改性木质素部分取代苯酚制备酚醛泡沫保温材料的研究

为改善酚醛泡沫性能,降低成本,以改性木质素、苯酚、多聚甲醛为原料合成可发性木质素酚醛树脂,通过发泡制备酚醛泡沫。当改性木质素取代苯酚的30%时,研究了缩合时间、缩合温度、催化剂用量、醛酚比和水量对树脂性能的影响,通过热重分析仪(TGA)和生物显微镜分别对酚醛泡沫的热稳定性和微观结构进行分析。结果表明:树脂合成的较佳条件为缩合时间80 min,缩合温度85℃,催化剂用量4%,醛酚比1.5,水量为25ml,泡沫具有较好的热稳定性和致密的微观结构;其力学性能较好,压缩强度为0.21 MPa,弯曲强度为0.15MPa;导热系数为0.030 W/(m?K),氧指数为38.2%,属于难燃型高效保温材料。     

木质素部分取代苯酚制备酚醛树脂及其泡沫的研究

为改善酚醛泡沫的性能,降低其成本,以改性木质素、多聚甲醛、苯酚为原料合成可发性木质素酚醛树脂,通过发泡制备木质素酚醛泡沫。研究了木质素酚化时间、温度及催化剂量对树脂性能的影响,通过红外光谱(FTIR)和热重分析仪(TG)分别对酚化木质素和泡沫的热稳定性进行了分析。木质素的取代量30%时,较佳的酚化条件:酚化时间40 min,温度110℃,催化剂量3%。用酚化木质素制备的木质素酚醛泡沫性能较好,其压缩强度为0.22 MPa,弯曲强度为0.17 MPa,氧指数为38.6%,导热系数为0.029 W/(m·K),属于难燃型高效保温材料。     

粗酚酚醛泡沫的制备及其性能研究

以粗酚、苯酚、多聚甲醛为原料合成了可发性粗酚酚醛树脂,发泡制备了粗酚酚醛泡沫。研究了粗酚用量对酚醛泡沫表观密度、吸水率、压缩强度、弯曲强度、阻燃性等性能的影响。并通过生物显微镜观察、TG分析对粗酚酚醛泡沫的结构和耐热性进行了表征。结果表明:粗酚的加入使泡沫的力学性能、泡孔分布均有所提高。其中粗酚质量分数为30%时,泡沫综合性能最佳,此时,压缩强度为0.206 MPa,弯曲断裂力为36 N,吸水率为5.99%,较纯酚醛泡沫有一定程度提高。粗酚酚醛泡沫氧指数大于40%,阻燃性能优异,导热系数0.031 W/(m.K),保温性能良好。     

催化剂用量对酚醛树脂及泡沫性能的影响

以苯酚、多聚甲醛为主要原料,氢氧化钠(Na OH)为催化剂合成了高固含量酚醛树脂,并以此制备了酚醛泡沫材料。通过粘度、氧指数、力学性能等测试研究了催化剂用量对酚醛树脂及酚醛泡沫性能的影响并采用电子扫描显微镜分析了泡沫的微观结构。结果表明:随着催化剂用量增加,树脂粘度增大,游离酚及游离醛含量降低,泡孔孔径减小且分布更为均匀。催化剂质量分数为4%时制备的酚醛泡沫力学性能较好,单位密度(kg·m-3)压缩强度为2.43 k Pa、弯曲强度为5.52 k Pa、拉伸强度为2.11 k Pa。     

腰果酚改性焦油粗酚酚醛泡沫塑料的研究

为降低酚醛泡沫塑料的成本,改善其性能,以焦油粗酚、苯酚、多聚甲醛为原材料,腰果酚为改性剂,合成可发性腰果酚改性焦油粗酚酚醛树脂,发泡制备出腰果酚改性焦油粗酚酚醛泡沫塑料。研究了腰果酚用量对改性焦油粗酚酚醛泡沫塑料保温性能、阻燃性能、吸水率、力学性能和耐热稳定性等的影响,并通过傅立叶变换红外光谱仪对合成改性焦油粗酚酚醛树脂进行了表征,通过生物显微镜、热重分析仪对改性焦油粗酚酚醛泡沫塑料的微观结构和耐热稳定性进行表征。结果表明,腰果酚的加入使改性焦油粗酚酚醛泡沫塑料的综合性能有较大改善,当腰果酚占混合酚的质量分数为15%时,改性焦油粗酚酚醛泡沫塑料的综合性能最佳,吸水率为4.51%,压缩强度为0.31 MPa,弯曲强度为0.55 MPa,导热系数为0.036 W/(m·K),极限氧指数为35.2%。改性焦油粗酚酚醛泡沫塑料的保温、阻燃性能和耐热稳定性较好,泡孔致密均匀。     

环氧腰果酚/硅氧烷对酚醛树脂及泡沫性能的影响

以环氧腰果酚(ECD)为酚原,替代部分苯酚,同时引入1,3-双(氨丙烷基)四甲基二硅醚(APTMDS),合成改性酚醛树脂,进而制备改性酚醛泡沫。分析APTMDS添加量一定时,ECD替代苯酚量对改性树脂的结构、游离酚含量、游离醛含量、黏度以及热稳定性的影响,研究ECD替代苯酚量对改性泡沫压缩强度、弯曲强度、易碎性能以及燃烧性能的影响。结果表明,当APTMDS添加量一定时,改性树脂体系的游离酚含量随着ECD的替代量的增加而呈下降趋势,游离醛随着ECD的替代量的增加而呈上升趋势,改性树脂体系的黏度随着ECD的替代量的增加有所上升。改性酚醛泡沫的压缩和弯曲强度有很大程度的提高,当ECD替代量为4%(wt)时,改性泡沫的压缩和弯曲强度最大,分别为0.281和0.363 MPa,与纯酚醛泡沫相比,分别提高了91.16%和62.05%。改性酚醛泡沫粉碎率有所降低,当ECD替代苯酚量为12%时,改性酚醛泡沫的粉碎率最小,19.81%,与纯酚醛泡沫相比,下降了24.13%。改性后的酚醛泡沫的阻燃性能略有下降。     

腰果酚改性酚醛泡沫树脂的研究

采用腰果酚作增韧剂对酚醛泡沫树脂进行增韧改性。通过改变反应温度、反应时间、催化剂用量等合成酚醛树脂并制备酚醛泡沫。测定其拉伸强度、固含量、红外光谱图并进行可发泡性试验,最终得到改性酚醛泡沫的最佳工艺条件。实验发现当腰果酚代替量(质量分数)35%,反应温度为100℃,反应时间为3.5 h,催化剂二水合草酸用量为1.65 g时,酚醛树脂的性能最好,拉伸强度为1.8MPa,且发泡效果比较好。     

复合改性酚醛树脂增韧酚醛泡沫的研究

通过在基础酚醛树脂的合成过程中同时引入长链酚(十五烷基酚)和长链醛(戊二醛),分别代替部分苯酚和多聚甲醛,制备了一种复合改性甲阶酚醛树脂,然后以之为改性剂对酚醛泡沫进行增韧。考察了该复合改性酚醛树脂对酚醛泡沫物理力学性能的影响。结果表明:复合改性酚醛树脂的引入显著改善了酚醛泡沫的韧性。另外,随着酚醛泡沫中复合改性酚醛树脂含量的增加,泡沫的弯曲位移增大、压缩强度下降、表观密度增加,吸水率则先减小后增大,而泡沫的氧指数仅略有下降。     

多聚甲醛合成热塑性酚醛树脂过程中游离酚含量的研究

在热塑性酚醛树脂合成过程中,由于苯酚过量,部分苯酚没有参与反应而是进入废液中,不仅导致苯酚的浪费,同时也使废液中的酚含量过高。研究反应体系中酚含量的变化,对提高苯酚的转化率以及减少树脂中游离酚的含量有重要的意义。在酚/醛物质的量比为1∶0. 75的条件下,用草酸做催化剂,催化苯酚与多聚甲醛合成热塑性酚醛树脂。研究了催化剂用量、反应温度和时间、后处理工艺等因素对游离酚的影响。结果表明,草酸用量为苯酚质量1%时,催化效果较好。同时延长低温反应阶段时间,可以提高苯酚的转化率。后处理工艺对最终树脂游离酚含量的影响较大,要保证树脂中的低游离酚含量,后处理的温度和时间是关键。     

生物油酚醛泡沫制备工艺研究

利用生物油中富含酚类物质的特性,将其与苯酚、多聚甲醛反应合成可发性生物油酚醛树脂,通过调整发泡工艺制备出综合性能优异的生物油酚醛泡沫。结果最佳发泡配方为:以树脂质量分数计,催化剂选用复配比例为m(对甲苯磺酸)/m(磷酸)=2∶1的催化剂体系,质量分数为10%~15%;发泡剂选用石油醚,用量为5%~10%;表面活性剂选用吐温-80,质量分数为5%,发泡温度控制在75℃。得到的生物油酚醛泡沫各项性能良好。     

多羟甲基苯酚的合成工艺研究

以苯酚和甲醛为原料，在催化剂存在下经羟甲基化制备多羟甲基苯酚。羟甲基化反应的较佳合成工艺条件为：摩尔比1：3.5、甲醛溶液浓度30％、反应温度30℃、反应时间40h、以丙酮为沉降剂。     

Separation of phenol and formaldehyde from industrial wastes. Modelling of the phenol extraction equilibrium

BACKGROUND: The manufacture of phenolic resins causes the generation of hazardous wastes composed of high concentrations of phenol and formaldehyde together with low molecular weight polymers in lower concentrations. The separation of phenol, mainly from synthetic aqueous solutions, has been successfully achieved by means of solvent extraction, 8 - 17 but few references tackle the treatment of industrial wastes because of their complex behaviour. This work aims at the experimental and theoretical analysis of the recovery of phenol from industrial aqueous wastes using CYANEX 923 as organic extractant. RESULTS: Aqueous condensates containing phenol in the concentration range 40–280 g L^?1, and formaldehyde in the range 30–110 g L^?1, were contacted with CYANEX 923 to analyse the influence of feed pH and of concentration of the selective extractant on the extraction equilibrium. Concerning the pH of the feed phase, it was observed that for values higher than 8.0 a decrease in the distribution ratio of phenol between the organic and the aqueous phases took place. Additionally, caustic conditions promoted formaldehyde degradation reactions in the feed phase. Phenol recovery from the loaded organic extractant was obtained by stripping with NaOH solutions. Best results were obtained working with a CYANEX 923 concentration 0.6 mol L^?1. CONCLUSION: Analysis of the experimental data established the optimum conditions of the selective extraction of phenol from industrial condensates. A mathematical model based on the extraction reaction of 2 moles of phenol per mole of Cyanex 923 described successfully the experimental results. The equilibrium parameter was estimated from the fitting of experimental data to the mathematical model obtaining a value of K = 750.9 (mol L^?1)^?2. Copyright © 2010 Society of Chemical Industry     

甲醛/苯酚配比对可发性甲阶酚醛树脂性能的影响研究

以苯酚、多聚甲醛、甲醛溶液为原料,NaOH为催化剂,采用逐步共聚的聚合工艺,制备可发性甲阶酚醛树脂,采用环保型发泡剂、匀泡剂、实验室自制复合酸固化剂制备阻燃保温酚醛泡沫材料。研究了甲醛/苯酚配比(物质的量之比即F/P)进行单因素分析,对可发性甲阶酚醛树脂的物理性能、有毒物质残余量、分子结构和活性的影响以及与树脂可发性的关系。结果表明,当F/P=2.0时,可发性甲阶酚醛树脂的粘度为2 680 mPa.s,游离甲醛含量为0.75%,游离苯酚含量为2.3%,羟甲基含量为34.83%,泡沫表观密度为0.050 7 g/cm3。     

混酚组成对腰果酚—苯酚—甲醛水溶液体系的初始相态及缩聚产物组成的影响

将腰果酚与液态来酚按不同比例混合形成混酚，再使之与甲醛水溶液在强酸催化下进行共缩聚反应，合成线性树脂，由于因果酚侧链的非极性效应的影响，随混酚中腰果酚的含量的不同，反应体系的初始相态呈均相或两相，影响了缩聚产物的组成。     

Study on adsorption characteristic of macroporous resin to phenol in wastewater

The removal of phenol from solution was investigated using macroporous resin. The effects of initial concentration, pH, and temperature on phenol removal were studied. The experimental results indicated that the adsorption capacity reached equilibrium state within 20 min and adsorption followed pseudo‐second‐order kinetic model. Langmuir isotherm model could be better to describe the isothermal adsorption of phenol, the maximum adsorption capacity (Q_m) and Langmuir constant (K_L) were 103.64 mg/g and 0.2719. Macroporous resin after reached to saturation has a high desorption percentage, indicating that H‐103 is an excellent reusing adsorption material. It provided theoretical references for practical application in phenolic wastewater treatment.     

受阻酚类抗氧剂的复配及发展方向

综述了受阻酚类抗氧剂在几种使用情况下的协同作用机理,并提出了今后受阻酚类抗氧剂的发展方向。     

Synthesis and structural characteristics of polycyclic aromatic hydrocarbon-containing phenol formaldehyde resites

To probe the formation of polycyclic aromatic hydrocarbons (PAHs) during the carbonization, gasification, and liquefaction of coals and other solid fuels, nonsoftening phenol—formaldehyde (PF) co-resites are ideal since they facilitate the incorporation of individual PAHs into a highly crosslinked matrix. A series of PAH and diphenylalkane-containing phenolic co-resites have been prepared using phenol with, as the second component, 2-naphthol, 4-hydroxy diphenylmethane, 4,4′-dihydroxydiphenylethane, 1-(4-hydroxybenzyl)naphthalene, 9-(4-hydroxybenzyl)anthracene, and 9-(4-hydroxybenzyl)phenanthrene. A mole ratio of 3 : 1 (phenol : second phenolic constituent) was adopted to ensure that a reasonably high degree of crosslinking was achieved. The virtually complete elimination of ether and methylol functions from the resoles by curing at 200°C was monitored by solid-state ¹³C-NMR. The resites were also characterized by Fourier transform infrared spectroscopy. The volatile-matter contents of the PAH-containing resites were all higher than that of the normal resite. The carbonization of the 9-(4-hydroxybenzyl)anthracene-containing resite in a fluidized-bed reactor is used to illustrate the potential applications of the PAH-containing resites in fuel science. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 663–671, 1997     

重氮盐水解制酚反应器的分析研究

结合重氮盐水解制酚反应机理及动力学,从化学反应工程的角度出发,对现有重氮盐水解制酚的反应器进行了简单阐述,讨论了现有水解反应器的优点及其局限性,并对其今后研究发展趋势进行了展望。     

Preparation of high viscosity thermoplastic phenol formaldehyde polymers for application in reactive extrusion

This work deals with the synthesis of high molecular weight, thermoplastic phenol formaldehyde (PF) resins for the application in the synthesis of polypropylene–PF compatibilizers by reactive extrusion. Phenol formaldehyde of high molecular weight is required in reactive extrusion with most polypropylene grades to meet the viscosity ratio (λ) requirement for best mixing. Special lab-grades of PF were therefore developed. The polymers synthesized were highly linear and in the M_w range of 10–30 000 g mole⁻¹.     

Modelling of resol resin polymerization with various formaldehyde/phenol molar ratios

The kinetics of polymerization of phenol and formaldehyde are modelled to account for the formation of resol resin with various initial formaldehyde/phenol molar ratios. The conversion of phenol and formaldehyde is used to determine the equilibrium constants for phenolate ion and methylene glycol. The relative concentration of each compound is obtained as a function of time. The molecular weight is also determined for each resol resin at the end of the reaction. The evaluation of substituted phenols, hydroxymethylol phenols and methylene bridges was carried out by infrared spectroscopy. The experimental tendencies are in agreement with the results of the model. © 2001 Society of Chemical Industry