三聚氰胺改性树脂的研究进展

三聚氰胺改性树脂是 类逐步发展起来的新型胶粘剂，用三聚氰胺改性脲醛树脂和酚醛树脂，可以提高它们的耐水性和其他性能。三聚氰胺改性树脂包括三聚氰胺-尿素-甲醛树脂(MUF)、苯酚-三聚氰胺-甲醛树脂(PMF)、苯酚-尿素-三聚氰胺-甲醛树脂(PUMF)、尿素苯酚-三聚氰胺-甲醛树脂(UPMF)等，主要介绍了以上各种树脂的合成机理、制备工艺及其应用的研究进展情况。     

配方精选

<正>改性聚醋酸乙烯酯乳液胶黏剂聚醋酸乙烯酯乳液70脲-三聚氰胺-甲醛树脂30三乙醇胺调pH值至7.5~8.0其他助剂适量性能及用途:该胶外观为白色,无粗颗粒,固含量为(41±1)%。干式复合水性聚氨酯胶黏剂     

骏化3万t／a三聚氰胺建成投产

河南骏化集团年产3万t三聚氰胺工程于2006年3月15日正式投产。三聚氰胺是重要的有机化工原料，广泛应用于塑料、木业、涂料、胶黏剂、造纸、纺织、建材、皮革等储多行业。三聚氰胺与甲醛反应可制得三聚氰胺甲醛树脂胶黏剂，具有耐热、耐水、耐磨、耐酸碱、耐老化、阻燃等优良性能。在脲醛树脂胶黏剂制备中加入三聚氰胺，可降低产品中游离甲醛含量，并提高耐水性和稳定性。     

不同合成方法对MUF共缩聚树脂性能的影响

以三聚氰胺、尿素、甲醛为主要原料,合成了三聚氰胺-尿素-甲醛(MUF)共缩聚树脂。考查了不同合成方法对MUF共缩聚树脂性能的影响。结果表明,不同合成工艺对树脂的甲醛含量以及稳定性有重要影响。DSC分析发现,在相同固化条件下,以工艺2合成的MUF树脂固化速度更快。用MUF制备的胶合木的性能,均可满足日本JAS中的规定。     

复合薄膜用双组分水性聚氨酯胶黏剂的制备和性能

制备了复合薄膜用双组分水性聚氨酯胶黏剂,初步研究了两种外加型交联剂环氧树脂6360、三聚氰胺-甲醛树脂对胶黏剂性能的影响。红外谱图和差示扫描量热法分析的结果表明在双组分水性聚氨酯胶黏剂中水性聚氨酯和交联剂发生了交联反应。外加交联剂可增加水性聚氨酯胶黏剂的交联度和黏度,从而有效提高胶黏剂的T型剥离强度和耐溶剂性能。环氧树脂较佳加入量在5%左右而三聚氰胺-甲醛树脂约为10%。由双组分水性聚氨酯胶黏剂黏合的PET/PE薄膜在较高温度下适当处理一段时间,其黏合效果更佳。     

三聚氰胺-尿素-甲醛共缩聚树脂胶黏剂性能的研究

探讨了三聚氰胺用量、反应温度、反应时间、pH值对三聚氰胺-尿素-甲醛共缩聚树脂胶黏剂性能的影响。结果表明：在三聚氰胺用量为30%,反应温度为90℃,反应时间为40min,pH值为5.5时合成的胶黏剂性能优良。     

MF合成工艺对MUF储存稳定性影响研究

从三聚氰胺甲醛树脂(MF)合成阶段的n(F)∶n(M)配比、缩聚时间、改性剂和稀释剂含量方面,探讨了MF合成工艺对MUF(三聚氰胺-尿素-甲醛树脂)储存稳定性的影响。研究结果表明:当MF制备过程中n(F)∶n(M)=1.8∶1、MF缩聚时间为120 min、pH值为9.5、PVA(聚乙烯醇)水溶液为稀释剂和使用双组分改性剂时,MUF的储存稳定性相对最好,并且相应胶合板的胶合强度相对最大。     

低物质量比甲醛-尿素-三聚氰胺树脂快速固化剂研制

用普通固化荆对低物质量比甲醛-尿素-三聚氰胺树脂胶粘剂进行固化已不能满足实际生产需要,通过对单一和复合固化剂的反复试验,找出了一种能够使低物质量比甲醛-尿素-三聚氰胺树脂胶粘剂快速固化,适用期又能满足实际生产需要的固化剂。     

微波辐射法合成葡萄糖苯酚树脂胶黏剂

以葡萄糖代替甲醛合成一种新的环保型酚醛树脂胶黏剂。在碱性条件下以微波加热法合成葡萄糖苯酚树脂胶黏剂、通过正交实验获得最佳反应条件,同时以此方法对树脂的固化条件进行了研究。微波加热条件下合成葡萄糖苯酚树脂胶黏剂的最佳条件是：葡萄糖：苯酚=7：1;pH：12;催化剂用量：1．4％;反应时间：6min。实验证明,微波辐射波法可以成功合成葡萄糖苯酚树脂胶黏剂,且该胶黏剂是一种环保型胶黏剂。     

低甲醛含量六羟基树脂植绒胶黏剂的研究

作为一种植绒胶黏剂,六羟基树脂胶黏剂因甲醛含量偏高而受到诸多限制。对六羟基树脂植绒胶黏剂的低甲醛化进行了研究。结果显示,以三聚氰胺和甲醛作为原料,采用3次投料法,并进行甲醚化可使所得胶黏剂甲醛含量降低至0.2%,含固量达到80%(质量分数),且耐干磨性、耐湿磨性及水溶性均良好。     

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。     

三聚氰胺-尿素-甲醛共缩聚树脂胶粘剂的研制

通过合成三聚氰胺-尿素-甲醛树脂(MUF)胶粘剂,探讨了三聚氰胺用量对该MUF胶粘剂耐水性和其它性能的影响。结果表明:随着三聚氰胺用量的增加,MUF胶粘剂的耐水性能提高、固含量增大、固化时间和储存期延长,并且胶合板剪切强度增大,但MUF胶粘剂中游离醛含量降低;当w(三聚氰胺)40%时,MUF胶粘剂性能提高并不明显,为了降低成本,选择w(三聚氰胺)=30%～40%时较适宜;三聚氰胺用量不同是影响MUF结构和基团含量的主要因素。     

改性三聚氰胺-尿素-甲醛共缩聚树脂胶粘剂的合成

通过三聚氰胺-尿素-甲醛(MUF)共缩聚树脂胶粘剂的合成,探讨了三聚氰胺的用量对该MUF树脂耐水性能的影响及其规律。实验结果表明,当w(三聚氰胺)=43%～65%时,该MUF树脂的湿强度从0.93 MPa增加到2.74 MPa,耐沸水性明显提高;但是,当w(三聚氰胺)>65%时,该MUF树脂的湿强度增长极其缓慢,其耐沸水性提高并不明显;通过引入复合改性剂和适量的水,可使该MUF树脂的游离甲醛含量降低50%、成本降低10%～15%、固含量基本不变、胶合强度和耐沸水性均有所提高且适用期良好。     

三聚氰胺添加方式对MUF胶粘剂性能的影响

以三聚氰胺作为脲醛树脂(UF)的共聚改性剂制备MUF(三聚氰胺甲醛树脂)胶粘剂。探讨了三聚氰胺的添加方式对MUF胶粘剂性能的影响,同时对其固化特性、分子结构和耐热性等进行了分析。结果表明:三聚氰胺2次投料法可有效降低MUF胶粘剂的甲醛释放量,但其胶接强度也随之下降;同时,该MUF固化体系的外推固化温度、表观活化能和反应级数均有所增加,耐热性降低;另外,2次投料体系使MUF的相对分子质量降低、相对分子质量分布变宽。     

Impact of curing condition on pH and alkalinity/acidity of structural wood adhesives

Nine formulations were selected for evaluating the effect of different curing methods on pH and alkalinity or acidity of various structural wood adhesives. These included four phenol–formaldehyde (PF) resins with high pH, one phenol–resorcinol–formaldehyde (PRF) resin with intermediate pH, two melamine–urea–formaldehyde (MUF) resins, and two melamine–formaldehyde (MF) resins with low pH. The four curing methods used in the study were: (1) curing at 102–105°C for 1 h (based on CSA O112.6‐1977), (2) four‐hour curing at 66°C followed by 1‐hour curing at 150°C (based on ASTM D1583‐01), (3) curing at room temperature overnight (based on ASTM D 1583‐01), and (4) cured adhesive squeezed out from glue lines of bonded shear block samples. The effect of the different methods on pH and alkalinity/acidity of the cured adhesive depended strongly on the individual adhesives. For the PF, the alkalinity was different for the different formulations in the liquid form, while in the cured form, the difference in the alkalinity depended on the curing method used. The MF and the MUF were the adhesives most affected by the method used. In particular, the MUF showed much higher cured film pH values when cured by method 2 compared to the other three methods, while both the cured MF and MUF exhibited quite variable acidity values when cured with the different methods. The PRF showed reasonably uniform cured film pH but varying acidity values when cured with the different methods. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Variation of MUF and PMUF resins mass fractions during preparation

The variation of molecular mass distribution with the progress of the reaction was studied for the following: (i) sequential‐type melamine–urea–formaldehyde (MUF) resin formulations in which the sequence of addition of chemicals follows well‐defined species reactivity principles; (ii) a nonsequential MUF formulation in which simultaneous melamine and urea competition for formaldehyde yields a MF resin cocondensed with small amounts of urea. This resin became soaked with reacted and unreacted monomeric urea species. (iii) A PMUF resin, namely a MUF resin with a small proportion of phenol (7.8% by weight on melamine and urea) cocondensed with the main MUF fraction. All the formulations used were industrial resins formulations in current use. Development and variation of molecular mass fractions, from which performance and other useful resin parameters depend, have been found to depend on the type of resin formulation used for these type of aminoplastic resins. The two very different MUF resin formulations yielded different variations in molecular mass fractions during the progress of the reaction and during the so‐called ambient temperature “maturing” of the resin. The PMUF resin also showed both similar and different fractions present during manufacturing and during short term ageing at ambient temperature. While similarities in recurrent fractions and in trends are common to all the three different formulations, differences between them are also clearly observed. A major proportion of the reaction of some of the aminoplastic resins examined also occurs on ageing (i.e.“maturing” of the resin at ambient temperature), this appearing to be an essential phase of the resin preparation process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4842–4855, 2006     

Diffusion hindrance vs. wood-induced catalytic activation of MUF adhesive polycondensation

The reaction of hardening of melamine–urea–formaldehyde (MUF) adhesive resins in the presence of wood and cellulose was confirmed to have a lower energy of activation than the MUF adhesive alone, both in the presence or absence of ammonium chloride hardener, thus both in mildly acid and mildly alkaline environments. DSC exotherms showed that during hardening of melamine to melamine, melamine to urea, and urea to urea crosslinks through methylene bridges occur. Only the earliest reaction, mainly melamine to melamine crosslinking, presents a decrease in energy of activation which can be assigned to catalytic activation by the cellulosic substrate. The other types of crosslinking reactions (i) appear not to occur due to the more favorable and rapid melamine to melamine reaction which precedes them at lower temperature or (ii) do not present catalytic activation by the substrate but rather hindrance by it or (iii) variation of their energy of activation appears to be due to increased diffusion hindrance by the substrate caused by the increasing molecular weight of the resin while hardening. This because the Kissinger equation plots of the resin alone are in the main linear, for all the exotherms, indicating that in hardening of the resin alone diffusion problems appear to be limited. © 1995 John Wiley & Sons, Inc.     

MF树脂羟甲基化度对MF/PVA共混纤维结构及性能的影响

采用不同羟甲基化度的三聚氰胺甲醛(MF)树脂与聚乙烯醇(PVA)溶液共混湿法纺丝,制备MF/PVA共混纤维;借助扫描电子显微镜研究了MF与PVA的相容性,凯氏定氮法分析了共混纤维在纺丝过程中氮流失率,并对纤维的力学性能、阻燃性能、耐热水性能及热稳定性进行了测试表征。结果表明:改变甲醛与三聚氰胺的比例可以获得不同羟甲基化度的MF树脂;随着MF树脂羟甲基化度的提高,共混纤维的氮流失率逐渐降低;当MF树脂的羟甲基化度增大至1.15时,共混纤维氮流失率为0.20%;高羟甲基化度MF制成的共混纤维经220℃处理后,断裂强度和断裂伸长率分别为3.19 cN/dtex和25.1%,极限氧指数为33.2%,水中软化点为86℃,在氮气氛围下的初始热分解温度为258.8℃,600℃时残炭量为24.63%。     

Low addition of melamine salts for improved melamine‐urea‐formaldehyde adhesive water resistance

The addition of melamine acetate salts to an adhesive glue mix can allow the use of melamine–urea–formaldehyde (MUF) resins of lower melamine contents (rather than just urea–formaldehyde resins) and lower total amounts of melamine. Performances can be obtained that are characteristic of the top‐of‐the‐line, generally higher melamine content MUF adhesive resins for the preparation of wood particleboard panels. Improvements in the panel internal‐bond strength of greater than 30% can be obtained by the addition of melamine acetate salts to top‐of‐the‐line MUF resins. The approach to the concept of increased melamine solubility with a melamine salt is compatible with the approach of increasing melamine solubility with solvents such as acetals (e.g., methylal). However, the synergy advantage of using the two approaches jointly is not very marked. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 287–292, 2003     

Chemical composition of melamine-urea-formaldehyde (MUF) resins assessed by near-infrared (NIR) spectroscopy

Melamine-urea-formaldehyde (MUF) resins are commonly used in the production of wood-based panels. The composition of the resin influences many properties of the final product. In industrial production, some properties, such as viscosity, pH, solid content, or molar ratio, are assessed after resin production in order to evaluate if they are within the desired parameters. These properties are useful for quality control of amino resins. However, almost no information is obtained if a certain type of reagent or filler is wrongly added to the formulation, even though the resin's final adhesive performance will be affected. Evaluation of the molar ratio of the reagents might be the only of the few industrially used tests capable of making this assessment. Near-infrared spectroscopy (NIR) is a fast and reliable technique for quality control of amino resins and can give a wide range of information regarding chemical composition of these products. This work intends to test the capability of NIR to assess several properties related to MUF resins’ chemical composition. The approach considered two types of problems: 1) whether there was a flaw on resin manufacture process and 2) which raw-material (amount or kind) was incorrectly added to the reactor. Using NIR spectra of a wide range of MUF resins, several models were established to predict the molar ratio of formaldehyde and urea (F/U), molar ratio of formaldehyde and melamine (F/M), molar ratio of formaldehyde and amino groups (F/(NH₂)₂), total urea (% U) and total melamine (% M). These models were constructed using the multivariate technique of Partial Least Squares (PLS) and could successfully determine the properties of a set of industrial resins. The coefficients of variation (CV) obtained were equal or lower than 5%, except for the property of F/M, which was 17%. A more thorough analysis of the established models reveals that spectral components of melamine are harder to extract by PLS than components of formaldehyde or urea.