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。     

低摩尔比脲醛树脂胶粘剂研究进展

从脲醛树脂胶粘剂的游离甲醛含量及其胶接制品的甲醛释放量,低摩尔比脲醛树脂的合成及不同固化体系下低摩尔比脲醛树脂的固化特性等方面,综述了近几年来低摩尔比脲醛树脂作为木材胶粘剂的研究进展。     

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。     

耐水级MUF的固化特性对胶合板胶接性能的影响

采用一步法制备耐水级的三聚氰胺/脲醛树脂(MUF),并对缩聚阶段的n(F)∶n(U1)比例、固化剂的种类等对固化物的热性能和力学性能的影响进行了探讨。结果表明:固化物的力学性能随着固化体系的不同而异;对A固化体系(氯化铵、甲酸)而言,其峰值温度最低,固化速率最快,固化比较完全,胶接强度最高;而对潜伏性的C固化体系(氯化铵、甲酸、对苯磺酸)而言,其甲醛释放量最高,固化速率最慢。随着缩聚阶段n(F)∶n(U1)比例的增加,固化物的胶接强度增加、甲醛释放量降低。当n(F)∶n(U)=1.3∶1、n(F)∶n(U1)=1.9∶1和V(A固化剂)∶m(胶液)=6 mL∶100 g时,胶合板的综合性能最好;此时,胶合板的胶接强度为0.80 MPa,甲醛释放量(为0.35 mg/L)达到了E0级的国家标准。     

不同固化剂下低摩尔比脲醛树脂热行为及胶接胶合板性能

通过对3种固化剂下5种低摩尔比脲醛树脂进行热分析和胶合板制造实验,研究了摩尔比、游离甲醛含量、固化剂种类等对低摩尔比脲醛树脂胶粘剂固化反应起始温度、峰顶温度、终止温度和胶合板胶合强度及其甲醛释放量的影响。实验结果表明:1)与传统的氯化铵固化剂相比,过硫酸铵催化的脲醛树脂的热分析曲线的起始温度和峰顶温度都很低,显示出良好的固化促进作用;2)以过硫酸盐作固化剂时,低摩尔比脲醛树脂固化过程中起始温度和峰顶温度受摩尔比的影响较小;3)摩尔比为1．0的脲醛树脂胶接胶合板的胶合强度也能够满足GB／T 9846．3-2004Ⅱ类胶合板的要求;4)用过硫酸盐作固化剂制备的胶合板的甲醛释放量较低。     

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。     

粉状脲醛树脂的制备及性能优化

采用M(三聚氰胺)对UF(脲醛树脂)改性,并经高温干燥过程制备粉状MUF(三聚氰胺改性脲醛)树脂,并对M掺量、M两次添加比例、树脂固含量与固化剂影响MUF树脂性能规律进行探究。结果表明:随三聚氰胺添加量增加,MUF粉状树脂甲醛释放量逐渐降低,胶接强度先增后降,并在w(M)=5%(相对于UF总质量而言)时达到最佳;当M两次添加比例m(M_1)∶m(M_2)=1∶4,树脂胶接强度最大,粉状树脂颗粒均匀,分散性较好;液体MUF树脂固含量为30%时,干燥后制备的粉状树脂胶接强度最大、甲醛释放量最低;m(固体固化剂)∶m(粉状树脂)=15∶100比例混合时,MUF树脂胶粘剂综合性能最佳。     

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。     

三聚氰胺改性脲醛树脂胶黏剂的固化性能

以三聚氰胺为改性剂,通过碱-酸-碱工艺合成了低游离甲醛含量的三聚氰胺改性脲醛树脂胶黏剂,研究了NH_4Cl用量对三聚氰胺改性脲醛树脂固化性能及固化物结构的影响。结果表明:三聚氰胺质量分数为2.5%,游离甲醛质量分数为0.14%,且w(NH_4Cl)为2.0%时对改性脲醛树脂的固化效果最佳。X射线衍射测试证实了固化物内部晶态与非晶态共存;拉曼光谱分析从结构上进一步证实了固化物结构上的差异性。     

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     

有机硅乳液改性脲醛树脂胶粘剂的研究

采用对比实验,考查有机硅乳液加入时间、加入量等因素对脲醛树脂的改性效果,将制成的改性脲醛树脂胶粘荆压制三层杨木胶合板,检测胶合板的甲醛释放量和胶合强度等指标。试验结果表明,改性效果最佳的nP／nU为1.2,当有机硅的加入量为树脂总量的5％,加入方式为树脂合成后期加入,对于提高树脂胶合强度、降低游离甲醛及甲醛释放量效果最佳。     

地板基材用MUF树脂胶聚合过程研究

以甲醛（ F）、尿素（ U）、三聚氰胺（ M）为原料,采用弱碱-弱酸-弱碱工艺合成了三聚氰胺-尿素-甲醛（ MUF）共聚树脂胶,配方中F与U物质的量之比为（1.2-1.5）∶1,F与（U＋M）物质的量比为（1.1-1.2）∶1。在不同的反应阶段取样,采用IR和13C NMR对过程中所取样品进行了分析。结果表明,反应开始的碱性阶段主要生成二羟甲基三聚氰胺,在弱酸性阶段缩聚反应时分子间以醚键和亚甲基键联接为主。用反应最终产物压制的杨木胶合板,胶合强度1.07 MPa,甲醛释放量0.38 mg/L,浸渍剥离试验无剥离,达到E0级,胶合强度达到Ⅱ类板的要求（0.7 MPa）。     

三聚氰胺含量对MUF性能的影响

MUF(三聚氰胺-尿素-甲醛共缩聚树脂)兼具UF(脲醛树脂)和MF(三聚氰胺甲醛树脂)的优点,通过调节m(三聚氰胺)/m(尿素)配比,可得到性价比较高的MUF;然后采用MUF胶粘剂制备刨花板,并考察了三聚氰胺含量对刨花板的内结合强度、耐水性和耐沸水性等影响。结果表明:三聚氰胺的引入,虽能有效提高MUF的性能,但并非加量越多越好;当w(三聚氰胺)=11.0%~14.0%时,MUF的性价比相对最高,相应刨花板的内结合强度、耐水性和耐沸水性俱佳。     

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.     

Dynamic mechanical analysis of urea formaldehyde resin modified by ammonium pentaborate as wood adhesive

Urea formaldehyde (UF) resins with varied molar ratio of formaldehyde (F) to urea (U), modified by ammonium pentaborate (APB) at different loading level, was analyzed by dynamic mechanical analysis (DMA) and evaluated via bonding properties of its glued plywood. The result indicated that a higher loading of APB made a slower gelling and improved the ΔE′ (the difference of storage modulus) of UF resin with F/U molar ratio of 1.8. Hexamethylenetetramine, generated from the ammonium ion in APB and formaldehyde in UF resin and characterized by the covalent bond connections, was considered as the main reason to improve the rigidity of the cured UF resin system. The bond strength result confirmed the DMA analysis that the addition of APB improved bonding performance of UF resin with higher F/U molar ratio such as 1.8. A specific recommendation loading level of APB was made to modify UF resins, of which 6.0 to 8.0% APB should be used to modify UF resin with F/U molar ratio of 1.8, then 6% and 4% loading level of APB to UF resin with F/U molar ratio of 1.50 and 1.25, respectively. Finally, APB was n'ot suggested to modify UF resin at F/U molar ratio less than 1.20. POLYM. COMPOS., 37:2404–2410, 2016. © 2015 Society of Plastics Engineers     

SiO_2改性胶合板用脲醛树脂的研究

研究利用SiO2对胶合板用脲醛树脂进行改性,考察了摩尔比、二氧化硅粒径和二氧化硅用量对胶合板胶合强度和游离甲醛的影响。结果表明:用机械共混方式将经硅烷偶联剂KH-550处理的微米级(8μm) SiO2导入摩尔比F／U=1.1:1的脲醛树脂中,当导入量为0．5％时,压制的杨木胶合板胶合强度显著提高,达到国家GB 9846-2004Ⅱ类胶合板标准要求,甲醛释放量达到国家El级标准。     

DSC法研究乙二醛-尿素树脂的固化性能

为从源头上降低UF树脂及其胶合板材的甲醛释放对环境和人体健康所造成的危害,选用乙二醛(G)取代甲醛(F)与尿素(U)反应,制备乙二醛-尿素(GU)树脂。用差示扫描量热分析(DSC)方法研究了原料物质的量比、反应pH、反应时间、反应温度、pH调节剂对所合成GU树脂固化性能的影响规律;并用不同原料物质的量比的GU树脂制备刨花板并测定了其各项性能。结果表明,GU树脂的较优合成条件为:在弱酸性条件下,乙二醛与尿素物质的量比(G/U)=1.2∶0～1.4∶1.0,反应温度70～80℃,反应时间3h;此条件下合成的GU树脂胶合的刨花板内结合强度IB达到0.44MPa、弹性模量MOE达2298MPa、静曲强度MOR为10.5 MPa,且无甲醛释放。