Properties of plywood panels bonded with ionic liquid-modified lignin–phenol–formaldehyde resin

The aim of this research was to investigate the physical and mechanical properties of plywood panels bonded with ionic liquid-modified lignin–phenol–formaldehyde (LPF) resin. For this purpose, soda bagasse lignin was modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid, and then, various contents of modified lignins (10, 15, and 20 wt%) were added as a substitute of phenol in phenol–formaldehyde (PF) resin synthesis. The properties of the synthesized resin were compared with those of a control PF resin. The changes in curing behavior of the resins prepared were analyzed by differential scanning calorimetry (DSC). The physical properties of the resins prepared, as well as the water absorption, thickness swelling, shear strength, and formaldehyde emission of the plywood panels bonded with these adhesives, were measured according to standard methods. DSC analysis indicated that in comparison with PF resins, curing of the LPF resin occurred at lower temperatures. The physical properties of the synthesized resins indicated that viscosity and solid content increased, while gel time and density decreased by addition of treated lignin to the PF resin. Although the panels containing resins with modified lignin yielded low formaldehyde emission, their dimensional stability was worse than those bonded with a commercial PF adhesive. The plywood prepared using IL-treated lignin PF resins has shear strength, which satisfy the requirements of the relevant standards specifications and significantly better than that of panels prepared with the control PF resin. The mechanical properties of the panels could be significantly enhanced with increased percentage of treated lignin content from 0 to 20 wt%.     

Improving the properties of ionic liquid-treated lignin-urea-formaldehyde resins by a small addition of isocyanate for wood adhesive

The aim of this research was to investigate the effect of polymeric 4, 4 diphenyl methane diisocyanate (pMDI) on the physical and mechanical properties of plywood panels bonded with an ionic liquid (IL)-treated lignin-urea-formaldehyde resin. Soda lignin modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) IL was added to a urea formaldehyde (UF) resin during resin synthesis to prepare a lignin-urea-formaldehyde (LUF) resin. pMDI at various contents (2, 4, and 6% on resin solids) was then added to prepare a LUF resin. The thermal and physicochemical properties of the resins prepared as well as the water absorption, shear strength, and formaldehyde emission of the plywood panels bonded with them were measured according to standard methods. DSC analysis indicated that the addition of pMDI decreases the gel onset and curing temperatures of the LUF resin. According to the results obtained, the addition of pMDI significantly increased the viscosity and solid content and accelerated the gelation time of LUF resins. Based on the findings of this research, the addition of pMDI dramatically improves the performance of LUF resins as a new adhesive for wood-based panels. The LUF resins with isocyanate added yielded panels presenting lower formaldehyde emission and lower water absorption content when compared to those bonded with the control LUF resins. Greater dry and wet shear strength can be obtained by a small addition of pMDI to LUF resins.     

The effect of soda bagasse lignin modified by ionic liquids on properties of the urea–formaldehyde resin as a wood adhesive

The aim of this research was to investigate the influence of lignin modified by ionic liquids on physical and mechanical properties of plywood panels bonded with the urea–formaldehyde (UF) resin. For this purpose, soda bagasse lignin was modified by the 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid and then the various contents of unmodified and modified lignins (10, 15, and 20%) were added at pH=7 instead of second urea during the UF resin synthesis. The physicochemical properties of the prepared resins as well as the water absorption, shear strength, and formaldehyde emission of the plywood panels made with these adhesives were measured according to standard methods. According to Fourier Transform Infrared (FTIR) Spectrometry, by treatment of lignin, the C=O, C–C, and C–H bonds decrease while the content of the C–N bond dramatically increases. Based on the finding of this research, the performance of soda bagasse lignin in UF resins dramatically improves by modification by ILs; as the resins with modified lignin yielded lower formaldehyde emission and water absorption when compared to those made from unmodified lignin and commercial UF adhesives, respectively. The shear strength as well as wood failure percentages are lower for the panels produced with modified lignin than for the panels produced with UF resins alone.     

Reduction of Formaldehyde Emission from Particleboard by Phenolated Kraft Lignin

The aim of this study was the reduction of formaldehyde emission from particleboard by phenolated Kraft lignin. For this purpose, the lignin was extracted from black liquor and then modified by phenolation. During the urea formaldehyde (UF) resin synthesis different proportions of unmodified and phenolated Kraft lignins (10%, 15%, and 20%) were added at pH = 7 instead of the second urea. Physicochemical properties and structural changes of resins so prepared, as well as the internal bond (IB) strength and formaldehyde emission associated with the panels bonded with them were measured according to standard methods. The Fourier transform infrared (FTIR) analysis of lignin indicated that the content of O–H bonds increased in phenolated lignin while the aliphatic ethers C–O bonds decreased markedly in the modified lignin. Since both synthesis of UF resins and lignin phenolation are carried out under acid conditions, phenolation is an interesting way of modifying lignin for use in wood adhesive. The panels bonded with these resins showed significantly lower formaldehyde emission compared to commercial UF adhesives. The UF resin with 20% phenolated lignin exhibited less formaldehyde release without significant differences in internal bond strength and physicochemical properties compared to an unmodified UF resin. XRD analysis results indicated that addition of phenolated lignin decreased the crystallinity of the hardened UF resins.     

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.     

低甲醛释放量人造板用改性脲醛树脂制备及应用研究

为了降低脲醛树脂的游离甲醛含量及其胶接制品的甲醛释放量,本研究在脲醛树脂合成过程中加入改性剂代替部分甲醛,通过尿素-甲醛-改性剂发生共缩聚反应,合成了改性脲醛树脂。研究了改性剂取代甲醛的摩尔比对改性脲醛树脂固化速度、游离甲醛含量的影响,以及在不同的热压条件下,对胶接胶合板的胶合强度和甲醛释放量的影响。研究结果表明,改性剂的加入不仅能有效降低改性脲醛树脂的游离甲醛含量及其胶合板的甲醛释放量,还能提高胶合板的胶合强度和耐水性。     

Influence of nanoclay on urea–glyoxalated lignin–formaldehyde resins for wood adhesive

In this research, the influence of nanoclay on urea–glyoxalated lignin–formaldehyde (GLUF) resin properties has been investigated. To prepare the GLUF resin, glyoxalated soda baggase lignin (15 wt%) was added as an alternative for the second urea during the UF resin synthesis. The prepared GLUF resin was mixed with the 0.5%, 1%, and 1.5% nanoclay by mechanically stirring for 5 min at room temperature. The physicochemical properties of the prepared resins were measured according to standard methods. Then the resins were used in particleboard production and the physical and mechanical properties of the manufactured panels were determined. Finally, from the results obtained, the best prepared resin was selected and its properties were analyzed by differential scanning calorimetry (DSC), Fourier transform infrared spectrometry (FTIR), and X-ray diffractometry (XRD). Generally the results indicated that the addition of sodium-montmorillonite (NaMMT) up to 1.5% appears to improve the performance of GLUF resins in particleboards. The results also showed that nanoclays improved mechanical strength (modulus of elasticity (MOE), Modulus of Rupture (MOR), and internal bond (IB) strength) of the panels bonded with GLUF resins. The panels containing GLUF resin and nanoclay yielded lower formaldehyde emission as well as water absorption content than those made from the neat GLUF resins. XRD characterization indicated that NaMMT only intercalated when mixed with GLUF resin. Based on DSC results, the addition of NaMMT could accelerate the curing of GLUF resins. The enthalpy of the cure reaction (ΔH) of GLUF resin containing NaMMT was increased compared with neat GLUF resin. Also the results of FTIR analysis indicated that addition of NaMMT change the GLUF resins structures.     

尤戎(Uron)树脂及其用法对脲醛树脂性能的影响

以不同工艺制备了三种含尤戎结构的脲醛树脂(Uron树脂),通过其与普通脲醛树脂的混合制得多种混合脲醛树脂。研究了Uron树脂及其使用方法对降低脲醛树脂胶粘剂游离甲醛含量及胶接胶合板甲醛释放量的作用与效果。结果表明:1)三种不同摩尔比的Uron树脂对脲醛树脂游离甲醛含量及胶接胶合板甲醛释放量都有明显的降低作用,游离甲醛含量最多可降低43％,甲醛释放量最多可降低61％;2)Uron树脂的添加量在10％-20％时对胶合强度的提高有利,强度最大可提高29％;3)低摩尔比Uron树脂对脲醛树脂的改性效果优于高摩尔比Uron树脂。     

Jute felt composite from lignin modified phenolic resin

Raw and dewaxed jute felt composites were prepared with resol and lignin modified phenol formaldehyde resin. Four different types of lignin modified resins were used by replacing phenol with lignin. The lignin modified resins were prepared from purified lignin obtained from paper industry waste black liquor. To investigate bonding between jute and resin, IR spectroscopy of jute felts and composites was carried out. The thermal stability of the composites was assessed by DSC and TGA. It was found that the lignin resin jute composite is thermally more stable than resol composite. XRD of jute felt and composite shows that the crystallinity of the jute fiber increases after composite preparation. The lignin resin composites were tested for water absorption and thickness swelling, and it was found that the results are comparable with those of resol jute composite. Composites prepared from lignin phenol formaldehyde resin with 50% phenol replacement has shown 75% tensile strength retention to that of pure resol jute composite.     

Kraft lignin in phenol formaldehyde resin. Part 1. Partial replacement of phenol by kraft lignin in phenol formaldehyde adhesives for plywood

The objective of this study was to investigate the potential for partially replacing phenol with kraft lignin in the phenol formaldehyde (PF) resin designed for application as an adhesive in the production of plywood. The kraft lignin, considered to be an environmentally friendly alternative to phenol, was precipitated from black liquor recovered from kraft pulping of softwood. Kraft lignin phenol formaldehyde (KLPF) resin was prepared in a one-step preparation with different additions of lignin. Replacing 50 wt% of the phenol with kraft lignin (50KLPF) was, under the conditions used, considered to be optimal with respect to resin viscosity, storage stability, and bonding ability. The resin consists of an integrated kraft lignin-phenol network. The hot-pressing time in the plywood manufacturing had to be increased by approximately 30% at 150°C for the 50KLPF resin compared with that normally used for PF resin, in order to comply with plywood standard demands. The mechanical properties of test samples made from KLPF resins were equal to or better than those of test samples made from PF resin only.     

含木质素的发酵残渣在脲醛树脂中的应用研究

对秸秆发酵乙醇残渣进行磺甲基化改性,可有效提高残渣中改性木质素的反应活性;然后将磺甲基化改性发酵残渣用于脲醛树脂(UF)胶粘剂配方中,制备木材用改性UF胶粘剂。结果表明:当m(发酵残渣)∶m(甲醛)=10∶1、m(发酵残渣)∶m(亚硫酸钠)=5∶1和磺甲基化改性发酵残渣替代率为20%时,相应胶合板的各项性能都达到GB/T 14074—2006标准中的指标要求,其水煮3 h后的胶合强度≥0.7 MPa;该改性UF胶粘剂具有制备工艺简单、游离甲醛含量较低等优点,其应用前景良好。     

Influence of glyoxal on curing of urea-formaldehyde resins

In the present paper, the effect of glyoxal on the gel formation within the adhesive systems based on urea-formaldehyde (UF) resins is shown. A reduction of formaldehyde content in wood-based panels by decreasing the formaldehyde/urea molar ratio in the UF resins leads to increasing of the UF resin gel time, and impairing the qualitative characteristics of the UF-based wood materials. Glyoxal is shown to speed up the crosslinking of the macromolecules as well as significant reduction of gel time of adhesive composition. The first reason is the result of reaction between glyoxal and ammonium ion leading to protons releasing. Another reason is that glyoxal and its interaction products react with macromolecules of the UF resin forming a three-dimension cross-linked structure. The gel time and the pot life of the UF resin are measured by the oscillatory viscometer. Formation of the UF cross-linked resin structure with glyoxal and a curing catalyst (ammonium sulfate) is studied using dispersion Raman scattering spectroscopy. Particleboards (PB) are produced using different amount of glyoxal and formaldehyde/urea molar ratio in the UF resin. The properties are evaluated according to the European Standards and include density, internal bond, thickness swelling moisture content and formaldehyde content.     

Influence of acrylamide copolymerization of urea–formaldehyde resin adhesives to their chemical structure and performance

To lower the formaldehyde emission of wood‐based composite panels bonded with urea–formaldehyde (UF) resin adhesive, this study investigated the influence of acrylamide copolymerization of UF resin adhesives to their chemical structure and performance such as formaldehyde emission, adhesion strength, and mechanical properties of plywood. The acrylamide‐copolymerized UF resin adhesives dramatically reduced the formaldehyde emission of plywood. The ¹³C‐NMR spectra indicated that the acrylamide has been copolymerized by reacting with either methylene glycol remained or methylol group of UF resin, which subsequently contributed in lowering the formaldehyde emission. In addition, an optimum level for the acrylamide for the copolymerization of UF resin adhesives was determined as 1%, when the formaldehyde emission and adhesion strength of plywood were taken into consideration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Use of organosolv lignin in phenol-formaldehyde resins for particleboard production: II. Particleboard production and properties

The objective of this work was to demonstrate the utility of lignin-based resins designed for application as an adhesive in the production of particleboard. Bond qualities of lignin-phenol-formaldehyde resins, phenolated-lignin-formaldehyde resins and commercial phenol-formaldehyde (PF-com) resin were assessed by using an automatic bonding evaluation system, prior to production of particleboards. In order to evaluate the quality of lignin-based resins, particleboards were produced and physical and mechanical properties were investigated. These physical properties included internal bond, modules of rupture and modulus of elasticity. Thickness swell and water absorption properties of particleboards bonded with lignin-based resins were also determined. The lignin-based resins have been reported previously in Part I of this study. The results showed that particleboards bonded with phenolated-lignin formaldehyde resins (up to 30% lignin content) exhibited similar physical and mechanical properties when compared to particleboards bonded with PF-com. The work has indicated that phenolated-lignin formaldehyde resins (up to 30% substitution level) can be used successfully as a wood adhesive for constructing particleboard. The performance of these panels is comparable to those of boards made using PF-com resin.     

Reduction of formaldehyde emission from plywood

The aim of this work is to evaluate performances of tannin-based resins designed as adhesive in the plywood production. For this purpose, a part of phenol formaldehyde (PF) and melamine formaldehyde (MF) in the classic adhesive formulation was replaced by tannin. The physical properties of the formulated resins (rheological characterization, etc.) were measured. In order to analyze the mechanical performance of tannin-based resins, plywood panels were produced and the mechanical properties including tensile strength wood failure and three-point bending strength were investigated. The performance of these panels is comparable to those of plywood panels made by commercial PF and MF. The results showed that the plywood panels bonded with tannin–PF (PFT) and tannin–MF (MFT) resins exhibited better mechanical properties in comparison to the plywood panels made of commercials PF and MF. The introduction of small properties of tannin in PF and MF resins contribute to the improvement of the water performance of these adhesives. The formaldehyde emission levels obtained from panels bonded with tannin-based resins were lower than those obtained from panels bonded with control PF and MF. Although there are no actual reaction at all between PF, MF, and tannin, addition of tannin significantly improves the water resistance of PF and MF resins. This is a novel finding that manifests the possibility of replacing a convention PF and MF resins by tannin. Modified adhesive is one of the goals in the plywood production without changing any of their production conditions with improvement to their overall properties.     

Modification of urea-formaldehyde resin adhesives with blocked isocyanates using sodium bisulfite

Polymeric 4-4 diphenyl methane diisocyanate (pMDI) was blocked with an aqueous sodium bisulfite solution to obtain water-dispersible blocked pMDI (B-pMDI) resin with different HSO₃/–NCO mole ratios for the modification of urea-formaldehyde (UF) resin. Fourier transform infrared (FTIR) spectra of the B-pMDI resin clearly showed that all isocyanate groups of the pMDI resin were successfully blocked by sodium bisulfite. As the HSO₃/–NCO mole ratio increased, the de-blocking temperature of the B-pMDI resin also increased. Two addition levels (1% and 3%) of the B-pMDI resin with different HSO₃/–NCO mole ratios were mixed with UF resins and used as an adhesive for plywood. The gel time of the UF/B-pMDI resins decreased to a minimum at a mole ratio of 0.9 and then increased with the HSO₃/–NCO mole ratio, and was consistent with the peak temperature (Tp). However, as the HSO₃/–NCO mole ratio increased, the viscosity of the modified UF resins by 1% B-pMDI resin addition slightly increased, whereas those of modified resins with 3% B-pMDI resin addition rapidly increased. The adhesion strengths of plywood bonded with the hybrid resins were greater for 1% B-pMDI resin addition than for 3% B-pMDI resin addition. Formaldehyde emission of plywood bonded with the UF/B-pMDI resins significantly decreased up to 34% by the addition of B-pMDI resin at a mole ratio of 1.8. These results suggest that the modification of UF resins by mixing with water-dispersible B-pMDI resin can be a method for improving the water resistance and formaldehyde emission of UF resins for wood-based composites.     

Hydrolytic stability of cured urea‐formaldehyde resins modified by additives

Urea‐formaldehyde (UF) resins are prone to hydrolysis that results in low‐moisture resistance and subsequent formaldehyde emission from UF resin‐bonded wood panels. This study was conducted to investigate hydrolytic stability of modified UF resins as a way of lowering the formaldehyde emission of cured UF resin. Neat UF resins with three different formaldehyde/urea (F/U) mole ratios (1.4, 1.2, and 1.0) were modified, after resin synthesis, by adding four additives such as sodium hydrosulfite, sodium bisulfite, acrylamide, and polymeric 4,4′‐diphenylmethane diisocyanate (pMDI). All additives were added to UF resins with three different F/U mole ratios before curing the resin. The hydrolytic stability of UF resins was determined by measuring the mass loss and liberated formaldehyde concentration of cured and modified UF resins after acid hydrolysis. Modified UF resins of lower F/U mole ratios of 1.0 and 1.2 showed better hydrolytic stability than the one of higher F/U mole ratio of 1.4, except the modified UF resins with pMDI. The hydrolytic stability of modified UF resins by sulfur compounds (sodium bisulfate and sodium hydrosulfite) decreased with an increase in their level. However, both acrylamide and pMDI were much more effective than two sulfur compounds in terms of hydrolytic stability of modified UF resins. These results indicated that modified UF resin of the F/U mole ratio of 1.2 by adding acrylamide was the most effective in improving the hydrolytic stability of UF resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

木质素在脲醛树脂胶粘剂中的应用

为解决脲醛树脂(UF)胶粘剂中游离甲醛含量偏高等问题,首先确定了n[甲醛(F)]∶n[尿素(U)]的合适比例,然后以羟甲基化木质素作为UF的改性剂,制备木质素改性UF胶粘剂。研究了木质素的种类及用量对UF各项性能的影响。结果表明:UF中游离甲醛含量随n(F)∶n(U)比例增加而增大;在UF改性过程中,硝酸木质素对游离甲醛的捕捉能力优于硫酸木质素,当w(硝酸木质素)=30%(相对于尿素总质量而言)时,游离甲醛含量(0.126%)相对最低;木质素加入的同时还有助于提高改性UF胶粘剂的胶接强度和耐水性。     

DSC法研究乙二醛-尿素树脂的固化性能

为从源头上降低UF树脂及其胶合板材的甲醛释放对环境和人体健康所造成的危害,选用乙二醛(G)取代甲醛(F)与尿素(U)反应,制备乙二醛-尿素(GU)树脂。用差示扫描量热分析(DSC)方法研究了原料物质的量比、反应pH、反应时间、反应温度、pH调节剂对所合成GU树脂固化性能的影响规律;并用不同原料物质的量比的GU树脂制备刨花板并测定了其各项性能。结果表明,GU树脂的较优合成条件为:在弱酸性条件下,乙二醛与尿素物质的量比(G/U)=1.2∶0～1.4∶1.0,反应温度70～80℃,反应时间3h;此条件下合成的GU树脂胶合的刨花板内结合强度IB达到0.44MPa、弹性模量MOE达2298MPa、静曲强度MOR为10.5 MPa,且无甲醛释放。     

Properties of phenol‐formaldehyde resins prepared from phenol‐liquefied lignin

In this study, alkaline lignin (AL), dealkaline lignin (DAL), and lignin sulfonate (SL) were liquefied in phenol with sulfuric acid (H₂SO₄) or hydrochloric acid (HCl) as the catalyst. The phenol‐liquefied lignins were used as raw materials to prepare resol‐type phenol‐formaldehyde resins (PF) by reacting with formalin under alkaline conditions. The results show that phenol‐liquefied lignin‐based PF resins had shorter gel time at 135°C and had lower exothermic peak temperature during DSC heat‐scanning than that of normal PF resin. The thermo‐degradation of cured phenol‐liquefied lignin‐based PF resins was divided into four temperature regions, similar to the normal PF resin. When phenol‐liquefied lignin‐based PF resins were used for manufacturing plywood, most of them had the dry, warm water soaked, and repetitive boiling water soaked bonding strength fitting in the request of CNS 1349 standard for Type 1 plywood. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011