structure of obtained materials has been analyzed and compared with that of nonmodified resins. Results reveal that cure reactions of resin modified with chestnut tannin are different when compared with nonmodified novolacs not only in the cure kinetics values but also in final chemical structure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2034–2039, 2006     

Low Formaldehyde Emitting Biobased Wood Adhesives Manufactured from Mixtures of Tannin and Glyoxylated Lignin

Abstract

Kraft (LN-T-CO₂-2) and wheat straw (CIMV) glyoxalated lignin mixed with mimosa tannin and hexamine as a hardener were used as wood adhesive resins in particleboard fabrication. The adhesive systems proportion used were 40/60 and 50/50 w/w for lignin and tannin, respectively. The gel time test was determined by knowing the polymerization time between the different mixes under the controlled conditions. The results showed a slower polymerization with the kraft lignin/mimosa tannin blending than with the wheat straw lignin/mimosa tannin one. Thermomechanical analyses (TMA) tests were carried out as an indication of the final strength of the adhesive systems revealed by the elasticity modulus (MOE). The MOE results have demonstrated the best mechanical resistance values in 40/60 lignin/mimosa tannin proportion with respectively 3.422 and 3.347 (MPa), for CIMV and LN-T-CO₂-2, and 2.122 (MPa) for 50/50 proportion. Particleboards were prepared and the internal bond (IB) tests were carried out according to the European Standard EN 312. The IB tests confirmed the TMA results. The higher mechanical results of the IB were .43 and 0.53 (MPa), for CIMV and LN-T-CO₂-2 lignin in a 40/60 lignin/mimosa tannin proportion. They were classified as interior panel P2 in according with the standard request EN-312. Free-formaldehyde was determined through the flask method EN 717-3. Particleboards prepared with these natural adhesive resins registered emissions at least 87 and 75% lower than the commercial UF and MUF dhesive resins. The panels were classified as E0.     

A novel fiber–veneer-laminated composite based on tannin resin

Natural nonwoven fiber was impregnated with a tannin resin and laminated with wood veneer for preparation of laminated composites. The tannin resin used showed a good compatibility with the natural fiber, and was easy to assemble with the wood veneers. The tannin resin penetration into the wood veneer was observed by light microscopy. The laminated composite shows very good mechanical properties and water resistance. Shear force–displacement testing demonstrates that the laminated composite had a ductile behavior under wet testing conditions. The laminated composite was prepared using 100% natural biorenewable raw materials and had good properties compared to conventional plywood bonded with synthetic resin.     

Synthesis and cure kinetics of liquefied wood/phenol/formaldehyde resins

Wood liquefaction was conducted at a 2/1 phenol/wood ratio in two different reactors: (1) an atmospheric three‐necked flask reactor and (2) a sealed Parr reactor. The liquefied wood mixture (liquefied wood, unreacted phenol, and wood residue) was further condensed with formaldehyde under acidic conditions to synthesize two novolac‐type liquefied wood/phenol/formaldehyde (LWPF) resins: LWPF1 (the atmospheric reactor) and LWPF2 (the sealed reactor). The LWPF1 resin had a higher solid content and higher molecular weight than the LWPF2 resin. The cure kinetic mechanisms of the LWPF resins were investigated with dynamic and isothermal differential scanning calorimetry (DSC). The isothermal DSC data indicated that the cure reactions of both resins followed an autocatalytic mechanism. The activation energies of the liquefied wood resins were close to that of a reported lignin–phenol–formaldehyde resin but were higher than that of a typical phenol formaldehyde resin. The two liquefied wood resins followed similar cure kinetics; however, the LWPF1 resin had a higher activation energy for rate constant k₁ and a lower activation energy for rate constant k₂ than LWPF2. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Wood-induced catalytic activation of PF adhesives autopolymerization vs. PF/wood covalent bonding

The reaction of polycondensation of phenol-formaldehyde (PF) resins in the presence of wood was confirmed to have a lower energy of activation than of the PF resin alone. Under the low temperature and short curing times characteristic of the application of PF resins as thermosetting wood adhesives DSC, TGA, chemical kinetics, and IR of PF resins and relevant model compounds were carried out. These indicated that two effects appear to be present when a PF resin cures on a wood surface, both induced by the polymeric constituents of the substrate, namely carbohydrates and lignin. These appear to be (1) the catalytic activation of the resin self-condensation induced particularly by carbohydrates such as crystalline and amorphous cellulose and hemicelluloses and (2) the formation of resin/substrate covalent bonding, particularly in the case of lignin. The first appears to be, by far, the major cause of the lowering of the activation energy of PF resins curing. The contribution of the second has been found to be very small and often negligble under the conditions pertaining to thermosetting wood adhesives applications. Molecular mechanics results appear to indicate that the marked catalytic activation of PF resins autocondensation and curing appears to be induced by the strong set of PF adhesive/substrate secondary forces interactions which appear to weaken bonds which, by cleavage, lead to PF resins autocondensation. © 1994 John Wiley & Sons, Inc.     

Influence of wood extractives on two-component polyurethane adhesive for structural hardwood bonding

ABSTRACT

When bonding wood for structural applications, the wood–adhesive bond is influenced by a variety of factors. Besides the physical and mechanical properties of wood species, their chemical composition, e.g. wood extractives, can play a role in bonding wooden surfaces. A two-component polyurethane system (2C PUR) was chosen to better adapt to the current adhesion problem. The influence of extractives on crosslinking was determined by Attenuated Total Reflection-Fourier Transform Infrared Spectrometer (ATR-FTIR) and on the rheological behavior in terms of gel point and storage modulus. Therefore, 2C PUR was mixed with 10% of eight common wood extractives separately. Furthermore, the mechanical properties of beech wood (Fagus sylvatica L.) bonded with extractive enriched adhesive were tested by means of tensile shear strength tests and evaluation of wood failure. These results of ATR-FTIR clearly show that the majority of crosslinking was terminated after 12 hr. Acetic acid and linoleic acid expedited the isocyanate conversion during the first 2.5 hr. The curing in terms of gel point and storage modulus of 2C PUR was accelerated by starch, gallic acid, linoleic acid, and acetic acid. Heptanal, pentanal, 3-carene, and limonene decelerated the curing. All extractives lowered the storage modulus determined after 12 hr. The bonding of beech wood with extractive–adhesive blends showed a slight decrease of the mechanical properties, with the exception of a marginal increase in the case of linoleic acid and pentanal.

In summary, it can be said that 2C PUR is sensitive to the influence of wood extractives and can therefore be partly held responsible for adhesion problems occurring when extractives in surface-wide and higher contents are available.     

Cure kinetics of aqueous phenol‐formaldehyde resins used for oriented strandboard manufacturing: Effect of wood flour

The effect of wood flour on the cure kinetics of commercial phenol‐formaldehyde resins used as oriented strandboard face and core adhesives was studied using differential scanning calorimetry. The wood flour did not change the cure mechanism of the face resin, but lowered its cure temperature and activation energy and increased its cure reaction order. For the core resin (CR), the wood flour lowered the onset cure temperature, and caused separation of the addition and condensation reactions involved in curing of CR. Compared with neat CR, the addition reaction of CR/wood mixture also followed an nth‐order reaction mechanism but with a lower reaction order, while the condensation was changed from an autocatalytic reaction to an nth‐order one. The addition reaction happened at temperatures lower than 90°C, and the condensation reaction was dominant at temperatures higher than 110°C. The proposed models fitted the experimental data well. Relationships among cure reaction conversion (cure degree), cure temperature, and cure time were predicted. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3774–3781, 2006     

Phenolic resin adhesives based on chestnut (Castanea sativa) hydrolysable tannins

Chestnut hydrolysable tannins are phenolic materials that have been considered too unreactive to compete in the phenolic resin adhesives market for exterior boards for the building industry. However, an article in 1973 describing 3?years industrial application of chestnut hydrolysable tannins during the first oil crisis indicated that this was not the case. We have extended this old work by using superior phenolic resins formulations and producing phenol–formaldehyde–chestnut tannin adhesives where a substitution of up to 80% of the phenol is possible with remarkably good results. The reactions involved were clarified by ¹³C NMR and MALDI-TOF mass spectrometry.     

Phenol–formaldehyde resin curing and bonding in steam-injection pressing. I. Resin synthesis,characterization, and cure behavior

Two different phenol–formaldehyde (PF) resole resins are serving as models in a study aimed at establishing the effects of moisture, temperature, pressure, and time on resin cure and bonding during the pressing of wood flakeboard. This phase of the program had two goals: first, to characterize the two resins in terms of their structure and chemistry during synthesis, aging, and cure—using viscosity measurement, gel permeation chromatography (GPC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and dynamic mechanical analysis (DMA); second, to make a preliminary evaluation of the utility of DSC, FTIR, and DMA for measuring the degree of resin cure. The two resins differed significantly in relative amounts of hydroxymethyl groups and methylene linkages (NMR), in molecular weight and its distribution (GPC), and in reaction rate (as measured by viscosity, DSC, FTIR, or DMA). The degree of cure developed during constant heating rate DSC scans was calculated for a series of maximum DSC temperatures from both the loss in hydroxymethyl groups (FTIR) and the decrease in available exothermic heat (DSC). Agreement between the two methods was quite good, considering the inherent difficulties in quantifying infrared data. For comparison, the degree of cure developed during constant heating rate DMA scans was calculated for a series of maximum DMA temperatures from both the increase in storage modulus (DMA) and the decrease in exothermic heat (DSC after rewetting). Samples that apparently achieved complete cure in the DMA still exhibited significant residual cure potential in the DSC. We attribute the lower apparent cure in the DMA to loss of moisture from samples during the DMA scan, with consequent loss in plasticization and molecular mobility.     

The chemistry and development of tannin/urea–formaldehyde condensates for exterior wood adhesives

Novolak-like materials were prepared by condensation of urea–formaldehyde resins with resorcinol and/or resorcinolic A-rings of polyflavonoids such as condensed tannins. The copolymers formed were used as thermosetting and cold-setting exterior-grade wood adhesives. Condensation of tannins with small amounts of urea–formaldehyde resins can prevent the water deterioration normally experienced by the latter resins. Conversely, urea–formaldehyde resins improve crosslinking and strength of wood tannin–formaldehyde networks.     

Synthesis and properties of polyurethane resins based on liquefied wood

Three polyurethane resins were synthesized from liquefied wood and three diisocyanates, i.e., TDI, IPDI, and HDI. The liquefied wood was obtained by the liquefaction of benzylated wood wastes using Dibasic esters (DBE) as solvent with hydrochloric acid as catalyst for 3 h, at 80°C. The thermal stability and microphase morphology of polyurethane films were investigated by TG, DSC, WAXD, and SEM methods. The experimental results indicated that polyurethane resins from liquefied wood had higher thermal stability than traditional ones, and the special structure and the difference of chemical structure of diisocyanates resulted in the crytallinity and microphase separation of obtained polyurethanes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 351–356, 2004     

Induced accelerated autocondensation of polyflavonoid tannins for phenolic polycondensates. II. Cellulose effect and application

Polyflavonoid tannin autocondensation was found to be facilitated by the reaction occurring on cellulose and lignocellulosic substrates. Although the mechanism of polyflavonoid autocondensation induced by cellulose differs from that induced by the action of Lewis acids, the subsequent reaction of autocondensation appears to be similar. The determining step of tannin rearrangement pathways under alkaline conditions in cellulose-induced highertemperature autocondensation is the favoring of the heterocycle pyran ring opening over the normal interflavonoid bond cleavage and catechinic acid rearrangement. This is caused by relevant bond weakening and easier cleavage induced by strong attractive forces between flavonoid and cellulosic substrate. Applied bonding of cellulosic substrates by polyflavonoid tannin autocondensation reaction appear to be feasible and to occur as predicted from theoretical predictions. © 1995 John Wiley & Sons, Inc.     

Physicomechanical and thermal properties of moldings made from liquefied wood‐based novolak PF resins under various hot‐pressing conditions

The wood powder of Cryptomeria japonica (Japanese cedar) was liquefied in phenol, with H₂SO₄ and HCl as a catalyst. The liquefied wood was used to prepare the liquefied wood‐based novolak phenol formaldehyde (PF) resins by reacting with formalin. Furthermore, novolak PF resins were mixed with wood flour, hexamethylenetetramine, zinc stearate as filler, curing agent, and lubricating agent, respectively, and hot‐pressed under 180 or 200°C for 5 or 10 min to manufacture moldings. The results showed that physicomechanical properties of moldings were influenced by the hot‐pressing condition. The molding made with hot‐pressing temperature of 200°C for 10 min had a higher curing degree, dimensional stability, and internal bonding strength. The thermal analysis indicated that using a hot‐pressing temperature of 180°C was not sufficient for the liquefied wood‐based novolak PF resins to completely cure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ionic polycondensation effects on the radical autocondensation of polyflavonoid tannins: An ESR study

An electron spin resonance (ESR) study of the presence or lack of interference by ionic hardening mechanisms and ionic coreactants on the polyflavonoid tannin radical autocondensation reaction indicated that in certain cases hardening by ionic coreactants can be coupled with the simultaneous hardening of the tannin by radical autocondensation. Some coreactants tend to depress the tannin radical autocondensation while still leaving a small contribution of this reaction to the formation of the final crosslinked network. Other coreactants instead appear to enhance formation of the final network by synergy between ionic and radical mechanisms, while still others do not show any interference between the two types of reaction. Mechanisms describing the interaction between the two reactions are proposed and discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2623–2633, 1997     

Synthesis and characterization of phenolic novolacs modified by chestnut and mimosa tannin extracts

The possibility of reacting chestnut and mimosa tannins with the intermediates of the synthesis reaction for phenolic novolacs under acid conditions has been proved using differential scanning calorimetry (DSC). The amount of intermediate compounds and the percentage of free phenol and formaldehyde in the reaction mixture is decisive for the determination of the stage in which the addition of tannin is suitable. Synthesis of novolac resins modified with 14 wt % mimosa tannin extract or with several percentages (until 40 wt %) of chestnut tannin have been performed. The reaction pathways have been investigated by DSC, fourier transformed infrared spectroscopy and gel permeation chromatography. Ester groups of chestnut tannin result in a reaction pathway different from the one for mimosa‐modified resins and nonmodified resins. Preliminary studies of curing reactions of synthesized resins with hexamethylenetetramine indicate that the cure of modified‐resins is even more favorable than the one for nonmodified resins. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4412–4419, 2006     

Structural silicone sealant modelling for wood frames: influence of adhesion on bonding strength

This paper provides a quantitative measure of the bonding strength of structural silicone sealant applied to wood–double glazing glass joints for wood frame applications. The joint strength is assessed by tensile and shear experimental tests. The paper aims to characterize the joint behaviour through experimental tests in order to implement and validate a finite element (FE) model of the joint that can be used for whole frame characterization. The experimental tests are carried out on three wood species (Meranti, White Oak and Pine), and two different FE models of the wood–silicone–glass joint are implemented: the first basic model assumes the modulus of elasticity and modulus of rupture of the silicone as provided by the manufacturer, while the second model assumes the results of the experimental tensile tests. The results of the first FE model do not fit well with the tests carried out, while the second FE model proves to be more reliable and is validated by experimental results. The results report that, when modelling wood–double glazing glass joints by FE methods, the equivalent structural sealant modulus of elasticity assigned in the model should be about 50% lower than what is declared by the manufacturer. This result can be useful when modelling whole wood frames and dimensioning sealant depth and thickness in wood–glass joint applications.     

Mechanical characterization of industrial particleboard panels glued with cornstarch–mimosa tannin–urea formaldehyde resins

The aim of this work was to validate the utility and performance of optimal laboratory cornstarch–mimosa tannin-based resins in the industrial particleboard production. In this way, the cornstarch and mimosa tannin was introduced in the classic adhesive formulation in order to supply a part of urea-formaldehyde (UF). Our results show that industrial particleboard panels (8.2?m?×?1.85?m?×?19?mm) bonded with optimal cornstarch–mimosa tannin–UF (10:4:86; mass ratio) resins exhibited comparable mechanical properties to those of boards bonded with commercial UF resins and largely satisfied the exigencies of European norms EN 312. The formaldehyde emission levels obtained from panels bonded with cornstarch–mimosa tannin–UF were lower to those obtained from panels bonded with control UF. Finally, the addition of cornstarch and mimosa tannin improves markedly the water resistance of UF resins.     

CHT and TTT curing diagrams of polyflavonoid tannin resins

TTT and CHT curing diagrams for tannin-based adhesives were built by thermomechanical analysis (TMA) by following the in situ hardening directly in a wood joint, and the curve trends observed were similar to those previously observed for synthetic polycondensation resins on lignocellulosic substrates. Of the parameters that most influence the relative position of vitrification and gel curves on the diagrams (i.e., where the influence has been quantified), chief among them is the reactivity of the tannin with formaldehyde and any factor influencing it: thus, the inherent higher reactivity of the A-ring of the tannin (such as in procyanidins versus prorobinetinidins) and the pH of the tannin solution. The percentage formaldehyde hardener has some influence in CHT diagrams, especially for the slower-reacting tannins, but practically no influence in TTT diagrams within the 4–10% formaldehyde range used. As in the case of synthetic polycondensation adhesive resins, regression equations relating the internal bond strength of a wood particleboard, prepared under controlled conditions, with the inverse of the minimum deflection, obtained by constant heating rate TMA of a wood joint during resin cure, have been obtained for the two types of tannins of lower reactivity (profisetinidins/prorobinetinidins) but not for the faster-reacting procyanidin and prodelphinidin tannins. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3220–3230, 2001     

木质纤维的冷冻活化及其制备无胶板材

利用氢氧化钠-聚乙二醇-尿素混合溶液对木质纤维进行冷冻活化处理,然后制备无胶纤维板,通过对比无胶胶合纤维板力学性能,确定木质纤维较佳冷冻活化工艺,并利用傅里叶变换红外光谱、X射线衍射分析、差式扫描量热分析、热重分析、X射线光电子能谱分析对木质纤维的冷冻活化效果进行表征。研究结果表明:木质纤维较佳冷冻活化工艺为氢氧化钠、聚乙二醇、尿素的质量比7∶4.2∶12,活化剂质量(以氢氧化钠与尿素的总质量计)与木质纤维的质量比1∶12,冷冻温度-15℃,冷冻时间45 min;以此工艺活化处理的木质纤维为原料,所制备纤维板的吸水厚度膨胀率、内结合强度、静曲强度、弹性模量分别优于GB/T 11718—2009《中密度纤维板》性能要求(各指标数值分别提升了45%、238%、177%和129%);冷冻活化处理会破坏木质纤维中纤维素间的氢键,提高羟基的反应活性并增加活性羟基的数量,在扩张纤维素晶格的同时产生新的结晶并且降低木质纤维的热稳定性。     

Curing of low level melamine‐modified urea‐formaldehyde particleboard binder resins studied with dynamic mechanical analysis (DMA)

Effects of resin formulation, catalyst, and curing temperature were studied for particleboard binder‐type urea‐formaldehyde (UF) and 6 ～ 12% melamine‐modified urea‐melamine‐formaldehyde (UMF) resins using the dynamic mechanical analysis method at 125 ～ 160°C. In general, the UF and UMF resins gelled and, after a relatively long low modulus period, rapidly vitrified. The gel times shortened as the catalyst level and resin mix time increased. The cure slope of the vitrification stage decreased as the catalyst mix time increased, perhaps because of the deleterious effects of polymer advancements incurred before curing. For UMF resins, the higher extent of polymerization effected for UF base resin in resin synthesis increased the cure slope of vitrification. The cure times taken to reach the vitrification were longer for UMF resins than UF resins and increased with increased melamine levels. The thermal stability and rigidity of cured UMF resins were higher than those of UF resins and also higher for resins with higher melamine levels, to indicate the possibility of bonding particleboard with improved bond strength and lower formaldehyde emission. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 377–389, 2005