改性单宁酸制备UF树脂胶粘剂的性能研究

首先,加入对甲苯磺酸对单宁酸进行处理,制备得到改性单宁酸,再以改性单宁酸作为改性剂制备改性UF胶粘剂(TUF),研究不同添加阶段和不同添加量对树脂性能的影响。用热重分析(TGA)和红外光谱(FT-IR)对树脂的结构和固化性能进行了表征。结果显示,选择在UF树脂制备过程中随第二批尿素添加,单宁酸用量为6%时,改性UF树脂的游离甲醛含量最低,干、湿结合强度均符合胶合板胶粘剂国家标准。     

双组分豆粕胶粘剂的固化粘弹性能研究

采用旋转流变仪分别研究了改性胶液、豆粕粉添加量、G试剂添加量对双组分豆粕胶粘剂粘弹性的影响。结果表明,双组分豆粕胶粘剂的固化粘弹性变化趋势不受改性胶液的影响,始终保持G'G";随着豆粕粉添加量的增加,双组分豆粕胶粘剂的粘弹性能逐渐增大,其交联产物的热稳定性在高温区域逐渐减弱;随着G试剂添加量的增大,双组分豆粕胶粘剂的凝胶固化行为逐渐增强,固化温度逐渐降低。通过UF树脂、PF树脂和双组分豆粕胶粘剂的性能对比发现,双组分豆粕胶粘剂的凝胶固化行为及胶合强度和耐水性能均近似介于UF树脂和PF树脂之间。     

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。     

有机蒙脱土改性脲醛树脂胶粘剂的制备及性能研究

将不同投料比的OMMT(有机蒙脱土)引入脲醛树脂(UF)合成的3个阶段(加成、缩聚和缩聚后期)中,制备出相应的OMMT改性UF胶粘剂。研究结果表明:该改性UF胶粘剂的耐热性高于未改性UF胶粘剂,其游离甲醛含量随OMMT投料比增加而降低,粘接强度随之增大。加成阶段投入OMMT后,该改性UF胶粘剂的降醛效果明显;缩聚阶段投入OMMT后,该改性UF胶粘剂的补强效果显著。OMMT较佳的投入阶段为缩聚阶段,较佳的投料比为2%~3%(相对于尿素总质量而言)。     

氯化铵用量对酸化蒙脱土改性低摩尔比脲醛胶粘剂性能的影响

为考察氯化铵对蒙脱土改性UF(脲醛树脂)胶粘剂固化性能的影响,先对蒙脱土进行酸化改性,再将一定量的H-MMT(酸化蒙脱土)以原位聚合的方式投入到UF合成的不同阶段,以此制备改性效果不同的UF胶粘剂,并考察氯化铵用量对改性UF胶粘剂固化时间、适用期、胶合强度的影响。研究结果表明:反应第二阶段投入H-MMT改性的UF胶粘剂在3%氯化铵作用下固化性能较好,其固化时间为75.92 s,适用期为325 min,胶合强度为1.09 MPa;H-MMT改性的UF胶粘剂中存在未反应的游离尿素,加入固化剂氯化铵后,体系游离尿素量有所降低。     

改性脲醛树脂对提高淀粉胶粘剂耐水性能的研究

为进一步提高淀粉胶粘剂的耐水性能,在传统脲醛树脂(UF)和淀粉胶粘剂合成工艺的基础上,以环氧氯丙烷(ECH)作为UF的接枝共聚改性剂,制备环氧型UF;然后将环氧型UF与传统淀粉胶粘剂进行复配,制备改性淀粉胶粘剂。以耐水剪切强度作为考核指标,采用正交试验法优选出制备改性UF的较佳工艺条件。结果表明:当n(F)∶n(U)=2.0∶1、m(ECH)=8 g、缩聚温度为90℃和接枝共聚时间为75 min时,制成的改性UF可明显提高复配淀粉胶粘剂的耐水性能。     

玉米淀粉的氧化工艺对改性低毒脲醛树脂性能的影响

为了进一步降低胶合板中的游离甲醛释放量和提高其胶接强度,采用湿法自制的氧化玉米淀粉对胶合板用低毒脲醛树脂(UF)胶粘剂进行改性。通过改变氧化体系的酸碱性、氧化时间以及氧化淀粉用量,优选出制备改性UF胶粘剂的较佳工艺条件。结果表明:在碱性条件下将玉米淀粉氧化40 min,然后将其作为UF胶粘剂的改性剂,当w(氧化淀粉)=15%(相对于尿素质量而言)时,改性UF胶粘剂的综合性能较好。     

基于膨润土的脲醛树脂填料的开发与性能研究

比较了面粉、膨润土及其用量对脲醛(UF)树脂胶粘剂的pH值、固含量、固化时间和胶合强度的影响,探讨了膨润土用作胶粘剂填料的可行性。研究结果表明:随着膨润土用量的增加,UF树脂胶粘剂的pH值、固化时间和固含量呈递增趋势,游离甲醛含量明显下降;随着面粉用量的增加,UF树脂胶粘剂的固含量和固化时间呈递增趋势(但增幅比膨润土体系小),pH值有所降低;用添加膨润土的UF树脂胶粘剂生产的胶合板,当w(膨润土)≤20%、施胶量为280～300 g/m2时,胶合板的湿态胶合强度(1.69 MPa)比面粉体系(1.53 MPa)和纯UF树脂胶粘剂体系(1.09 MPa)的高,其湿态胶合强度能达到GB 9 846-1988的标准,而干态胶合强度则远高于GB 9 846-1988标准。     

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。     

氨基硅烷偶联剂改性凹凸棒石在UF胶粘剂中的应用研究

利用不同硅烷偶联剂改性ATP(凹凸棒石)或SiO2-ATP,并制备了相应的UF(脲醛树脂)胶粘剂。探讨了改性ATP或SiO2-ATP的工艺条件及其对UF胶粘剂的甲醛释放量、剪切强度等影响。结果表明:含氨基的硅烷偶联剂(A-1160和KH-792)对ATP/UF或SiO2-ATP/UF胶粘剂的甲醛释放量、剪切强度的影响较大;当w(A-1160或KH-792)=15%(相对于ATP质量而言)、w(改性ATP)=10%(相对于甲醛和尿素总质量而言)时,经60℃、3 h吸附后,相应UF胶粘剂的甲醛释放量分别下降了53.27%或53.04%,剪切强度分别增加了57.27%或46.73%;当w(A-1160或KH-792)=15%、w(改性SiO2-ATP)=10%时,经60℃、2 h吸附后,相应UF胶粘剂的甲醛释放量分别下降了34.84%或48.82%,剪切强度分别增加了68.88%或55.38%。     

Particulate reinforcement and formaldehyde adsorption of modified nanocrystalline cellulose in urea-formaldehyde resin adhesive

In this study, nanocrystalline cellulose (NCC) was used for reinforcement and formaldehyde (HCHO) adsorption of urea-formaldehyde (UF) resin adhesive in fiberboard. The original NCC was modified by 3-aminopropyltriethoxysilane for improving the wetting property with UF resin adhesive. The UF resin adhesive with modified NCC was analyzed by X-ray powder diffraction, thermogravimetric analysis, and Fourier transform infrared. The HCHO emission and bending and bonding strength of the UF resin adhesive with modified NCC were tested according to Chinese National Standard GB/T 17657-1999. Compared with the original UF resin adhesive, modified NCC led to limited effects on the crystal structure, thermal stability, and characteristic absorption peaks of UF resin adhesive. The HCHO emission of the UF resin adhesive with 1.0% modified NCC decreased by 13.0%, while the bending and bonding strength increased by 40.5 and 158.3%, respectively. The improvements of modified UF resin adhesive were destroyed by the reunion of NCC when the content was more than 1.5%.     

皮胶蛋白增量剂对脲醛树脂胶合性能的影响

研究了化学改性皮胶加入脲5醛（UF）树脂对胶合性能的影响,旨在提高普通脲醛树脂应用性能。讨论了pH值、黏度、固化时间、耐水性、拉伸剪切强度等胶黏剂指标。结果表明：改性剂的加入使得改性合成的脲醛树脂在耐水性、胶合强度等方面优于未改性的脲醛树脂。改性皮胶的含量为3％时,改性脲醛树脂胶黏剂的主要的技术性能和指标均已达到国家标准。确定了改性皮胶做为增量剂的加入会使脲醛树脂本身的耐水性能和胶合强度均有提高。     

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     

改性脲醛树脂胶的研制

本文介绍了一种用共聚乳液对醛脲树脂进行改性的方法，研制出一种耐水的耐老化的脲醛树脂胶粘剂。     

脲醛树脂的研究进展

综述了近年来脲醛树脂的研究进展,从低甲醛脲醛树脂的合成工艺研究、改性脲醛树脂的合成工艺研究、环保脲醛树脂的合成工艺研究等方面进行了归纳和评述,展望了脲醛树脂未来的研究方向和发展前景。     

改性脲醛树脂新进展

综述了改性脲醛树脂胶粘剂研究的最新成果,报道了为降低产品毒性,提高ＵＦ树脂的粘接强度,耐水性和抗老化性能所采取的措施,阐述了扩大改性ＵＦ树脂应用领域的良好的前景。     

Effect of microfibrillated cellulose addition on thermal properties of three grades of urea-formaldehyde resin

Three grades of liquid urea-formaldehyde (UF) resin with different formaldehyde emission levels such as super E0 (SE0), E0 and E1 were modified by adding different amounts of microfibrillated cellulose (5 wt% MFC and 95 wt% water) that had been isolated by mechanical disintegration of pulp fibers. Thermal properties of these UF resins were investigated to understand thermal curing and degradation behaviors of the modified UF resins, using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DSC thermograms showed an exothermic curing reaction, and the curing peak temperature of modified UF resins heavily depended on the emission resin grade with an increasing order from E1, E0 to SE0. The addition of MFC suspension into the UF resins gradually increased curing peak temperature suggesting a decrease in the resin reactivity. TGA results showed three main thermal degradation temperatures for the modified UF resins except the SE0 UF resin, which had four degradation temperatures.     

Hydrolytic and thermal stability of urea-formaldehyde resins based on tannin and betaine bio-fillers

In this work, betaine (trimethyl glycine) and tannin (complex biomolecules of polyphenolic nature) were used as bio-fillers. Urea-formaldehyde (UF) resin with a molar ratio of formaldehyde versus urea (FA/U) of 0.8 was synthesized in situ with tannin and betaine as bio-fillers, to obtain UF resin with reduced free FA content and increased hydrolytic and thermal stability by the principles of sustainability. The samples TUF (with tannin) and BUF (with betaine) were characterized by using X-ray diffraction analysis (XRD), non-isothermal thermogravimetric analysis (TGA), and differential thermal analysis (DTA), supported by data from Fourier Transform Infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM). The percentage of free FA in modified BUF resin is 0.1%, while the percentage of free FA in tannin-modified resin is 0.8%. The hydrolytic stability of the modified UF resins was determined by measuring the concentration of liberated FA in the modified UF resins, after acid hydrolysis. The modified BUF resin is hydrolytically more stable because the content of released FA is 3.6% compared to the modified TUF resin, where it was 7.4%. Based on the value for T_5%, the more thermally stable resin is the modified TUF resin (T_5% = 123.1°C), while the value of the T_5% for the BUF resin is 83.1°C. This work showed how UF bio-composite with reduced free FA content and increased hydrolytic and thermal stability can be obtained using tannin and betaine as bio-fillers.     

Thermoplastic modification of urea–formaldehyde wood adhesives to improve moisture resistance

Urea–formaldehyde (UF) resins are prone to hydrolytic degradation, which limits their use to indoor applications. This study examined the modification of UF resin with various thermoplastics as a means to increase the moisture resistance of the adhesive. UF adhesives were modified in situ with various hydrophobic and hydrophilic thermoplastic formulations, using either polar or nonpolar initiators. Unmodified and modified UF resins were characterized in terms of viscosity, pH, and gel time in their prepolymer suspension state. Cured solid UF resin plaques were prepared to isolate moisture sorption effects of the cured UF resin from that of the wood component in composites, which dominates their moisture uptake. Relative crosslink density and moisture sorption tests were run on cured UF resin plaques. Results indicated that viscosity increased after modification in most cases, with higher viscosities resulting from formulations using an acidic (polar) initiator. In all cases, activation energies of the curing reactions of thermoplastic‐modified UF suspensions were lower than the unmodified UF. High relative crosslink density compared to the unmodified UF was found for one sample, which correlated well with lower overall moisture sorption. Higher relative crosslink density of cured UF resin plaques appeared to be an indicator of lower moisture uptake. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4222–4229, 2006