环保型脲醛树脂的优化合成条件设计

对环保型脲醛树脂的优化合成条件进行了探索。通过实验方法研究了原料配比对产品树脂性状(固含量、游离甲醛、粘度)的影响,分析得出原料中甲醛与尿素的优化摩尔比为1.4,并研究了在该优化配比下尿素的分批加料方案,从降低游离甲醛含量以及提高产品固含量两方面优化了尿素的分批加料比例,最终获得了综合性能优良的脲醛树脂产品。     

三聚氰胺改性脲醛树脂胶黏剂的合成

介绍了在温度和pH值等条件不变的情况下,不同的甲醛(F)和尿素(U)配比对合成的脲醛树脂(UF)胶黏剂性能的影响,以及通过用不同质量分数的三聚氰胺(M)对脲醛树脂进行改性以达到合成低游离甲醛胶黏剂的目的.结果表明:F与U物质的量比升高,甲醛含量明显提高;随着F与U物质的量比以及三聚氰胺质量分数的增加,甲醛释放量明显降低.当n(F)∶n(U)=1.5,三聚氰胺的加入质量分数为5％时,甲醛含量最低.     

三聚氰胺改性脲醛树脂胶黏剂的合成工艺研究

介绍了在温度和pH值等条件不变的情况下,不同的甲醛(F)和尿素(U)配比对合成的脲醛树脂(UF)胶黏剂性能的影响,以及通过用不同质量分数的三聚氰胺(M)对脲醛树脂进行改性以达到合成低游离甲醛胶黏剂的目的。结果表明:随着F与U物质的量比增加,甲醛含量明显提高;随着F与U物质的量比以及三聚氰胺质量分数的增加,甲醛释放量明显降低。当n(F)∶n(U)=1.5、三聚氰胺的加入量为5%时,甲醛含量最低。     

树脂型甲醛捕捉剂的研制

在常规脲醛树脂制备工艺基础上,成功制备了树脂型甲醛捕捉剂。借助13C-NMR和GPC分析方法,研究了甲醛捕捉剂的结构特点及分子质量分布。将其与自制的低物质量比脲醛树脂混合使用,考查了甲醛捕捉剂对脲醛树脂性能的影响。结果表明,该甲醛捕捉剂不含游离甲醛,已实现一定程度的树脂化。甲醛捕捉剂中大量游离尿素及一羟甲基脲等低分子质量物质的存在能有效降低刨花板的甲醛释放量,但对混合树脂的最终强度不利。添加甲醛捕捉剂对脲醛树脂的固化行为影响较小。当脲醛树脂与甲醛捕捉剂质量比为85/15、热压时间为4min时,刨花板性能较佳。     

脲醛树脂预聚体对甲维盐微囊结构影响

以脲醛树脂为壁材,采用原位聚合法制备甲维盐脲醛树脂微囊悬浮液。利用13C NMR分析不同甲醛、尿素摩尔比（F/U）所制备的预聚体结构及对微胶囊包封率的影响。结果表明,二羟甲基脲为微胶囊网状交联的主要成分,甲醛、尿素摩尔比为1.8时所制备的预聚体中,二羟甲基脲含量最高。该物料比下制备的甲维盐微胶囊悬浮液包封率为96.3%,高于其他比例下制备的微胶囊悬浮液。表明甲醛、尿素摩尔比控制在1.8时,可制备出包封率较理想的微囊悬浮液。     

碱性阶段起始F/U配比对UF最终结构影响的~(13)C-NMR研究

采用两种工艺[如传统工艺(记为A工艺)、低起始n(甲醛或F)∶n(尿素或U)比例工艺(记为B工艺)]合成脲醛树脂(UF),并用定量13C-NMR(核磁共振碳谱)法跟踪检测UF的结构变化。研究结果表明:当碱性阶段起始n(F)∶n(U)≥2.0∶1.0时,A工艺合成的UF最终结构中亚甲基醚键含量比B工艺高11%。这是由于前者在碱性缩聚阶段中醚键生成占优势,而后者因亚甲基桥键生成参与竞争反应而使醚键含量下降,并且两者在该阶段醚键含量差异贯穿整个树脂的合成过程中。由于空间位阻效应,碱性阶段N,N′-二羟甲基脲间的反应主要生成醚键,而含游离氨基的一羟甲基脲自聚或与其他羟甲基化合物的缩聚可生成亚甲基桥键。     

三聚氰胺改性脲醛树脂工艺条件对体系游离甲醛含量的影响研究

本文采用"弱碱-弱酸-弱碱"工艺,以三聚氰胺为改性剂,制备了脲醛树脂胶粘剂,考察了甲醛与尿素摩尔比、出料p H值、三聚氰胺用量、尿素投料次数对UF树脂胶粘剂中游离甲醛含量的影响。结果表明,当U/F摩尔比为1.2、三聚氰胺改性剂用量2.5%、尿素分3批次投料时,合成的UF稳定性最好,UF中游离甲醛的含量为0.14%。     

钠催化热固性酚醛树脂的合成与表征

采用苯酚和37%甲醛水溶液为原料并以30%氢氧化钠溶液为催化剂制备了高羟甲基含量、低残留甲醛和工艺稳定的热固性酚醛树脂。通过测试合成的树脂中游离酚、游离醛和羟甲基含量研究了醛、酚物质的量比(F/P)、催化剂用量、反应时间和反应温度对酚醛树脂合成的影响,并通过傅里叶变换红外光谱对合成树脂的结构进行了分析。结果表明:当F/P=1.5,催化剂添加质量分数为5%,反应时间2.5 h,反应温度85℃时,制备的树脂性能最佳,其羟甲基含量最高,树脂活性最大,主要为高邻位结构。     

摩尔比对脲醛树脂初期产物结构影响的研究

使用高分辨＾１３Ｃ核磁共振仪研究碱性环境下摩尔比对脲醛树脂初期产物结构的影响。结果表明尿素与甲醛摩尔比对初期产物结构有很大影响，即使在摩尔比为０．８的初期产物中，仍观测到大量的三羟甲基脲或交联的羟甲基和亚甲基包括交联的亚甲基存在，而此时尚有大量的游离尿素存在。     

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。     

Effects of formaldehyde to urea mole ratio on thermal curing behavior of urea–formaldehyde resin and properties of particleboard

As a part of abating the formaldehyde emission (FE) of urea–formaldehyde (UF) resin, this study was conducted to investigate the effects of formaldehyde to urea (F/U) mole ratio on thermal curing behavior of UF resins and properties of PB bonded with them. UF resins synthesized at different F/U mole ratios (i.e., 1.6, 1.4, 1.2, and 1.0) were used for the manufacture of PB. Thermal curing behavior of these UF resins was characterized using differential scanning calorimetry (DSC). As the F/U mole ratio decreases, the gel time, onset and peak temperatures, and heat of reaction (ΔH) increased, while the activation energy (E_a) and rate constant (k) were decreased. The amount of free formaldehyde of UF resin and FE of PB prepared decreased in parallel with decreasing the F/U mole ratio. The internal bond strength, thickness swelling, and water absorption of PB was slightly deteriorated with decreasing the F/U mole ratio of UF resins used. These results indicated that as the F/U mole ratio decreased, the FE of PB was greatly reduced at the expense of the reactivity of UF resin and slight deterioration of performance of PB prepared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1787–1792, 2006     

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     

Syntheses and properties of low‐level melamine‐modified urea–melamine–formaldehyde resins

Syntheses of urea–melamine–formaldehyde (UMF) resins were studied using 2–12% melamine levels and UF base resins that were preadvanced to various different extents. The melamine reaction was carried out at pH 6.3 with F/(U + M) mole ratio of 2.1 until a target viscosity of V was reached (Gardener–Holdt) and then the second urea added at pH 8.0 to give a final F/(U + M) mole ratio of 1.15. Analyses with ¹³C‐NMR and viscosity measurements showed that MF components react fast and the UF components very slowly in the melamine reaction. Therefore, as the extent of preadvancement of UF base resin was decreased, the reaction time to reach the target viscosity became longer and the MF resin components showed high degrees of polymerization. The overpolymerization of MF components resulted in increasingly more opaque resins, with viscosity remaining stable for more than a month. As the preadvancement of UF base resin was increased, the extent of advancement of MF components decreased, to give clearer resins, with viscosity slowly increasing at room temperature. Overall, preadvancing the UF base resin components to an appropriate extent was found to be a key to synthesizing various low‐level melamine‐modified UMF resins. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2559–2569, 2004     

低游离甲醛含量脲醛树脂胶粘剂的合成工艺研究

研究了在弱酸-弱碱-弱酸条件下,加入改性剂合成脲醛(UF)树脂胶的工艺过程。实验结果表明,甲醛与尿素的配比[即n(F)/n(U)比值]、体系pH值、尿素的加料方式和改性剂对UF树脂胶中游离甲醛的含量和胶合强度有很大的影响;当n(F)/n(U)=1.06、缩聚反应阶段体系的pH值为4.75～4.80、尿素分3批加入、反应温度为90℃、加入适量的聚乙烯醇(PVA)和三聚氰胺改性剂时,制得的UF树脂胶中游离甲醛的含量不大于0.10%(符合GB/T14 074.16-1993标准中的指标要求)、粘接强度为4.70 MPa且综合性能优良。     

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     

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.     

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     

Quantification of hydrolytic degradation of cured urea-formaldehyde resin adhesives using confocal laser scanning microscopy

This study reports a method of measuring the extent of hydrolytic degradation of cured urea-formaldehyde (UF) resins trapped in the lumen of softwood tracheids, using confocal laser scanning microscopy (CLSM) which enables quantitative determination of the area of a cured UF resin in the lumen as a function of acid etching time. Two formaldehyde/urea (F/U) mole ratios (1.6 and 1.0) and two hardener levels were employed to compare the extent of hydrolytic degradation of cured UF resins. For comparison, we also measured the mass loss of cured UF resin films after acid etching. Cured UF resins with a 1.6 F/U mole ratio resulted in greater hydrolytic degradation than those with a 1.0 F/U mole ratio. The hardener level also showed a clear influence on the extent of degradation with a limited consistency. These results indicate that cured UF resins with higher F/U mole ratios are more easily hydrolyzed than those with low F/U mole ratios, which could be ascribed to a more branched network structure of cured UF resins with a high F/U mole ratio.     

Evaluation of melamine‐modified urea‐formaldehyde resins as particleboard binders

Particleboards bonded with 6 and 12% melamine‐modified urea‐formaldehyde (UMF) resins were manufactured using two different press temperatures and press times and the mechanical properties, water resistance, and formaldehyde emission (FE) values of boards were measured in comparison to a typical urea‐formaldehyde (UF) resin as control. The formaldehyde/(urea + melamine) (F/(U + M)) mole ratio of UMF resins and F/U mole ratio of UF resins were 1.05, 1.15, and 1.25 that encompass the current industrial values near 1.15. UMF resins exhibited better physical properties, higher water resistance, and lower FE values of boards than UF resin control for all F/(U + M) mole ratios tested. Therefore, addition of melamine at these levels can provide lower FE and maintain the physical properties of boards. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007