可发性改性三聚氰胺–甲醛树脂的制备工艺及配方优化

将甲醛溶液和多聚甲醛按质量比1∶1与一定量的三聚氰胺、改性剂(聚乙二醇200、己内酰胺、一缩二乙二醇、乙二醇)在一定的反应条件下制得可发性改性三聚氰胺–甲醛(MF)树脂,并在80℃下对其进行发泡制备泡沫塑料。采用正交实验考察了反应温度、p H值、甲醛/三聚氰胺物质的量之比(F/M)、改性剂种类及其用量对改性MF树脂固含量、黏度、储存期以及泡沫塑料表观密度的影响,在此基础上通过改变F/M、提高反应温度等单因素实验确定了制备可发性改性MF树脂的适宜优化工艺及配方,即反应温度90℃,p H=9,F/M=2.8,改性剂己内酰胺用量为三聚氰胺质量的14%。在优化工艺及配方下得到的改性MF树脂溶液黏度为1 547.5 m Pa·s,固含量为70.5%,储存期76 h,改性MF树脂发泡性能优良,发泡后泡沫塑料的表观密度为32.76 kg/m3。     

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。     

密胺模塑料的制备与性能研究

用树脂共缩聚的改性方法制备了密胺模塑料,以改善其力学性能。密胺模塑料中纤维素用量为55 phr时,其力学性能最佳;密胺树脂的甲醛/三聚氰胺(F/M)越大,密胺模塑料的力学性能越好,挥发分越高;随着固化剂用量的增加密,胺模塑料的力学性能先提高后降低当,其用量为1.0 phr时密,胺模塑料的综合性能最好。     

低醛三聚氰胺树脂的制备与工艺研究

以三聚氰胺(M)、甲醛(F)和乙二醇(EG)为主要原料,三乙醇胺为催化剂,己内酰胺、H2O2为甲醛吸收剂,采用低n(F)∶n(M)比例、乙二醇醚化MF(三聚氰胺-甲醛)树脂、三聚氰胺分次加料和添加甲醛吸收剂等手段,制备MF树脂。研究结果表明:当n(F)∶n(M)=2.5∶1、n(EG)∶n(M)=2.0∶1、pH值为8～9、反应温度为80℃、三聚氰胺分次加料量为50∶40∶10(质量比)和n(己内酰胺)∶n(H2O2)∶n(甲醛)=10∶5∶100时,制成的MF树脂具有相对较低的游离甲醛含量(0.13%)和相对较长的储存稳定期(>120 d)。     

多聚甲醛与苯酚物质的量比对可发性甲阶酚醛树脂性能的影响

采用多聚甲醛代替37%的甲醛溶液,在20%NaOH水溶液催化下与苯酚逐步加成聚合,合成了可发性甲阶酚醛树脂。研究了多聚甲醛与苯酚物质的量比(F/P)对合成树脂固含量、粘度、游离苯酚、游离甲醛、凝胶时间、分子结构、分子质量、树脂热性能及泡沫性能的影响。结果表明,F/P值为1.8时,可得到性能优良成本较低的可发性甲阶酚醛树脂,树脂粘度1.4 Pa.s,游离甲醛质量分数1.17%,游离苯酚质量分数6.72%,羟甲基指数1.41,树脂分子质量在240左右,耐热性较好。     

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。     

乙二醇体系下三聚氰胺-甲醛树脂的合成与表征

以乙二醇(EG)为溶剂,三聚氰胺(M)和多聚甲醛(F)为主要原料,氢氧化钾和三乙醇胺为催化剂,合成了三聚氰胺-甲醛(MF)树脂。采用红外光谱(IR)、高效液相色谱(HPLC)、核磁共振(13C-NMR)、热重分析等对EG在MF树脂中的反应机理以及MF树脂的热性能进行了分析。研究表明:乙二醇可以与羟甲基化后的三聚氰胺反应,形成亚甲基桥和醚键结构。当m(EG)∶m(M+F)=0.6∶1、n(F)∶n(M)=2.5∶1、pH值为9~10、反应温度为95℃时,合成的MF树脂固体质量分数高(90.2%)、游离甲醛低(0.51%)、储存稳定性好(240 d)。树脂的热失重温度约为345℃,800℃残炭率为17.24%。     

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。     

日用级三聚氰胺甲醛模塑料的制备

以三聚氰胺甲醛树脂为胶粘剂,纤维素为增强材料,制得三聚氰胺甲醛模塑料。通过测试模塑料的力学性能、流动性、挥发分及模收缩率和吸水率等,研究了三聚氰胺与甲醛配比、反应终点控制、纤维素含量、干燥温度、模塑粉细度等对模塑料性能的影响。结果表明,三聚氰胺与甲醛物质的量比为1∶2.5、终点控制在水浊度1∶3,纤维素用量42%~48%,干燥温度70℃,球磨至100~120目时,制得的模塑料性能良好,符合国家日用级产品相关标准。     

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     

Influence of chemical composition on the rheological behavior of condensation reaction resins

In this paper, the chemorheological and dynamic mechanical behavior of melamine‐formaldehyde (MF) resins of four different formaldehyde/melamine (F/M) molar ratios (1.25, 1.5 1.75 and 2.00) are investigated. MF resins polymerize via a polycondensation reaction involving formation of up to 10 wt% of H₂O on cure. This typically results in rapid and extensive foaming of the resin when it is cured under atmospheric pressure. Experimental adaptation for the foaming behavior of MF resins is used to gather rheological information concerning the curing kinetics and the mechanical response of neat MF resins of different molar ratios. Likewise, the procedures developed allow curing of the resins under atmospheric pressure, hence allowing volatile evacuation as occurs during venting procedures (commonly used during compression molding of MF molding compounds) or as a result of absorption by hydrophilic fillers or substrates. The results show that increased moisture content in the B‐stage leads to faster reaction rates and greater foaming. Gelation and vitrification times are identified for each molar ratio, and are found to increase with decreasing molar ratio. The dynamic mechanical behavior of carefully molded neat MF samples of different molar ratios is studied using DMTA. T_g is found to be 200°C for the resin with the lowest formaldehyde content (F/M = 1.25), and around 230°C for the other resins. The storage shear modulus above T_g is studied, and the results show that the crosslink density increases with increasing molar 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     

多指标正交实验优化可发性三聚氰胺甲醛树脂的制备

用己内酰胺作改性剂,通过正交实验设计考察了甲醛和三聚氰胺摩尔比(F/M)、溶液pH值、反应温度(T)和反应时间(t)对可发性三聚氰胺甲醛(MF)树脂的储存期、固含量、黏度、MF泡沫密度及泡孔尺寸均匀性的影响,运用综合评分法和综合平衡法对正交实验结果进行了分析,得出最优水平组合:F/M=2.5,pH=8.0,T=90℃,t=60min。最优条件下合成的MF树脂可发泡性良好,制得的泡沫性能优良。     

酶解木质素改性三聚氰胺脲醛树脂的制备与应用

以酶解木质素（EL）、尿素（U）、甲醛（F）和三聚氰胺（M）为原料,采用碱反应工艺制备了酶解木质素改性三聚氰胺脲醛树脂（ELMUF）。分别考查了EL用量对制备的ELMUF树脂的固化时间、固化温度、游离甲醛量及其制备胶合板胶合强度和甲醛释放量等性能的影响,随着EL用量的增加,ELMUF树脂游离甲醛量从0.26%逐渐降低至0.12%,固化时间从96 s逐渐延长至152 s,黏度由86 mPa·s迅速升高至1 140 mPa·s。通过DSC测定不同EL用量的脲醛树脂固化过程,结果表明：随着EL用量的增加脲醛树脂的反应活性逐渐降低,固化温度由120.6℃逐渐升高至132.0℃,对热压工艺要求更加苛刻。     

腰果酚、三聚氰胺改性酚醛树脂的制备

以苯酚与甲醛作为原料,采用腰果酚、三聚氰胺对酚醛树脂进行改性,研究了腰果酚含量、三聚氰胺含量、催化剂加入方式以及干燥温度等对其性能的影响,得出改性酚醛树脂的适宜生产工艺条件:n(总酚量):n(醛)=1:0.91,n(苯酚):n(甲醛):n(腰果酚):n(三聚氰胺)=1:1:0.1067:0.0541,催化剂含量3.1%,反应时间约为2.5h,真空干燥温度为100℃。     

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）。     

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     

甲醚化MF改性MF/PVA阻燃纤维的结构与性能

以甲醚化三聚氰胺甲醛(MF)树脂、MF树脂和聚乙烯醇(PVA)在一定条件下制得纺丝原液,经湿法纺丝得到甲醚化MF改性的MF/PVA纤维;研究了纺丝过程中氮流失率和纤维的形貌结构、力学性能、热性能以及阻燃性能.结果表明:甲醚化MF的加入可以降低MF树脂在凝固浴中的溶出;随甲醚化MF比例的增加,氮流失率逐渐降低,纤维表面更...