茶叶废料在脲醛树脂中的应用研究

将不同颗粒度的茶叶废料粉添加到脲醛树脂胶中,研究了茶叶废料的颗粒度、加入量等对脲醛树脂胶黏剂的游离甲醛含量、黏接胶合板的甲醛释放量及胶合强度的影响。实验结果表明,茶叶废料作为填料添加到脲醛树脂胶黏剂中,能够降低其游离甲醛含量以及其黏接胶合板的甲醛释放量;茶叶废料颗粒度越小,与脲醛树脂混合性越好,消除甲醛效果越显著;茶叶废料的适量加入不会降低胶合板胶合强度。     

Study of glycidyl ether as a new kind of modifier for urea‐formaldehyde wood adhesives

In this work, the multiepoxy functional glycidyl ether (GE) modified urea‐formaldehyde (UF) resins were synthesized via a traditional alkaline‐acid process under low formaldehyde/urea (F/U) molar ratio. The synthesized resins were characterized by ¹³C magnetic resonance spectroscopy (¹³C‐NMR), indicating that GE can effectively react with UF resins via the ring‐opening reaction of epoxy groups. Moreover, the residual epoxy groups of GE could also participate in the curing reaction of UF resins, which was verified by Fourier transform infrared spectroscopy. The storage stability of GE‐modified UF resins and the thermal degradation behavior of the synthesized resins were evaluated by using optical microrheology and thermogravimetric analysis, respectively. Meanwhile, the synthesized resins were further employed to prepare the plywood with the veneers glued. For the modification on bonding strength and formaldehyde emission of the plywood, the influences of addition method, type, and amount of GE were systematically investigated. The performance of UF adhesives were remarkably improved by the modification of GE around 20–30% (weight percentage of total urea) in the acidic condensation stage during the resin synthesis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Melamine‐bridged alkyl resorcinol modified urea–formaldehyde resin for bonding hardwood plywood

A powdery product was obtained by the reaction of methylolated melamine with alkyl resorcinols to form melamine‐bridged alkyl resorcinols (MARs). The effects of the addition of this powder on the bonding strength and formaldehyde emission of urea–formaldehyde (UF) resins were investigated. Three types of UF resins with a formaldehyde/urea molar ratio of 1.3 synthesized by condensation at pH 1.0 (UF‐1.0), pH 4.5 (UF‐4.5), and pH 5.0 (UF‐5.0) were fabricated. The addition of MAR to UF‐4.5 and UF‐5.0 for bonding hardwood plywood enhanced the bonding strength and reduced formaldehyde emission. For UF‐1.0, the addition of MAR adversely affected the bonding strength. However, the UF‐1.0 resin yielded the lowest formaldehyde emission of all of the UF resins in the study. The effects of the MAR addition were related to the molecular structures of the UF resins. UF‐1.0 contained a large amount of free urea, a considerable number of urons, and a highly methylene‐linked, ring‐structured higher molecular weight fraction and had a smaller number of methylol groups. Therefore, the addition of MAR was considered to cause a shortage of the methylol groups, which in turn, led to incomplete resin curing. In contrast to UF‐1.0, UF‐5.0 contained a smaller amount of free urea and a linearly structured higher molecular weight fraction and had a larger number of methylol groups. In this case, MAR was considered to effectively react with the methylol groups to develop a three‐dimensional crosslinked polymer network to enhance the bonding strength and suppress the generation of free formaldehyde to reduce formaldehyde emission. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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。     

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.     

低nF/nM三聚氰胺-甲醛低聚物对脲醛树脂性能的影响

采用自制的可溶性三聚氰胺-甲醛低聚物作为脲醛树脂的添加剂,通过DSC及压制胶合板等方法评价该低聚物对脲醛树脂的固化特性、游离甲醛释放量和胶合强度的影响.结果表明,对于nF/nU为1.1的脲醛树脂UF1.随着三聚氰胺-甲醛低聚物加入量的增加,树脂固化活化能和胶合板的甲醛释放量都呈现先降低后增加的趋势,而胶合强度变化趋势不...     

三聚氰胺草酸盐与氯化铵作为UF固化剂的性能对比

以三聚氰胺草酸盐(MOX)和氯化铵分别作为脲醛树脂(UF)的固化剂,然后以相应的改性UF胶粘剂压制胶合板,并探讨了不同固化剂对UF的固化时间、胶合板的胶接强度和甲醛释放量等影响。结果表明:以MOX作为固化剂时,相应UF的固化速率相对较慢,由该改性UF胶粘剂压制而成的胶合板,其胶接强度相对较高,甲醛释放量略高于含氯化铵体系;含MOX固化剂的UF胶粘剂,其DSC曲线峰顶温度(86.22℃)和吸热量(51.14 J/mg)低于含氯化铵体系,并且含MOX体系的固化反应比较平稳。     

The effect of hydrolyzed soy protein isolate on the structure and biodegradability of urea–formaldehyde adhesives

The hydrolyzed soy protein isolate (HSPI) was used to partially substitute urea to synthesis modified urea–formaldehyde (UF) adhesives via copolymerization process, in order to reduce the dependency on petroleum-based chemicals and mitigate possible environmental pollution. The soy protein isolate (SPI), HSPI, and modified UF adhesives were characterized by attenuated total reflection Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), and thermo-gravimetric analysis (TGA). The bonding strength, adhesive properties, biodegradability, and micrographs of the UF and HSPI-modified UF after degradation were also measured. The results show that the SPI native structure is unfolded during the treatment with sodium hydroxide. The thermal stability of HSPI is better than SPI. HSPI can incorporate into the structure of cured UF adhesives with three different feeding methods. And the best bonding strength of modified UF adhesives is 1.31?MPa when HSPI is added at the first step. The formaldehyde emission of modified UF adhesives is lower compared with UF. The earlier the HSPI is added, the better the properties for modified UF adhesives can be obtained. The degradation rate of modified UF adhesives improved nearly two times compared to the UF after six months of degradation in biologically active soil. There are microorganisms adhering to the surface of modified UF from the SEM micrographs.     

Influence of nanoclay on urea‐formaldehyde resins for wood adhesives and its model

The addition of small percentages of Na⁺‐montmorillonite (NaMMT) nanoclay appears to improve considerably the performance of thermosetting urea‐formaldehyde (UF) resins used as adhesives for plywood and for wood particleboard. X‐ray diffraction (XRD) studies indicated that NaMMT loses the periodic atomic structure when mixed in small proportions in the acid‐curing environment characteristic of the curing of UF resins. This can be interpreted as becoming exfoliated under such conditions. The partly crystalline structure of the ordered zones of the UF resins is maintained but at a slightly lower level. Differential scanning calorimetry (DSC) indicated that NaMMT has an accelerating effect on the curing of the UF resin. It also appears to lead to a more controlled rate of crosslinking implying a more regular hardened network. The influence of NaMMT addition was particularly noted in plywood by the increase in water resistance of the UF‐bonded panel. In the case of wood particleboard even the dry internal bond strength of the panel, a direct indication of the performance of the resin, improved with small additions of NaMMT. A hypothesis and model of the reasons why such improvement to the performance of UF resins by addition of nanoclay should occur has been presented. This is based on the application of percolation theory to the networking capability of the clay nanoplatelets. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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。     

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     

气膜法低醛化脲醛树脂合成及木材胶合性能

采用中间加入起泡剂鼓泡,进行气液传质交换的方法,合成环保型脲醛胶,游离甲醛降到0．05％以下,胶合板胶合强度达0．7MPa以上,并且对板材生产工艺可操作性强,其制品甲醛释放量都达到1．5mg,／L(干燥器法)以下,符合GB18580-2001E1标准要求。红外(IR)光谱进一步证实,气膜法可提高脲醛树脂、尿素中-NH2的加成反应率以及树脂固化的交联度,降低游离甲醛。     

The aminolysis of styrene–maleic anhydride copolymers for a new modifier used in urea-formaldehyde resins

Styrene (St) and maleic anhydride (MA) alternating copolymers with different molecular weights (MW) were synthesized via radical copolymerization. The copolymers were subsequently transferred into water-soluble maleic amic acid derivatives (SMAA) via the aminolysis of anhydride groups using (NH₄)₂CO₃ as the ammonia sources. The synthesized polymers were applied as a new kind of macromolecular modifier and added into the reaction system during the synthesis of urea-formaldehyde (UF) resins via the traditional alkaline–acidic–alkaline three-step process. The UF resins modified with SMAA were characterized using Fourier Transform Infrared Spectroscopy (FT-IR), ¹³C nuclear magnetic resonance (¹³C-NMR) spectroscopy, and thermal gravimetric analysis (TGA). All the results confirmed the successful incorporation of SMAA chains into the crosslinking network of the UF resins. The modified UF resins were further employed as wood adhesives and the effect of synthesis parameters on their performance was investigated. Meanwhile, the influence of SMAA molecular weight (MW) on the properties of the modified UF resins was also studied. When the UF resins were synthesized with a low molar ratio of formaldehyde/urea (F/U) and a predetermined amount of SMAA added into the reaction system at the second step, plywood bonded using these modified UF resins showed much improved bonding strength (BS) and depressed formaldehyde emission. Moreover, the as-modified UF resins showed good storage characteristics.     

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     

木材胶接用三聚氰胺改性脲醛树脂胶黏剂性能研究

针对实际应用,以=三聚氰胺作为改性剂对脲醛树脂进行共聚和共混改性.在不同固化体系下,采用不同摩尔比低毒脲醛树脂分别与三聚氰胺混合,对混合比例变化对胶合强度和甲醛释放量的影响进行了具体研究.结果表明:固化体系不同,胶接强度也不相同.随着摩尔比的升高,胶接强度提高,甲醛释放量亦相应提高.用三聚氰胺改性的脲醛树脂的胶接强度与甲醛释放量均优于纯脲醛树脂.混合胶液中随三聚氰胺比例减少,胶接性能有所下降,甲醛释放量变化逐渐趋于平稳.     

Lignin–phenol–formaldehyde resin adhesives prepared with biorefinery technical lignins

In this study, four biorefinery technical lignins were used to synthesize lignin–phenol–formaldehyde (LPF) resin adhesives with a proposed formulation that was designed based on accurate analysis of the active sites in lignin with ³¹P nuclear magnetic resonance (NMR). The properties of the LPF resin adhesives and the plywoods prepared with them were tested. The structural features and curing behavior of the LPF resin adhesives were thoroughly investigated by solution‐ and solid‐state ¹³C NMR. Results indicated that the proposed formulation exhibited favorable adaptability for all four of these technical lignins for synthesis of LPF resin adhesives. High‐performance plywood with low emissions of formaldehyde could be successfully prepared with the synthesized LPF resin adhesives. All the LPF resin adhesives exhibited similar structure and curing behavior with the commercial phenol–formaldehyde (CPF) resin adhesive. However, the LPF resin adhesives showed relatively higher curing temperatures as compared with the CPF resin adhesive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42493.     

A comparison between lignin modified by ionic liquids and glyoxalated lignin as modifiers of urea-formaldehyde resin

The aim of this research was to compare the influence of modified lignin by ionic liquid (IL) on the physical and mechanical properties of wood-based panels bonded with urea-formaldehyde (UF) resin with the effect of glyoxalated lignin (GL) on UF properties. For this purpose, soda bagasse lignin was respectively modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) IL and glyoxal and then the various content of modified lignins (10, 15, and 20%) were added at pH=7 during the UF resin synthesis instead of the second urea . The changes in the structure and thermal properties of lignin, after and before modification with glyoxal and IL, were analyzed by Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry (DSC). 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 the FTIR spectra, the content of C=O bond increased in GL while in the IL-treated lignin the content of C–N bond markedly increased. DSC analysis indicated that lignin modified by IL had lower glass transition temperature (T_g) value compared to those modified with glyoxal and unmodified lignin, respectively. The UF resins containing IL-treated lignin exhibit a faster gel time compared to those prepared with GL. Equally, the plywood panels prepared with an IL had lower formaldehyde emission and higher mechanical strength compared to those made from UF resin containing GL. There were no significant differences in dimensional stability of the panels bonded with UFs modified with GL and those with IL-modified lignin.     

Decreasing the formaldehyde emission in urea‐formaldehyde using modified starch by strongly acid process

The incorporation of the modified starch (MS) in urea‐formaldehyde resins at different stage of the synthesis was studied in this article. The synthesized resins were characterized by Fourier transform infrared spectroscopy, indicating that the ester bond can be introduced into the UF structure after the addition of MS. The curing reactions were examined with differential scanning calorimetry and it reveals that curing temperature of UF resin are slightly shifted to higher temperatures. To study the bonding strength and formaldehyde emission of the bonded plywood, the addition method and amount of MS are systematically investigated. The performance of the UF resins is remarkably improved by the addition of MS around 15% (weight percentage of the total resin) in the second stage. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40202.     

三聚氰胺添加方式对MUF胶粘剂性能的影响

以三聚氰胺作为脲醛树脂(UF)的共聚改性剂制备MUF(三聚氰胺甲醛树脂)胶粘剂。探讨了三聚氰胺的添加方式对MUF胶粘剂性能的影响,同时对其固化特性、分子结构和耐热性等进行了分析。结果表明:三聚氰胺2次投料法可有效降低MUF胶粘剂的甲醛释放量,但其胶接强度也随之下降;同时,该MUF固化体系的外推固化温度、表观活化能和反应级数均有所增加,耐热性降低;另外,2次投料体系使MUF的相对分子质量降低、相对分子质量分布变宽。     

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.