Synthesis of wood‐based epoxy resins and their mechanical and adhesive properties

Wood‐based epoxy resins were synthesized from resorcinol‐liquefied wood. Wood was first liquefied in the presence of resorcinol with or without a sulfuric acid catalyst at high temperature. Because of the hydroxyl groups, the resorcinol‐liquefied wood was considered as a precursor for synthesizing wood‐based epoxy resin. Namely, the phenolic OH groups of the liquefied wood reacted with epichlorohydrin under alkali condition. By the glycidyl etherification, epoxy functionality was introduced to the liquefied wood. The epoxy functionality of the resins was controlled by the concentration of phenolic OH groups in the liquefied wood, which would be a dominant factor for crosslink density and properties of the cured epoxy resins. The flexural strength (150–180 MPa) and the modulus of elasticity (3.2 GPa) of the highly crosslinked wood‐based epoxy resin were equivalent to those of the commercially available epoxy resin, diglycidyl ether of bisphenol A (DGEBA). Also, the shear adhesive strength of the wood‐based epoxy resin was higher than that of DGEBA when plywood was used as the adhesive substrates. The mechanical and adhesive properties suggested that the wood‐based epoxy resins would be well suited for matrix resins of natural plant‐fiber reinforced composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2285–2292, 2006     

Synthesis and properties of copolymer epoxy resins prepared from copolymerization of bisphenol A,epichlorohydrin, and liquefied Dendrocalamus latiflorus

Dendrocalamus latiflorus Munro (ma bamboo) was liquefied in phenol and polyhydric alcohol (polyethylene glycol/glycerol cosolvent) with H₂SO₄ as catalyst. Liquefied bamboos reacted with bisphenol A and epichlorohydrin were then employed to prepare copolymer epoxy resins. The curing property and thermal property of copolymer epoxy resins were investigated. The results showed that copolymer epoxy resins could cure at room temperature after the hardener was added, and its curing process was an exothermic reaction. Comparison showed that copolymer epoxy resins prepared with phenol‐liquefied bamboo as raw material had higher heat released than those prepared with polyhydric alcohol‐liquefied bamboo during curing. The DSC analysis showed that heat treatment could enhance the crosslinking of copolymer epoxy resins cured at room temperature. However, resins prepared with polyhydric alcohol‐liquefied bamboo had a lower glass transition temperature. The TGA analysis showed that resins prepared with phenol‐liquefied bamboo had better thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Bonding properties of epoxy resins containing two mesogenic groups

Liquid‐crystalline epoxy resins, with introduced aliphatic chains between two mesogenic groups, were synthesized and their adhesive bonding properties were compared to those of the bisphenol‐A–type epoxy resin and the liquid‐crystalline epoxy resin, previously reported. The bonding strength of the former resin system was higher than that of the two later systems. We suggest that the high bonding strength of the twin mesogenic epoxy resins, cured with an aromatic amine, was attributable to the large plastic deformation of the adhesive layer in the fracturing process. We also investigated the effects of the aliphatic chain length in the twin mesogenic epoxy resin on their dynamic mechanical and bonding properties. The bonding strength of the cured twin mesogenic epoxy resins increased with an increase in the aliphatic chain length. We suggest that the high bonding strength of the system introduced by the long aliphatic chain was attributable to the large plastic deformation of the adhesive layer because of the higher network mobility. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3721–3729, 2004     

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     

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     

Synthesis of liquefied corn barn-based epoxy resins and their thermodynamic properties

The liquefied corn barn-based epoxy resin (LCBER) was synthesized through the glycidyl etherification reaction from liquefied corn barn (LCB), which has groups of bound phenol, and epichlorohydrin under alkali conditions. The average molecular weights of LCB and LCBER in various liquefaction conditions were examined. The thermodynamic properties of thermosetting resin cured by polyamide-650 (PA-650) were evaluated. It was found that the macromolecular chain and epoxy function of the resins would be a dominant factor for crosslinking density and properties of the cured LCBER. The cured liquefied CB-based epoxy resin (LCBER-30) using the corresponding LCB at 30 min (LCB-30) as raw materials had much macromolecular exhibited higher glass-transition and decomposition temperatures at 5% weight loss (T_d), but worse shear strength in comparison with the other LCBER ones. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Physical properties of moldings from liquefied wood resins

The liquefied wood resins obtained by liquefying wood in the presence of phenol using phosphoric acid as a catalyst were applied to prepare the moldings by using hexamine as a hardener. The effects of the molding conditions and the moldings' compositions on flexural properties and water-sorption kinetics of the moldings were investigated. It was found that the liquefied wood resins had satisfactory and almost uniform curing reactivity, although they were composed of different kinds of wood components. The flexural properties of the liquefied wood moldings were enhanced with an increase in the amount of combined phenol within the liquefied wood and became comparable to those of the commercial novolak when the amounts of combined phenol were larger than 75%. Furthermore, it was also found that with an increase in the content of wood fillers the flexural properties of the liquefied wood moldings were enhanced more effectively than were the cases of the commercial novolak moldings, exhibiting that the liquefied wood resins could gain a greater reinforced effect from compounding with the wood fillers than did the commercial novolak resins, and the greater the amount of combined phenol, the higher the reinforcing performance of wood fillers. In addition, water-sorption measurements and the SEM observations of the moldings indicated that the liquefied wood resins had much greater hydrophilicity than that of the novolak and revealed a greater compatibility with wood fillers. © 1995 John Wiley & Sons, Inc.     

Phenol–formaldehyde‐type resins made from phenol‐liquefied wood for the bonding of particleboard

Liquefaction of southern pine wood in phenol in 30–40 : 70–60 weight ratios resulted in homogeneous liquefied materials, which were directly used to synthesize phenol–formaldehyde (PF)‐type resins. The synthesized resins showed good physical and handling properties: low viscosity, stability for storage and transportation, and resin applicable by a common sprayer. Particleboard panels bonded with the synthesized resins showed promising physical properties and significantly lower formaldehyde emission values than those bonded with the urea–formaldehyde resin control. One deficiency observed for the synthesized resins was lower internal bond values, which might be overcome the use of a hot‐stacking procedure. Overall, the process of wood liquefaction with limited amounts of phenol as a solvent was shown to have the potential of providing practical, low‐cost PF‐type resins with very low formaldehyde emission potentials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

含芳醚芴二胺/环氧树脂固化反应动力学及性能研究

以9,9-双[4-4-氨基苯氧基苯基]芴(BAOFL)作为固化剂,采用非等温DSC技术,研究了BAOFL/环氧树脂(E-51、TDE-85和芴基环氧树脂)体系的固化反应动力学,利用动态热机械分析仪(DMA)和热重分析仪(TGA)测试了固化树脂的力学性能和热稳定性。结果表明,固化反应活化能与环氧树脂和固化剂的结构密切相关,芳醚的引入提高了氨基与环氧基的反应性,固化树脂呈现出优良的热性能和力学性能,其玻璃化转变温度(T)达到206~248℃,贮能模量为2.54~2.94 GPa,初始热分解温度312~375℃,700℃g时的残炭率达到15.2%~31.7%。()     

Thermo-adjusted self-healing epoxy resins based on Diels–Alder dynamic chemical reaction

Micro-damage in materials could be repaired by endowing materials with self-healing performance. Herein, an epoxy resin with excellent self-healing performance grounded on thermo-reversible Diels–Alder dynamic chemical reaction was developed. Results showed that the bending strength and adhesive behavior of epoxy resin were influenced dramatically upon treatment with various temperatures. More importantly, damages created in epoxy resin could be repaired completely after suitable heat treatments. What is more, the healed epoxy resin exhibited much higher bending strength and adhesive performance than the pristine one did. The materials could be damaged and then repaired repeatedly. Meanwhile, the as-prepared self-healing epoxy resin exhibited excellent thermal reversibility and controllable adhesion. The thermo-adjusted self-healing performance endowed epoxy resin with recyclable and reusable performance. Therefore, the research made it possible of recycling waste epoxy resins.     

Synthesis and properties of cationic resins derived from aniline-modified epoxy resins and various amines

Aniline-modified epoxy resin which contains tertiary amine in the middle of the polymer chain was synthesized by the reaction of aniline and epoxy resin. The resulting aniline-modified epoxy resin and two commercial epoxy resins with different epoxy equivalent weights were reacted with 2-ethylhexanol-blocked toluene diisocyanate (2-EH-blocked TDI) to obtain thermally crosslinkable epoxy resins. These epoxy resins were subsequently reacted with various secondary amines and partially neutralized with acetic acid to give thermally crosslinkable cationic resins. The resulting cationic resins were dissolved in suitable solvents and mixed with deionized water to form emulsions. The crosslinking properties, emulsion, and electrodeposition properties of these resins were studied in some detail. The electro-deposition yields of the emulsions prepared from aniline-modified epoxy resins were higher than those of other emulsions. The crosslinked films prepared from aniline-modified epoxy resins were also glossier than those prepared from commercial epoxy resins. High deposition yield and high glossiness were the characteristic properties of the aniline-modified epoxy resins. Thermal properties were not affected by aniline-modified epoxy resins.     

Thermally reversible and self‐healing novolac epoxy resins based on Diels–Alder chemistry

The modified novolac epoxy resins with furan pendant groups were prepared by novolac epoxy resin and furfuryl alcohol and then crosslinked by bifunctional maleimide via Diels–Alder (DA) chemistry to obtain the thermally reversible and self‐healing novolac epoxy resins. The as‐prepared crosslinked novolac epoxy resins were characterized by FT‐IR, NMR, TGA, and DMA. The results indicate that the novel crosslinked novolac epoxy resins present higher storage modulus (2.37 GPa at 30°C) and excellent thermal stability (348°C at 5% mass loss). Furthermore, the thermal reversible and self‐healing properties were studied in detail by DSC, SEM, thermal re‐solution, and gel–solution–gel transition experiments. All the results reveal that the crosslinked novolac epoxy resins based on DA reaction can be used as smart material for the practical application of electronic packaging and structural materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42167.     

Fast advancement and hardening acceleration of low‐condensation alkaline PF resins by esters and copolymerized urea

Low‐condensation phenol‐formaldehyde (PF) resins coreacted under alkaline conditions with up to 42% molar urea on phenol during resin preparation yielded PUF resins capable of faster hardening times than equivalent pure PF resins prepared under identical conditions and presented better performance than the latter. The water resistance of the PUF resins prepared seemed comparable to pure PF resins when used as adhesives for wood particleboard. Part of the urea was found by ¹³C‐NMR to be copolymerized to yield the alkaline PUF resin; whereas, especially at the higher levels of urea addition, unreacted urea was still present in the resin. Increase of the initial formaldehyde to phenol molar ratio decreased considerably the proportion of unreacted urea and increased the proportion of PUF resin. A coreaction scheme of phenolic and aminoplastic methylol groups with reactive phenol and urea sites based on previous model compounds work has been proposed, copolymerized urea functioning as a prebranching molecule in the forming, hardened resin network. The PUF resins prepared were capable of further noticeable curing acceleration by addition of ester accelerators; namely, glycerol triacetate (triacetin), to reach gel times as fast as those characteristic of catalyzed aminoplastic resins, but at wet strength values characteristic of exterior PF resins. Synergy between the relative amounts of copolymerized urea and ester accelerator was very noticeable at the lower levels of the two parameters, but this effect decreased in intensity toward the higher percentages of urea and triacetin. ¹³C‐NMR assignements of the relevant peaks of the PUF resins are reported and compared with what has been reported in the literature for mixed, coreacted model compounds and pure PF and urea‐formaldehyde (UF) resins. The relative performance of the different PUF resins prepared was checked under different conditions by thermomechanical analysis (TMA) and by preparation of wood particleboard, and the capability of the accelerated PUF resins to achieve press times as fast as those of aminoplastic (UF and others) resins was confirmed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 359–378, 1999     

Biolignin™ based epoxy resins

Wheat straw Biolignin? was used as a substitute of bisphenol‐A in epoxy resin. Synthesis was carried out in alkaline aqueous media using polyethyleneglycol diglycidyl ether (PEGDGE) as epoxide agent. Structural study of Biolignin? and PEGDGE was performed by solid‐state ¹³C NMR and gel permeation chromatography, respectively, before epoxy resin synthesis. Biolignin? based epoxy resins were obtained with different ratios of Biolignin? : PEGDGE and their structures were analyzed by solid‐state ¹³C NMR. The crosslinking of PEGDGE with Biolignin? was highlighted in this study. Properties of Biolignin? based epoxy resins were analyzed by differential scanning calorimetry and dynamic load thermomechanical analysis as well as compared with those of a bisphenol‐A epoxy‐amine resin. Depending on the epoxy resin formulation, results confirmed the high potential of Biolignin? as a biosourced polyphenol used in epoxy resin applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Properties of compression‐molded plates made from wood powders impregnated with liquefied wood‐based novolak‐type phenol‐formaldehyde resins

Novolak‐type phenol‐formaldehyde (PF) resins with solution form were prepared by reacting phenol‐liquefied Cryptomeria japonica (Japanese cedar) wood with formalin in the presence of methanol. Wood powders of Albizzia falcate (Malacca albizzia) impregnated with these resins were air dried followed by an oven‐dried at 60°C. DSC analysis showed the PF resin existing in wood powders could be melted, and could be cured if hexamine was mixed and heated at high temperature. Compression‐molded plates made with PF resin impregnated woods had a high degree of curing reaction. However, compression‐molded plates hot‐pressed at 180°C for 8 min or 200°C for 5 min had better internal bonding strength and dimensional stability than others. Premixing hexamine with PF resin and impregnating into wood powders simultaneously could enhance the reactivity of PF resin, but it was not useful for improving the properties of compression‐molded plates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Heterocyclic‐based epoxy‐terminated structural adhesive. II. Curing,adhesive strength,and thermal stability

We studied the curing behavior of heterocyclic‐based epoxy‐terminated resins using diaminodiphenyl ether, diaminodiphenyl sulfone, benzophenone tetracarboxylicdianhydride, and the commercial hardener of Ciba‐Geigy's two‐pack Araldite as curing agents. The adhesive strength of the adhesives was measured by various ASTM methods such as lap‐shear, peel, and cohesive tests on metal–metal, wood–wood, and wood–metal interfaces. All of these results were compared with those of an epoxy resin prepared from bisphenol‐A and epichlorohydrin resin with an epoxy equivalent value of 0.519. The thermal stability of both the virgin resin and its cured form was also studied by thermogravimetric analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3520–3526, 2002     

New heat-resistant polytriazole adhesives: investigation of adhesion of polytriazole resins to metals

Crosslinkable polytriazole resins (CPTs) were synthesized by 1,3-dipolar cycloaddition reaction between azide and alkyne monomers. Adhesion properties of CPTs and an epoxy resin to different metal substrates (copper, iron and aluminium) were evaluated in terms of the tensile lap shear strength. CPTs to aluminium and iron substrates have higher adhesion strength than those to copper substrates. The effect of temperature and humidity on adhesion strength has been investigated. The resin CPT-3 has the best heat resistance among CPTs, whose retentions of adhesion strength are approximate 80% at 150?°C and 70% at 180?°C to all the substrates. CPTs have high adhesion properties at high temperature and humidity as compared with an epoxy resin.     

核壳聚合物粒子对环氧树脂热膨胀系数的影响

采用核壳聚合物(Core-Shell Polymer,CSP)粒子改性环氧树脂,通过红外光谱、热力学分析和扫描电镜研究了CSP粒子对环氧树脂基体热膨胀系数(CTE)的影响。结果表明:CSP粒子壳材料分子链中的羰基在环氧树脂固化过程中可与环氧分子侧链上的羟基形成氢键作用,从而加强了核壳聚合物粒子与环氧树脂的界面作用。随着CSP粒子质量分数的增加,改性环氧树脂基体的玻璃化转变温度呈下降趋势;相对于纯环氧树脂,改性环氧树脂在玻璃化转变温度下的CTE呈现先下降后上升的趋势,添加质量分数为0.5%的CSP后,其CTE值降低了12.88%。但在玻璃化转变温度上的热膨胀系数均高于纯环氧树脂。     

Adhesive and thermal characteristics of maleimide-functional novolac resins

A novel, addition-curable maleimide-functional novolac phenolic resin was evaluated for adhesive properties such as lap shear strength and T-peel strength using aluminium adherends, when thermally self-cured and cocured with epoxy resins. The adhesive properties of the self-cured resin, although inferior at ambient temperature, improved at high temperature and were found to depend on the cure conditions. When cocured with epoxy resin, the adhesive properties improved significantly and showed a strong dependence on the nature of the epoxy resin used, on the stoichiometry of the reactants, on the concentration of imide groups in the phenolic resin, and on the extent of polymerization of the maleimide groups. Optimum adhesive properties were obtained for novolac resins with a moderate concentration of maleimide groups, taken on a 1 : 1 hydroxyl–epoxy stoichiometry with a novolac epoxy resin. In comparison to the conventional novolac, the imide–novolac contributed to improved adhesion and better adhesive property retention at higher temperature when cured with the novolac–epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 695–705, 1999