Complexation Between Borate ion and Hydroxyl Groups of Phenol-Formaldehyde Resol Resin

The complexation reaction between borate ions and phenol-formaldehyde resol resin in aqueous solution was studied by pH measurement, small model molecules and infrared spectroscopy. The results show that the complexation can proceed completely and rapidly at room temperature. Borate ion attacks phenol hydroxyl groups and adjacent position hydroxymethyl groups on the phenol ring of the resin, and forms the coordinate bond between boron atom in borate ion and oxygen atom in the hydroxyl groups. The complexation is a quantitative reaction. The complex is a six member ring containing two oxygens and one boron. The complexation can release hydrogen ions resulting in the decreasing pH in the resin solution.

Curing reaction and mechanism of phenol-formaldehyde novolac resins for foundry

In this study on the curing dynamics of phenol-formaldehyde novolac resins(PFNR) and hexamethylene tetramine(HMTA), two typical commercial PFNR were selected as examples and the curing reactions of the resins with HMTA were studied by differential scanning calorimetry(DSC). Based on the data calculated by the Kissinger equation and the Crane equation, a thermocuring dynamic model was established, from which the process conditions, activation energy, reaction kinetics equation and a f irst-order reaction of the curing reactions were derived.

Study on binder system of CO_2-cured phenol-formaldehyde resin used in foundry

A new aqueous alkaline resol phenol-formaldehyde resin has been prepared from phenol and formaldehyde using NaOH as catalyst; the optimum synthetic process has been determined. With addition of some cross-linking agents, after passing carbon dioxide gas through the resin bonded sand, high as-gassed strength and 24 h strength are achieved. The bonding bridge of the resin bonded sand fracture has been analyzed by using SEM.

Reinforcement of Lignin-Based Phenol-Formaldehyde Adhesive with Nano-Crystalline Cellulose (NCC): Curing Behavior and Bonding Property of Plywood

The curing behavior of lignin-based phenol-formaldehyde (LPF) resin with different contents of nano-crystalline cellulose (NCC) was studied by differential scanning calorimetry (DSC) at different heating rates (5, 10 and 20&degC/min) and the bonding property was evaluated by the wet shear strength and wood failure of two-ply plywood panels after soaking in water (48 hours at room temperature and followed by 1-hour boiling). The test results indicated that the NCC content had little influence on the peak temperature, activation energy and the total heat of reaction of LPF resin at 5 and 10&degC/min. But at 20&degC/min, LPF0.00% (LPF resin without NCC) showed the highest total heat of reaction, while LPF0.25% (LPF resin containing 0.25% NCC content) and LPF0.50% (LPF resin containing 0.50% NCC content) gave the lowest value. The wet shear strength was affected by the NCC content to a certain extent. With regard to the results of one-way analysis of variance, the bonding quality could be improved by NCC and the optimum NCC content ranged from 0.25% to 0.50%. The wood failure was also affected by the NCC content, but the trend with respect to NCC content was not clear.

Impregnated Paper-Based Decorative Laminates Prepared from Lignin-Substituted Phenolic Resins

High Pressure Laminates(HPL)panels consist of stacks of self-gluing paper sheets soaked with phenol-formaldehyde(PF)resins.An important requirement for such PFs is that they must rapidly penetrate and saturate the paper pores.Partially substituting phenol with bio-based phenolic chemicals like lignin changes the physico-chemical properties of the resin and affects its ability to penetrate the paper.In this study,PF formulations containing different proportions of lignosulfonate and kraft lignin were used to prepare paper-based laminates.The penetration of a Kraft paper sheet was characterized by a recently introduced,new device measuring the conductivity between both sides of the paper sheet after a drop of resin was placed on the surface and allowed to penetrate the sheet.The main target value measured was the time required for a specific resin to completely penetrate the defined paper sample(“penetration time”).This penetration time generally depends on the molecular weight distribution,the flow behavior and the polarity of the resin which in turn are dependent on the manufacturing conditions of the resin.In the present study,the influences of the three process factors:(1)type of lignin material used for substitution,(2)lignin modification by phenolation and(3)degree of phenol substitution on the penetration times of various lignin-phenolic hybrid impregnation resins were studied using a complete twolevel three-factorial experimental design.Thin laminates made with the resins diluted in methanol were mechanically tested in terms of tensile and flexural strains,and their cross-sections were studied by light microscopy.

NaOH and Ba(OH)_2 Compound Catalyzed PhenolResorcinol-Formaldehyde Copolycondensation Resin Adhesive for Recombined Bamboo

In order to reduce the curing temperature, shorten the curing time of phenol-formaldehyde(PF) resin adhesive, and ensure the good water-solubility, NaOH and Ba(OH)_2 were used as compound catalysts. The influences of the adding time of Ba(OH)_2, the adding amount of NaOH, Ba(OH)_2 and resorcinol on the properties of adhesives were studied. The properties of NaOH catalyzed phenol-formaldehyde(PF) adhesive, NaOH and Ba(OH)_2 compound catalyzed PF adhesive, NaOH and Ba(OH)_2 compound catalyzed phenol-resorcinol-formaldehyde(PRF) adhesive, and the prepared recombinant bamboo with three kinds of adhesives were compared. The experimental results show that NaOH and Ba(OH)_2 compound catalyst not only shortens the curing time of PF adhesive, but also guarantees the suitable water solubility of adhesive. After copolycondensation with resorcinol, the curing time of adhesive is further shortened, the water solubility is improved obviously, and the highest bonding strength is obtained. Infrared spectrum analysis shows that the reaction activity point of NaOH and Ba(OH)_2 compound catalyzed PRF adhesive will increase, so that both the curing temperature and curing enthalpy decrease.

聚合物热裂解碳材料结构对电化学性能的影响

Carhons were prepared at different temperatures by pyrolytic treatment of phenolformaldehyde resin molded with ZnCl2 in advance. X-ray structure analyses have shown that these carbon are essentially amorphous with rather loose structure of molecular size order with an interlayer distance of 0.36—0.37 nm. Using electrochemical methods, we have studied the insertion of lithium within these materials. Resole resins, heated to 580 ℃, have a reversible capacity of about 400 mA·h/g, which is beyond the theoretical capacity of graphite（372 mA·h/g） and discover that carbons with a smaller crystallite size and large interlayer distance have the larger discharge capacity.

低密度支撑剂用酚醛/环氧树脂改性复合材料的研究

采用液体酚醛树脂浸渍,再用环氧树脂包覆的方法制备了以坚果壳为基体的低密度支撑剂用复合材料,通过IN STRON万能材料试验机,TGA,SEM等测试手段测试了复合材料的性能。研究表明,浸渍的酚醛树脂溶液浓度达到70%时,复合材料在60M Pa压力下变形量有一最小值;随着颗粒表面包覆层环氧树脂量的增加,复合材料在60M Pa压力下变形量逐渐减少,当树脂量大于25%时,变形量变化不大;TGA表明复合材料耐热性提高;SEM发现未包覆改性的颗粒表面有较多孔洞,包覆改性后的复合材料表面较光滑,孔洞明显减少;显微镜照片显示未包覆改性的颗粒60M Pa压力下严重破裂,而复合材料没有破裂现象,且颗粒表面有明显的树脂层;吸水能力由30.45%降至6.58%,耐溶剂性能明显提高。

硼酸盐含量对CO_2固化甲阶酚醛树脂粘结剂性能的影响

利用溶解度、溶液粘度和砂芯抗压强度的测定,粘结剂固化膜和粘结桥断口的扫描电镜(SEM)分析,研究了硼砂在碱性水溶液中的溶解现象、对CO2固化甲阶酚醛树脂粘结剂性能的影响以及过量硼酸盐在粘结桥中的存在状态。结果表明,在碱性水溶液中硼砂的溶解度比纯水中要大得多,碱性越强,硼砂的溶解度越大;随着硼砂含量的增大,粘结剂的粘度逐渐增大,而粘结强度则先增大,后减小,在含量为11%时出现极大值;过量的硼酸盐会以结晶盐的形式存在于粘结桥中,使粘结剂的粘结强度下降。

炭化温度对酚醛树脂基活性炭孔结构及电化学性能的影响研究

以酚醛树脂为炭前驱体,KOH作活化剂,通过调节炭化温度在相同活化条件下制备了具有不同孔隙结构的活性炭材料。N2吸附测试表明随着炭化温度降低,活性炭材料比表面积先增大后减小,孔容则不断增大。其中,550℃炭化样品与KOH反应活性最佳,可制得比表面积为2983m2/g,总孔容为1.58cm3/g,中孔孔容达到0.59cm3/g的活性炭材料。采用直流充放电法、交流阻抗法和循环伏安法测定以上述多孔炭为电极材料的双电层电容器的电化学性能,结果表明,PF550活性炭材料电容性能最佳,在有机电解液中100mA/g充放电时,比电容达到160F/g,电流密度增大50倍容量保持率达到82%,显示出良好的功率特性;活性炭材料中存在一定比例的中孔不仅可以改善电极材料的功率特性,而且可以提高微孔的利用率。

催化剂对Resole酚醛树脂结构与性能的影响

分别以氨水、三乙胺、氢氧化钠为催化剂合成了3种Resole酚醛树脂,通过pH值,凝胶色谱、红外光谱分析等方法,讨论了不同催化剂的催化反应机理,催化剂对Resole树脂的分子质量及分布以及树脂结构的影响。将3种树脂通过浸渍和热压工艺制备了酚醛树脂层压板,测试了其弯曲性能。结果表明,3种催化剂的催化效率依次为是NaOH>三乙胺>氨水。采用3种催化剂所合成的树脂具有相似的化学结构。采用三乙胺为催化剂时,所制备的层压板具有最佳的工艺性和力学性能。

酚醛树脂热裂解碳阳极的不可逆容量损失

用酚醛树脂热裂解得到的无序碳为阳极研究了在第一次循环时不可逆容量损失的原因 .实验结果表明 ,不可逆容量损失是由于溶剂分解产生了 Li2 CO3和在碳表面上形成了含—COO-基和 C—H基的化合物以及在碳主体上形成了含— OLi,—

尿素增韧改性甲阶酚醛树脂的合成及其泡沫

在合成阶段用不同量的尿素增韧改性甲阶酚醛树脂,并将改性后的树脂制备成泡沫,测试改性泡沫的性能。结果显示:随着尿素用量的增加,泡沫的吸水率、韧性、阻燃性上升,压缩强度下降,热稳定性有所改善;合成过程中的最佳尿素用量为3%。

硼酸与甲阶酚醛树脂的配位反应及配合物的结构

本文通过对溶液pH值的测定和红外光谱分析 ,研究了硼酸与甲阶酚醛树脂的配位反应。结果表明 :在室温下硼酸能与甲阶酚醛树脂中的羟基发生配位反应 ,并产生H+ 使溶液的pH值降低 ;溶液的酸性强弱与甲阶酚醛树脂中的羟甲基含量和硼酸的用量有关 ;硼酸以硼酸根离子的形式与树脂中的酚羟基和邻位羟甲基发生配位反应 ,形成了一个含有两个氧原子和一个硼原子的六元环 。

改性热固性酚醛树脂热熔胶膜成膜工艺及其性能

针对低成本且环保的热熔预浸工艺,研制一种满足热熔工艺成膜性和高耐热性要求的改性热固性酚醛树脂(MPF)胶膜。采用流变仪和差示扫描量热仪,对MPF的固化反应特性和凝胶特性进行分析,利用粘度预测函数,建立粘度-温度-时间的函数关系模型,预测胶膜树脂的低粘度平台,可指导热熔MPF胶膜的制备及成膜性能研究。为保证树脂充分浸渍纤维,热熔预浸工艺树脂浸润纤维预制体的温度应在95~135℃(粘度小于1 000 mPa·s)。热熔法MPF胶膜的成膜温度在75~95℃(粘度范围在1 000~3 000 mPa·s),75℃条件下,MPF低粘度保持时间可达到120 min。固化后的MPF在1 200℃的氮气气氛中,残炭率可达到65%。此类新型热熔法MPF可为其在高性能树脂基复合材料领域的应用提供参考。

碱对CO_2固化甲阶酚醛树脂粘结剂性能的影响

利用溶液粘度和砂芯抗压强度的测定、粘结桥断口的扫描电镜(SEM)和盐成分的电子能谱(ESCA)分析,研究了碱在CO2固化甲阶酚醛树脂粘结剂中的作用及对性能的影响。结果表明,碱是甲阶酚醛树脂水溶液的一种有效分散剂,与NaOH和LiOH相比,用KOH配制的树脂溶液粘度较低;随着KOH浓度的增大,树脂溶液的粘度逐渐增大,粘结剂的粘结强度则先增大,后减小,在25%时出现极大值;在强碱性粘结剂的作用下,砂粒表面会部分溶解,溶解部分固化后与粘结剂中的碱一起形成复盐;碱对甲阶酚醛树脂/硼砂水溶液的稳定性有较大的影响,只有在较强的碱性条件下体系才能稳定存在。

低分子量水溶性酚醛树脂的合成及表征

以Ba(OH)2.8H2O为催化剂,在苯酚与甲醛摩尔比为1∶2的条件下,采用一次逐步加入甲醛的方式合成了低分子量水溶性酚醛树脂。使用13C_NMR对产物结构进行表征,通过GPC、DSC测量最终产物的分子量及分布和热行为。结果表明:在Ba2+催化作用下的羟甲基化反应中,苯酚的邻位活性更高。合成的水溶性酚醛树脂是聚合度为2～4的聚合体的混合物,这些聚合体以邻-对位和对-对位方式连接形成亚甲基桥,有大量的高邻位取代羟甲基苯酚,树脂多分散指数为1.17,分子量分布较窄,DSC谱图分别在144～168℃和186～199℃出现两个独立的放热峰,树脂通过两步反应实现最终固化。

高羟甲基含量甲阶酚醛树脂的合成

利用KOH作催化剂 ,以甲醛和苯酚为原料合成了一种高羟甲基含量的甲阶酚醛树脂 ,通过羟甲基含量、可被溴化物含量、固有粘度的测定和甲醛转化率的计算 ,研究了反应条件对合成的影响。结果表明 :随着反应温度的升高、甲醛和KOH用量的增加、反应时间的延长 ,树脂中的羟甲基含量先增加 ,后减小 ,树脂的固有粘度则逐渐增大 ,其中反应温度和催化剂用量的变化对树脂固有粘度的影响较大。在 6 5℃的条件下 ,n(甲醛 )∶n(苯酚 )∶n(氢氧化钾 )为 2 .5∶1∶0 .1时 ,反应 3h ,甲阶酚醛树脂中的羟甲基质量分数可以达到 32 .8% ,固有粘度达到2 .6 8ml·g-1。

pH值对酚醛甲阶树脂固化速率的影响

利用碱土金属镁的氧化物或氢氧化物作为酚醛树脂缩聚反应的催化剂，制成酚醛甲阶树脂，通过加入酸度调节剂，探讨了pH值对酚醛甲阶树脂的固化特性的影响。结果表明：与氢氧化钠-酚醛树脂不同，对于镁-酚醛树脂，加入合适的酸度调节剂可以使树脂固化速度加快，聚合时间明显缩短。在中性或接近中性条件下，树脂在150℃的聚合时间基本在35—60s之间。

高分子量热固性酚醛树脂的合成与性能

采用两步法,先合成热塑性酚醛树脂母体,再对其进行羟甲基化反应得到相对分子量800以上的热固性酚醛树脂。随树脂分子量增大,其凝胶时间缩短,在150℃可以实现<3 min内完全固化。同时随着原料Novolac树脂分子量增大,其改性后树脂溶液的黏度呈增长趋势,凝胶时间缩短;羟甲基化率(决定于甲醛用量)的增加可显著降低改性后树脂溶液的凝胶时间,但对溶液黏度的影响不明显;而反应时间在12 h后对于凝胶时间和溶液黏度影响很小。