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。     

低毒脲醛树脂的合成

针对脲醛树脂在制板过程以及人造板材在使用过程中不断释放甲醛,危害人体健康的环保问题,采用二次缩聚的工艺合成脲醛树脂,并对合成反应的脲醛比、pH值、温度等工艺条件进行了研究。实验结果表明：二次缩聚能有效降低树脂中游离甲醛的含量,控制适宜的脲醛比,pH值以及反应温度等工艺条件,可以使脲醛树脂中游离甲醛的浓度控制在0．5％,树脂的各项指标均达到要求。     

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。     

工业固废脲醛树脂降解处理及再生树脂性能初探

采用热降解处理工业固废脲醛树脂,研究处理条件对树脂降解效果的影响。结果表明,在强酸性(pH≤3)处理环境下,控制甲醛溶液和固废脲醛树脂质量比为4∶1,热处理温度为70～85℃,渗透剂添加量为3%时,树脂的降解率可达99%。继续将其用于脲醛树脂合成用起始原料,在本实验工艺条件下,添加量为甲醛溶液质量5%时,工业试验生产的7层胶合板胶合强度、甲醛释放量等指标可满足国标要求。     

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。     

低温合成聚乙烯醇改性脲醛树脂的研究

探讨了低温弱酸性条件下聚乙烯醇改性脲醛树脂的合成,研究了聚乙烯醇加入量、加入的顺序对脲醛树脂胶粘剂的影响。结果表明,甲醛与尿素的摩尔比F/U=1.87,pH=4.5和温度40℃的反应条件下,加入聚乙烯醇量为0.2 g时,脲醛胶质量最好,游离甲醛含量低至0.64%,耐水时间为14 h,且稳定性好。而传统高温工艺的游离甲醛含量为1.14%,耐水时间3.4 h。本工艺节能环保,提高生产效率。     

弱酸性条件起始合成脲醛树脂的工艺研究

对按设计工艺合成的脲醛树脂进行了性能测定,采用化学和红外方法分析了树脂的官能团,并定性分析了几种树脂固化过程中的热行为,结合实验现象分析了从弱酸性起始合成脲醛树脂的工艺特点。证明从弱酸性起始可以合成具有良好工艺性能的脲醛树脂;合成工艺与传统工艺相比有成本优势;通过工艺的完善可以控制制品的甲醛释放;采用该类工艺能够合成出适合冷固化的木材胶粘剂。     

Uron型和三聚氰胺改性脲醛树脂胶粘剂的对比研究

在强酸条件下,以尿素(U)和甲醛(F)为原料合成Uron(尤戎)环衍生化合物,然后与采用常规碱-酸-碱工艺合成的三聚氰胺(M)改性脲醛树脂(UF)胶粘剂进行了性能对比,同时还根据市场原料价格估算了两者的成本。研究结果表明:强酸条件下合成的UF胶粘剂含有Uron型环状结构(可明显提高胶合板的胶接强度,降低F释放量),具有胶接性能优异、生产成本低廉等特点。     

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。     

酸-碱-酸-碱工艺合成脲醛树脂

以酸-碱-酸-碱工艺合成一种聚乙烯醇(PVA)、三聚氰胺改性脲醛树脂,研究了原料配比、pH值、反应时间等对产品性能的影响。结果发现,当n甲醛:n尿素=1.6:1,聚乙烯醇加入量为甲醛和尿素总质量的1%,三聚氰胺加入量为甲醛和尿素总质量的3%,酸性条件下pH=5.5,碱性条件pH=8.5～9.0,反应温度为80℃左右时,合成的脲醛树脂的机械强度较好,游离甲醛的含量较低。     

人造板甲醛释放研究

提出了一种脲醛树脂合成思路,并合成出游离甲醛含量高于0．3％的树脂。使用这种树脂压制的胶合板甲醛释放量在0．2mg/L以下,达到了日本2003年修订的JIS中F五星级要求。与按普通工艺合成的树脂对照,利用GPC、DSC等方法对树脂进行了分析,认为树脂发生固化时的固化程度更高,固化后形成的交联结构更加致密是制品低甲醛释放的主要原因。为脲醛树脂的生产、使用和研究人员控制制品的甲醛释放提供了一种可操作的方法。     

脲醛树脂化学构造与胶接性能、甲醛释放量及固化特性关系的研究

采用3种典型的脲醛(UF)树脂合成方法合成UF树脂,并对合成UF树脂的性能、化学构造、胶接性能、甲醛释放量及其固化历程进行了研究。揭示了UF树脂化学构造与合成方法、胶接性能、固化特性及甲醛释放量之间的相关关系,证明UF树脂的胶接性能、固化历程、甲醛释放量与UF树脂的化学构造直接相关,尤其是树脂中羟甲基含量与结合方式、亚甲基的构造对树脂性能影响最大。     

Study of hybrid isocyanate and high-mono-hydroxymethyl urea content urea-formaldehyde resins

Based on the difference in the reaction rate of different groups of urea-formaldehyde resins and isocyanate resins, this study designed two different urea-formaldehyde resins: a normal urea-formaldehyde resin (UF) and one with high mono-hydroxymethylurea content (UF*) to react with polymeric methylene diphenyl diisocyanate (pMDI) resin. The difference in mono- and di-hydroxymethyl urea content between UF and UF* resins was analyzed by nuclear magnetic resonance (NMR) spectroscopy, and results showed that the mono-hydroxymethyl urea content of the UF* resin was much higher than that of the conventional UF resin. The fourier transform infrared spectrometer (FTIR) analysis of differences between UF* and UF resin showed that the UF* process did not change the main structure of the conventional urea formaldehyde resin. Differential scanning calorimeter (DSC) analysis showed that the curing temperature of the hybrid UF*-pMDI resin was reduced 27.3°C compared to that of the UF-pMDI resin. When these hybrid resins were used to bond plywood respectively, test results showed that the UF*-pMDI resin improved the dry and wet bonding strength by 2.6% and 3.9%, respectively, compared with the UF-pMDI resin under the condition of hot pressing time (3 min) and temperature (140°C), meeting the requirement of Chinese standard of GB/T 9846–2015 for Class III board. This study provides a new path for further improving the performance and design of hybrid resins based on isocyanate and urea-formaldehyde resin.     

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...     

Synthesis of urea-formaldehyde resin by melt condensation polymerization

Traditional method of synthesizing urea-formaldehyde (UF) resins is condensation polymerization with formaldehyde and urea in aqueous solution, which leads to the low resistance of UF resins against the influence of water and moisture and results in the high formaldehyde emission. A new method of melt condensation polymerization was used to synthesis UF resin by paraformaldehyde with urea. Fourier-transform infrared spectroscope and Carbon-13 nuclear magnetic resonance were performed to elucidate the uron rings structural characteristics of UF resin by the synthetic route. The stability during storage and application were characterized by measuring concentration of methanol and free formaldehyde, and DSC and TG analysis, respectively. The results show that UF resin synthesized by melt condensation polymerization has lower content of free formaldehyde, high thermal stability and better stability during storage.     

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