Curing mechanism of alkaline phenolic resin with organic ester

To study the curing mechanism of alkaline phenolic resin with organic ester, three esters were chosen to react with three systems - alkaline phenolic resin, potassium hydroxide aqueous solution containing phenol, and potassium hydroxide aqueous solution. The variations of pH, heat release and gel pH during the reactions were monitored and measured. Infrared spectroscopy （IR） and thermal gravity analysis （TG） techniques were used to characterize the curing reaction. It was found that organic ester is only partial y hydrolyzed and resin can be cured through organic ester hydrolysis process as wel as the reaction with redundant organic ester. The sequential curing mechanism of alkaline phenolic resin cured by organic ester was identified as fol ows： a portion of organic ester is firstly hydrolyzed owing to the effect of the strong alkaline; the gel is then formed after the pH decreases to about 10.8-10.88, meanwhile, the redundant organic ester （i.e. non-hydrolysis ester） starts the curing reaction with the resin. It has also been found that the curing rate depends on the hydrolysis velocity of organic ester. The faster the hydrolysis speed of the ester, the faster the curing rate of the resin.

Application conditions for ester cured alkaline phenolic resin sand

Five organic esters with different curing speeds:propylene carbonate(i.e.high-speed ester A);1,4-butyrolactone;glycerol triacetate(i.e.medium-speed ester B);glycerol diacetate;dibasic ester(DBE)(i.e.lowspeed ester C),were chosen to react with alkaline phenolic resin to analyze the application conditions of ester cured alkaline phenolic resin.The relationships between the curing performances of the resin(including pH value,gel pH value,gel time of resin solution,heat release rate of the curing reaction and tensile strength of the resin sand)and the amount of added organic ester and curing temperature were investigated.The results indicated the following:(1)The optimal added amount of organic ester should be 25 wt.%-30 wt.%of alkaline phenolic resin and it must be above 20 wt.%-50 wt.%of the organic ester hydrolysis amount.(2)High-speed ester A(propylene carbonate)has a higher curing speed than 1,4-butyrolactone,and they were both used as high-speed esters.Glycerol diacetate is not a high-speed ester in alkaline phenolic resin although it was used as a high-speed ester in ester cured sodium silicate sand;glycerol diacetate and glycerol triacetate can be used as medium-speed esters in alkaline phenolic resin.(3)High-speed ester A,medium-speed ester B(glycerol triacetate)and low-speed ester C(dibasic ester,i.e.,DBE)should be used below 15°C,35°C and 50°C,respectively.High-speed ester A or lowspeed ester C should not be used alone but mixed with medium-speed ester B to improve the strength of the resin sand.(4)There should be a suitable solid content(generally 45 wt.%-65 wt.%of resin),alkali content(generally 10 wt.%-15 wt.%of resin)and viscosity of alkaline phenolic resin(generally 50-300 mPa·s)in the preparation of alkaline phenolic resin.Finally,the technique conditions of alkaline phenolic resin preparation and the application principles of organic ester were discussed.

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.

WHEAT STRAW ALKALINE LIGNIN AND ITS DERIVATIVES AS RETENTION AID

In this paper, a new type of retention system of PEO/cofactor retention system is introduced, the cofactors used are phenol-formaldehyde resin, wheat straw alkaline lignin and its derivatives such as hydroxymethylated lignin, sulfited lignin and lignin-based phenol-formaldehyde resin. The first pass retention of newsprint slurry and the properties of handsheet are improved by using the system. The results indicate that a new application field for lignin has been exploited.

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.

碱性酚醛树脂砂表面安定性的试验研究

碱性酚醛树脂砂作为一种环保型树脂砂,在铸钢件生产上得到了广泛应用,但存在表面安定性差的问题,容易导致生产的铸钢件易发生夹砂和粘砂缺陷。为此,首先以碱性酚醛树脂砂为主要研究对象,确定达到实际生产需求的表面安定性为99%,其次筛选碱性酚醛树脂和粉末添加剂,选用了两种粉末添加剂,进行正交试验后得到的最佳工艺方案为:树脂加入量1.2%,原砂采用大林砂40/70号,氧化镁0.1%,可溶性淀粉0.1%。结果表明,相较于优化前,优化后的方案1 h强度提高至0.55 MPa,24 h强度提高至0.93 MPa,表面安定性提高至99.12%,最后进行浇注验证,与优化前相比,优化后的造型方案生产的铸钢件表面质量较好,无夹砂和粘砂缺陷。

基于妥尔油生产及碱辅助DES预处理的生物质全组分利用研究进展

通过成熟的妥尔油生产技术与绿色经济的木质纤维原料预处理技术相结合的方式,为实现天然树脂与纤维素、半纤维素、木质素这4种成分高效绿色分离提供了可能。本文在简单介绍妥尔油成分的基础上,总结了硫酸盐制浆中妥尔油的分离、生产和纯化及其改进方法,妥尔油向生物质化学品和生物质能源的转化应用情况,以及与妥尔油分离环境相似的碱辅助低共熔溶剂(DES)环境下预处理木质纤维原料的研究进展。最后分析了目前碱辅助DES预处理技术与妥尔油生产工艺结合过程中存在的问题,并提出未来的主要研究方向。

玻璃纤维桩树脂核联合E-max全瓷冠修复上前牙牙体缺损临床疗效分析

目的:观察玻璃纤维桩树脂核联合E-max全瓷冠修复上前牙牙体缺损的临床效果,并将其与铸造金属桩核联合E-max全瓷冠的修复效果进行对比。方法:选取2017年1月-2022年1月笔者医院收治的60例上前牙牙体缺损患者,采用计算机随机数字生成器分为A组和B组,每组30例。两组均采用E-max全瓷冠修复,A组采用铸造金属桩核,B组采用玻璃纤维桩树脂核。比较两组修复后1年的修复成功率、修复效果及不良事件发生率,比较修复前、后两组龈沟液基质金属蛋白酶-2(Matrix metalloproteinase-2,MMP-2)、碱性磷酸酶(Alkaline phosphatase,ALP)水平。结果:两组修复成功率比较,差异无统计学意义(P>0.05)。与A组比较,B组颜色匹配率、边缘适合率较高(P<0.05)。修复前两组龈沟液MMP-2、ALP水平比较,差异无统计学意义(P>0.05);修复后与A组比较,B组龈沟液MMP-2、ALP水平降低(P<0.05);与修复前比较,A组龈沟液MMP-2、ALP水平升高(P<0.05),B组水平变化不显著(P>0.05)。与A组比较,B组桩核断裂、牙龈着色及冠折或根折发生率较低(P<0.05)。结论:采用玻璃纤维桩树脂核联合E-max全瓷冠修复上前牙牙体缺损,可有效改善修复效果,减少对牙周组织的刺激及不良事件的发生。

螯合树脂塔再生废水回收工艺改进

优化了螯合树脂塔再生废水回收工艺:将酸性废水送至脱氯塔与淡盐水混合,淡盐水脱氯后,被送至盐水工序用于化盐;将碱性废水直接送至盐水工序用于化盐.工艺优化后,实现了酸性废水和碱性废水的高效回收利用.

碱性环境中BFRP筋耐腐蚀性能试验研究

针对玄武岩纤维增强树脂基复合筋材(BFRP筋)在碱性环境中的耐腐蚀性能和腐蚀机理进行了试验研究,试验变量包括树脂基体种类、碱性环境类别、腐蚀龄期等。碱性环境包括碱溶液浸泡和潮湿混凝土包裹两种,筋材分为环氧树脂基体复合筋(BE筋)和乙烯基酯树脂基体复合筋(BV筋),试验最长龄期为120d。为加速腐蚀效果,试验采用60℃的高温浸泡。并采用扫描电子显微镜(SEM)对腐蚀前后的筋材微观结构进行分析,对腐蚀机理进行了研究。试验结果表明:BE筋腐蚀前后强度均高于BV筋,BE筋的耐碱性能优于BV筋;SEM观察发现沿筋材径向,BE筋中出现明显的腐蚀层和未腐蚀层的分界,而BV筋中没有出现明显的纤维松散层,但是出现了大量的界面脱粘和微裂缝,分析认为强度退化主要是由纤维/树脂界面脱粘导致纤维不能协同受力引起;通过对BFRP筋在直接碱溶液浸泡和混凝土包裹环境下浸泡后的退化规律的比较分析得出,两种情况下的时间转换因子为2.67。

碱性环境下苯酚-尿素-甲醛共缩聚树脂结构形成研究

为了了解碱性环境中苯酚-尿素-甲醛(PUF)共缩聚树脂结构形成规律,为PUF树脂结构控制提供依据,使用13C NMR表征,采用分次加入苯酚、甲醛和尿素的技术路线,定量分析了PUF树脂合成过程中各种官能团的变化和聚合物分子链的构成。结果表明,碱性环境中各种加料方式合成的PUF树脂初聚物具有十分相近的化学结构,PUF树脂也具有十分相近的化学结构,但结构组分存在差异,在原料物质的量之比一定的条件下,最终反应进程基本接近。甲醛分次加入,减少了醚类的生成,有利于简化反应进程。初聚物的热机械性能分析表明不同加料方式对酚醛树脂固化性能无显著影响。

麦草碱木质素基环氧树脂的合成

以麦草碱木质素为原料,在碱性条件下,与环氧氯丙烷发生反应,生成木质素基环氧树脂,采用红外光谱对其结构进行定性分析,通过盐酸—丙酮测定环氧当量对其进行定量分析。考察了环氧氯丙烷的量,氢氧化钠的用量,反应温度和反应时间对环氧当量值的影响。单因素试验结果得出合成环氧树脂的条件为:环氧氯丙烷与碱木质素的质量比为12∶1,每克木质素用氢氧化钠(质量分数20%)5mL,反应温度80℃,反应时间3h。此时环氧值最大,为0.3623。

有机酯加速碱性酚醛树脂凝胶反应机理的研究

通过对凝胶时间的测定和红外光谱分析 ,研究了在室温和强碱性条件下 ,有机酯加速酚醛树脂的固化反应机理 .结果表明 :强碱性条件下 ,有机酯对甲阶酚醛树脂凝胶固化的促进作用 ,是通过快速促进树脂分子生成活性中间体亚甲基醌来实现的 ;同时伴有酚羟基的醚化反应 .有机酯分子中羰基碳原子的电正性越大、空间位阻越小 ;羟甲基含量越高 。

酯固化碱性酚醛树脂粘结剂及其固化机理的研究

研究了酯固化碱性酚醛树脂的合成工艺 ,得到了高强度的粘结剂 ;分析了硅烷偶联剂对粘结强度的影响 。

吸附法精制天然维生素E

对浓度为52.3%的天然维生素E(VE)浓缩液进行精制处理。根据其主要成分的化学性质,采用在乙醇溶剂中用强碱性离子交换树脂吸附其中VE的方法进行精制。通过静态吸附能力试验,发现该树脂对VE吸附能力较强,在25℃条件下,干树脂饱和吸附量为630 mg/g,35℃时干树脂饱和吸附量为450 mg/g。并在此基础上进行了固定床吸附初步探索性试验,在特定的操作条件下绘出该离子交换柱对VE的吸附曲线,洗脱曲线。将洗脱出的溶液浓缩后得到浓度为92.5%的VE浓缩液,树脂的利用率为35%。

三甲铵型阴离子交换树脂的制备及其对Cr(VI)的吸附性能

用氯乙酰化聚苯乙烯树脂代替传统的氯甲基化聚苯乙烯树脂,通过与三甲胺反应得到一种新型的三甲铵型强碱性阴离子交换树脂,对该树脂进行了红外光谱表征、元素分析及微孔结构的测定,同时研究了其对Cr(VI)的静态吸附性能.结果表明,该树脂对Cr(VI)的吸附量随pH的降低而增加,pH=2时最大吸附量达117mg/g.吸附过程在实验浓度范围内符合Langmuir和Freundlich方程,相关系数分别为0.9988和0.9769.动力学研究表明,吸附过程符合Boyd液膜扩散方程,相关系数为0.9927.热力学函数ΔG0<0,表明该吸附过程为自发过程;ΔH0=-3648.16J/mol,说明该吸附过程为放热过程,同时ΔS0=3.98J/(K·mol),说明吸附过程熵增加占主导作用.吸附后用5%的NaOH可以将Cr(VI)洗脱,洗脱率达96%以上.

新型弱碱性阴离子交换树脂对Cr(Ⅵ)的吸附性能

用氯乙酰化聚苯乙烯树脂(PS-Acyl-Cl)代替传统的氯甲基化聚苯乙烯树脂(PS-CH2-Cl),通过其与二乙胺(DEA)的胺化反应得到一种新型弱碱性阴离子交换树脂(PS-Acyl-DEA)。研究了该树脂对C(rⅥ)的静态吸附性能,以期处理含铬废水及铬的富集回收提供理论和实验依据。结果表明,该树脂对C(rⅥ)的吸附量随pH的降低而增加;吸附过程在实验浓度范围内符合Langmuir和Freundlich方程,且最大吸附量达263mg/g,大于文献报道。动力学和热力学研究表明,吸附过程为液膜扩散控制,自发且放热过程。