Improvement of storage stability of UF resins by adding caprolactam

During storage, the structure of urea-formaldehyde (UF) resins suffers modifications due to reactions between monomers, oligomers, polymer and free formaldehyde, leading to increase in viscosity and decrease in pH. Eventually, viscosity reaches a value that renders the resin unusable, and it must be disposed off. This aging process is accelerated if storage temperature increases.The aim of this work is to obtain UF resins with long storage stability, even when exposed to relatively high temperatures, such as 40 °C. The main strategy adopted was the addition of a chain growth blocker, caprolactam. This monofunctional compound reacts with end groups, blocking them and therefore reducing the polymer's reactivity. In addition, a weak base was added to adjust the pH value, instead of the traditional strong base, sodium hydroxide, therefore hindering the Cannizzaro reaction.The storage stability of UF resins with formaldehyde to urea molar ratio of 1.6–2.0 was monitored by pH and viscosity measurements. Caprolactam was added in different amounts and at different reaction stages. It was found that 10% addition at the beginning of condensation led to the best results, giving a much higher storage stability at 40 °C (2 months when compared to 4 days for a commercial UF resin with low F/U molar ratio). As expected, the resin reactivity decreased with caprolactam addition, demanding for longer pressing times for wood-based panel manufacture. These verified the internal bond strength specification for EN 312 - P2 standard class. Formaldehyde content in the panels was above the E1 class limit when fresh or one month old modified resins were used, implying addition of formaldehyde scavengers. The resin stored for 2 months allowed producing panels within E1 limit. These preliminary results demonstrate the concept that addition of an end-group blocker during UF synthesis is an effective strategy for improving storage stability, encouraging future work on alternative compounds and synthesis conditions optimization.     

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     

脲醛树脂改性工艺中的酸度条件控制

普通脲醛树脂及氧化淀粉改性脲醛树脂的合成工艺中 ,酸度控制条件对合成产物稳定性、剪切强度、游离甲醛含量等性能影响的研究表明 ,缩合反应阶段尿素投入时体系pH值对脲醛树脂合成过程以及产物稳定性都有显著性影响。缩合阶段体系的pH值控制范围直接影响脲醛树脂的稳定性、粘合强度与游离甲醛含量。从脲醛树脂稳定性考虑 ,投入第三批尿素后的pH值应控制在 6 .0以上     

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     

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     

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     

脲醛树脂胶粘剂复合改性研究

脲醛树脂(UF)胶粘剂是一种由尿素与甲醛通过缩聚反应而合成的热固性树脂,广泛应用于木材加工及涂饰行业。针对目前市售脲醛树脂存在的一些问题如游离甲醛含量高、耐水性差、贮藏稳定性差等进行了研究,在探讨合成机理的同时,通过分别加入聚乙烯醇(PVA)、糠醛、硫脲以及由PVA、糠醛和硫脲组成的复合改性剂对树脂进行改性。研究结果表明：复合改性剂的加入,使得改性合成的UF树脂在游离甲醛含量、耐水性、贮藏稳定性等方面优于未改性的UF树脂。     

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。     

Investigating the Extent of Urea Formaldehyde Resin Cure in Medium Density Fiberboard: Resin Extractability and Fiber Effects

The degree of resin cure achievable in urea formaldehyde (UF) resin is known to influence the hydrolytic stability of UF resin. In the current study, a significant difference in water extractable resin components has been observed between cured pure resin and that from medium density fiberboard (MDF) panels. Results show some 50 to 70% of resin components may be removed on water extraction from resinated MDF fiber and panel samples. In contrast, cured pure UF resins have only a small fraction of resin mass extractable into water with nitrogen-containing components remaining incorporated into the cured resin. The relatively high resin mass losses from panel material together with loss of nitrogen-containing components suggest not only free urea, but urea-methylene species are labile and readily extractable into water. Wax contributes to differing panel extractability when pressed at either 100 or 160°C, whereas panel resin loading has a significant effect on extractable resin components. A lower resin loading led to relatively greater resin extractability, which was corroborated by the extractability of resin-fiber mixtures up to 50% resin content. An assessment of extracted panel residues suggests a relative decrease of urea and urea-formaldehyde condensation products after water extraction. With UF resin highly mobile on fiber during MDF manufacture, the results suggest resin components may separate, leading to their incomplete incorporation into a cured, cross-linked UF resin matrix, with an implication that resin cure on fiber may not be complete compared to that found with pure resin.     

Examination of selected synthesis parameters for wood adhesive‐type urea–formaldehyde resins by 13C NMR spectroscopy. III

The varying polymer structures of wood adhesive‐type urea–formaldehyde resins resulting from different formaldehyde/first urea (F/U₁) mole ratios used in the first step of resin manufacture were investigated using ¹³C. As the F/U₁ mole ratio decreased progressively from 2.40 to 2.10 and to 1.80, the viscosity increase due to polymerization during resin synthesis became faster and resulted in decreasing side‐chain branches and increasing free urea amide groups in the resin structure. The resultant UF resins, with the second urea added to an overall F/(U₁ + U₂) of 1.15, showed viscosity decreases when heated with stirring or allowed to stand at room temperature that were also characteristic with the F/U₁ mole ratios used in resin synthesis. The formaldehyde emission levels of particleboards bonded with the freshly made UF resins showed relatively small but similarly characteristic variations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2800–2814, 2001     

脲醛树脂胶粘剂~(13)C核磁共振分析

采用常规化学分析和13C核磁共振相结合的方法,分析研究了脲醛树脂胶粘剂性能与结构的关系。结果表明:在摩尔配比F:U=1.2:1时,粘度越高,游离尿素的含量越低,羟甲基的含量越低,游离甲醛含量降低; 树脂产品的粘度低,聚合度也低,羟甲基的含量偏高,粘接性能下降,同时游离甲醛含量上升,而适量苯酚的添加可改善树脂结构,是一种优化树脂的途径。当增大摩尔配比到F:U=1.4:1时,尿素含量下降,游离甲醛含量上升。因此,摩尔配比的选择在很大程度上影响脲醛树脂的性能。     

Urea impregnated multiwalled carbon nanotubes; a formaldehyde scavenger for urea formaldehyde adhesives and medium density fiberboards bonded with them

Multiwalled carbon nanotubes (MWCNTs) were subjected to modification by urea to use as formaldehyde scavenger in urea formaldehyde (UF) adhesive and reducing the free formaldehyde emission of the medium density fiberboards (MDFs). Morphological differences besides elemental analysis was investigated using field emission scanning electron microscopy (FESEM) and energy dispersive X-ray spectroscopy. The effect of urea impregnated MWCNTs filler on the physical, morphological and thermal properties of the UF resin has investigated. Furthermore, characterization of the mechanical properties, free formaldehyde emission and thickness swelling were carried out for the MDF panels. From the results, the free formaldehyde of the UF resins was significantly decreased. The lowest free formaldehyde was belonged to the sample with 3 wt% of scavenger which was about 71% lower than the value for neat UF resin. Accordingly, the formaldehyde emission of the fiberboards was also showed a descending trend by incorporation of MWCNTs-U to the composite structure. It was decreased from 9.67 to 3.89 mg/100 g dried board. These results indicated that the prepared nano modifier was successfully performed as a formaldehyde scavenger for the UF resin and could prevent the hazards of the free formaldehyde emission from MDF panels.     

Influence of Ammonium Pentaborate (APB) on the Performance of Urea Formaldehyde (UF) Adhesives for Plywood

Ammonium pentaborate (APB) was used to modify urea formaldehyde (UF) resins, in which the formaldehyde to urea molar ratio was set at 1.80, 1.50, 1.25, and 1.05. Some specific properties, including gel time, free formaldehyde content in UF, bond strength, and formaldehyde emission levels from plywood were evaluated. The result showed that APB increased the gel time length, but also decreased free formaldehyde content and emission levels, which was reduced mostly by 79.0% and 81.4%, respectively. The result of bond strength indicated that APB was proper to modify high F/U molar ratio of UF resin regardless of the loading level, but a recommended loading level should be considered to relevantly lower the F/U molar ratio of UF. The suggested loading level of APB to UF is 8.0% to 6.0%, 6.0%, and 4.0% to UF resin with F/U molar ratio of 1.8, 1.5, and 1.25 separately.     

13C‐NMR, 13C‐13C gCOSY,and ESI‐MS characterization of ether‐bridged condensation products in N,N′‐dimethylurea‐formaldehyde systems

The reaction of urea with formaldehyde is the basis for the production of urea‐formaldehyde (UF) resins which are widely applied in the wood industry. The presence of ether‐bridged condensation products in the UF resin reaction system is an open question in the literature. It is addressed in the present work. The N,N′‐dimethylurea‐formaldehyde model system was studied since it is chemically similar to the UF resin reaction system but allows for a simple elucidation of all reaction products. It was analyzed by ¹³C‐NMR spectroscopy and ESI‐MS. In corresponding NMR and MS spectra, peaks due to methoxymethylenebis(dimethyl)urea and its hemiformal were observed. ¹³C‐¹³C gCOSY analysis was conducted using labeled ¹³C‐formaldehyde. The correlation spectra showed evidence for an ether‐bridged compound and mass spectra exhibited peaks agreeing with labeled methoxymethylenebis(dimethyl)urea and its hemiformal. Methoxymethylenebis(dimethyl)urea was characterized in N,N′‐dimethylurea‐formaldehyde systems in acidic and slightly basic media. As urea is very similar to N,N′‐dimethylurea, the results of this work strengthen the assumption that ether‐bridged condensation products are likely to form in UF resins. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

NMR study of the stabilities of urea–formaldehyde resin components toward hydrolytic treatments

The solid residues of nine urea–formaldehyde (UF) resins after hydrolytic treatment at pH4 and 86°C for 20 h and the solid residues of one UF resin after eight different hydrolytic treatments were examined by ¹³C-CP–MAS NMR. The relative stability toward hydrolysis of each structural component in each UF resin was established for various hydrolytic conditions. In general, UF resins prepared from starting mixtures with a formal F/U molar ratio of 1.00 show a high degree of stability toward hydrolysis. Cross-linking methylene linkages in the UF resins show a higher susceptibility to hydrolytic treatments at pH 4 and 86°C than do linear methylene linkages. UF resins prepared with an F/U molar ratio of 2.00 are susceptible to hydrolysis at pH 4 and 86°C. Dimethylene ether linkages, methylols attached to tertiary amides, and poly(oxymethylene glycol) moieties are probably the main formaldehyde emitters in UF resin products. © 1994 John Wiley & Sons, Inc.     

竹胶板用粘合剂的改性研究

随木材资源量日趋减少,竹胶板作为以竹代木的新型板材,有十分广阔的应用前景。针对竹胶板用脲醛树脂粘合剂存在游离甲醛含量高、耐水性差、贮存稳定性不好等缺点,选用苯酚对其合成改性并评价了主要性能。研究结果表明:甲醛/尿素摩尔比为1.3:1,尿素分两次加入,首次加入量为80%,苯酚加入量为反应物总质量的2%,合成树脂与酚醛树脂按10:1共混,可制得综合性能优良用做竹胶板粘结的脲醛树脂,其游离甲醛含量为0.18%,达到E2标准;耐沸水时间为302 min;胶合强度为4.16MPa。     

改性脲醛树脂的合成及性能

采用传统方法合成了脲醛树脂,得出甲醛与尿素的最佳摩尔比为2。采用不同改性剂合成了改性脲醛树脂,得出：随三聚氰胺、聚乙烯醇复合改性剂用量的增加,树脂的游离甲醛含量、固化时间呈逐渐下降趋势,当复合改性剂用量为8%时树脂性能最佳,压缩强度为9.0 MPa;苯酚改性剂的最佳用量为10%,材料的压缩强度为14.2 MPa;糠醛改性剂的最佳用量为15%,材料的压缩强度为19.5 MPa;综合比较,三聚氰胺、聚乙烯醇复合改性剂可以明显降低游离甲醛的含量和固化时间,但材料的压缩强度增加不大,而采用糠醛改性剂制得改性脲醛树脂的压缩强度较大。     

Production of melamine fortified urea‐formaldehyde resins with low formaldehyde emission

Melamine can be incorporated in the synthesis of urea‐formaldehyde (UF) resins to improve performance in particleboards (PB), mostly in terms of hydrolysis resistance and formaldehyde emission. In this work, melamine‐fortified UF resins were synthesized using a strong acid process. The best step for melamine addition and the effect of the reaction pH on the resin characteristics and performance were evaluated. Results showed that melamine incorporation is more effective when added on the initial acidic stage. The condensation reaction pH has a significant effect on the synthesis process. A pH below 3.0 results on a very fast reaction that is difficult to control. On the other hand, with pH values above 5.0, the condensation reaction becomes excessively slow. PBs panels produced with resins synthesized with a condensation pH between 4.5 and 4.7 showed good overall performance, both in terms of internal bond strength and formaldehyde emissions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Examination of selected synthesis parameters for typical wood adhesive‐type urea–formaldehyde resins by 13C‐NMR spectroscopy. II

A particleboard adhesive‐type urea–formaldehyde (UF) resin was made at a formaldehyde ratio of 2.10 and added with a second urea at low temperature to the typical final formaldehyde/urea ratio of 1.15. Time samples taken during heat treatments of the resin sample up to 70°C over a period of 250 min showed decreases in Type II/IIi hydroxymethyl group content, accompanied with decreases in resin sample viscosity and increases in formaldehyde emission of bonded particleboards. The results indicate that various hydroxymethyl groups of polymeric UF resin components migrate to the second urea to form Type I hydroxymethyl groups. Time samples taken during the room‐temperature storage of the resin sample over a period of 1 month behaved similarly initially, but in the later stage, some polymerization progressed, shown by increases in viscosity and methylene and methylene–ether group contents. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1243–1254, 2000     

低游离甲醛脲醛树脂合成工艺研究

脲醛(UF)树脂是一种广泛应用于木材加工业的胶黏剂,文章采用碱-酸-碱合成工艺,探讨了甲醛与尿素的摩尔比、pH、反应温度及尿素加料方式等因素对UF树脂黏度及游离甲醛含量的影响,发展了制备低毒(游离甲醛含量0.13%)UF树脂的新工艺,并用IR对UF树脂进行了确证。