双酚A催化剂技术进展

概述了用于合成双酚A的阳离子交换树脂催化剂的研究与发展过程,重点介绍了巯基改性的阳离子交换树脂催化剂。对离子交换树脂和巯基化剂的结构、改性的方式及其对催化性能的影响进行了评述。并归纳了导致树脂催化剂失活的常见原因。     

国内文献摘要

正双酚A合成催化剂及其制备方法本发明涉及离子交换树脂法合成双酚A的催化剂及其制备方法。其以苯乙烯或取代苯乙烯为单体,二乙烯基苯基甲烷等为交联剂,合成交联比较均匀的共聚体,共聚体磺化、耐温性改性后用作制备双酚A催化剂基础树脂,按照常规技术以巯基烷基胺为巯基化剂,通过部分中和法对基础树脂进行改性,获得双酚A合成催化剂。本发明在交联聚苯乙烯型     

离子交换树脂法合成双酚A

介绍巯基化强酸性离子交换树脂作催化剂生产双酚A的工艺及100吨/年装置生产运转情况。     

双酚A催化剂技术分析

双酚A作为一种重要化工原料,在化工生产中应用比较广泛,其主要组成部分是一个丙酮分子和两个苯酚分子,该合成反应中所用的催化剂为酸性。随着技术的不断发展与革新,催化工艺也逐渐由硫酸到氯化氢,然后是离子交换树脂。工业生产中,各种催化剂应用阶段构成了双酚A的技术发展历程,同时也体现出人类环保意识的增强。针对合成双酚A阳离子催化剂技术的发展过程进行研究,着重对巯基改性阳离子交换树脂催化剂进行分析,阐述了其不足之处及改性方法。     

由双酚A结晶母液的裂解产物合成双酚A反应过程研究

对反应过程所需催化剂种类及其各影响因素进行了考察。研究表明，大孔强酸性离子交换树脂可替代无机酸作为催化剂用于该反应，其中以未经硫基化处理者为佳；原料中水分的存在不利于产物收率和质量，应控制水的质量分数在1％以下。本研究确定的较佳工艺条件为反应温度65℃，停留时间15min、苯酚／对－异丙烯基苯酚摩尔比20，对应的反应收率为98．5％。对双酚A副产物的处理提供了有效方法。     

液态腰果壳油改性酚醛树脂的研究—双酚法树脂的合成

本文对用双酚法合成腰果壳油改性酚醛树脂进行了研究。对原料克分子比、水分、催化剂用量、反应时间对槚如双酚转化率的影响,以及催化剂种类、甲醛用量、pH值、双酚合成转化率对改性酚醛树脂产率、树脂化时间的影响进行了试验。结果表明,槚如双酚的转化率随苯酚、催化剂用量的增加,反应时间的延长而提高,随水分量的增加而降低,改性树脂的收率随甲醛用量和反应体系pH值的增大、双酚转化率的提高而提高,树脂化时间相应缩短。使用强碱类催化剂能获较高的产率,但树脂化时间较长。     

二甲氨基丙硫醇的合成及其在双酚A合成中的助催化效果

以二甲氨基氯丙烷盐酸盐和硫脲为原料合成了二甲氨基丙硫醇,将其作为巯基改性剂,对合成双酚A基础树脂催化剂进行了改性,并考察了其助催化效果。结果显示,当巯基改性率为15%时,改性后催化剂丙酮单程转化率达93.63%,较改性前高出30个百分点,双酚A选择性为97.01%,较改性前略有提高。     

固载杂多酸催化合成双酚芴

以固载磷钨酸为催化剂,芴酮和苯酚为原料催化合成了双酚芴,考察了影响反应的因素,采用FTIR、NMR和MS对产品结构进行了表征,并对自制双酚芴环氧树脂的湿热性能进行了评价。实验结果表明,活性炭固载磷钨酸用于催化合成双酚芴,催化活性高,催化剂易于回收。当固载磷钨酸用量为反应物总质量的15%,n(苯酚)∶n(芴酮)=10∶1,助催化剂β-巯基丙酸用量为0.2mL,反应温度95℃,反应时间12h时,经甲苯重结晶,双酚芴产品的质量分数及收率分别可达99.1%、81.5%。当共混树脂中芴基环氧树脂的质量分数为50%时,二氨基二苯砜(DDS)固化E-44、AG-80和F-44共混树脂的吸水率分别比纯树脂下降了15%、25%、28%,其中F-44共混树脂的玻璃化转变温度提高了近50℃,表明双酚芴作为环氧树脂单体可明显改善树脂的湿热性能。     

发展中的中国石油化学工业——四十一、双酚A

以酚A,简称2,2—双酚基丙烷或2,2—双(4’—羟基苯基)丙烷,英文缩写为BPA,是苯酚、丙酮的重要衍生物。BPA主要用于生产聚碳酸酯、环氧树脂,还可用于生产四溴双酚A和聚砜等重要的工程塑料。 1 工艺技术 世界上具有自己的双酚A技术的厂家有GE、Bayer、Dow化学、千代田(Chivota)、Blachownia等、这些厂家都有多年的双酚A开发和生产经验。其中GE、Bayer、Dow、千代田的技术代表了当今世界双酚A技术的先进水平。 双酚A由两分子苯酚、一分子丙酮缩合而成。此反应的催化剂为酸性催化剂。工业上获得应用的催化剂有硫酸、氯化氢和离子交换树脂,这些不同类型的催化剂在工业上的应用构成了双酚A技术发展的不同阶段。     

巯基助催化剂对双酚A催化剂活性影响

选择4种不同结构的巯基试剂青霉胺、二甲基色胺、N,N-二乙基-4-巯基丁胺和N,N-二甲基-3-巯基丙胺对主催化剂改性,并进行活性评价,结果表明,N,N-二甲基-3-巯基丙胺对双酚A催化剂改性效果最佳,在苯酚与丙酮物质的量比10∶1、反应温度(60~90)℃、空速1 h-1及催化剂用量20 m L条件下,丙酮转化率大于91%,双酚A选择性大于97%。在实验室条件下,助催化剂用量0.7 g和改性时间2 h时,双酚A催化剂活性最好。     

多段滴流床中苯酚丙酮缩合反应分离新工艺

<正> 引言 双酚A(BPA)是制造聚碳酸酯、聚砜及改性酚醛树脂等的重要中间体.工业上BPA均由苯酚和丙酮在酸性催化剂作用下缩合而成.其反应式为     

固载杂多酸树脂催化合成苯甲醛正己硫醇缩醛的研究

以离子交换树脂固载磷钨酸为催化剂合成了苯甲醛正己硫醇缩醛 ,考察了影响收率的因素。其最优条件为 :苯甲醛∶正己硫醇∶催化剂∶二氯甲烷 =1mol∶2 .15mol∶2 0g∶35 0ml,4 3℃回流下进行 ,反应时间 5 .0h ,收率可达 86 .3% ,催化剂可重复使用。     

The simulated moving-bed reactor for production of bisphenol A

Bisphenol A was produced from acetone and phenol over an ion-exchange resin catalyst at 50–90°C. Phenol was used as solvent. The reaction proceeded under the excess phenol condition. The reaction rate was proportional to the acetone concentration in the initial period of the reaction. After the acetone conversion exceeded approximately 50%, the reaction rate became lower than expected by the first-order reaction rate. This was ascribed to water adsorption onto the resin. Batch adsorption and breakthrough experiments showed that water was adsorbed approximately seven times stronger than acetone and that bisphenol A was not adsorbed. Using the reaction rate equation for bisphenol A production, the adsorption isotherms and overall mass transfer coefficients of the components, the numerical simulation of the 3-zone-type simulated moving-bed reactor was carried out. High resin flow rate was required in order to remove water out of the reaction zone, and a high liquid flow rate was also required to desorb water from the resin in the recovery zone. As far as the flow rates were set appropriately, water was successfully removed to prevent the catalyst deactivation and the long-term stable production of BPA was allowed.     

环保型水性酚醛树脂胶的研究

以苯酚与甲醛为原料,合成水溶性酚醛树脂,苯酚与甲醛的物质的量比为1：12-25,在碱性催化剂的作用下合成,其固含量高、黏度低、pH〈9。通过对催化剂的种类和用量、反应温度和时间等的控制,合成出生产过程中零排放的环保型水溶性酚醛树脂胶粘剂。     

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℃。     

Waste liquors from cellulosic industries. IV. Lignin as a component in phenol formaldehyde resol resin

The lignin separated from the spent liquor of soda pulping of rice straw can replace a part of phenol in the condensation reaction with formaldehyde in a basic medium to form phenol lignin–formaldehyde (PL–F) resol resin. The production of phenol lignin–formaldehyde resol resin was carried out in two stages: First was the formation of the adduct (lignin phenol) using different lignin percentages; second was the condensation of the adduct with formaldehyde. Reaction variables, i.e., molar ratio of formaldehyde to phenol lignin, polymerization time, amount of sodium hydroxide as a catalyst, and polymerization temperature in the polymerization step were studied. Solubility of the produced resol resin in different solvents, its viscosity, and yield were determined. Lignin could replace up to 40% of phenol in the produced resin. Infrared spectra of the prepared resin were determined. Structural similarity of phenol–formaldehyde to phenol lignin–formaldehyde resin was shown. Also, relative absorbance of characteristic bands of the resins were calculated and claimed too much on the effect of reaction parameters on the prepared resins.     

Study of heat of reaction between plasma-polymer-coated silica fillers and biphenyl epoxy resin

Silica fillers were coated by plasma polymer coatings of 1,3-diaminopropane, allylamine, pyrrole, 1,2-epoxy-5-hexene, allyl mercaptan and allyl alcohol using RF plasma (13.56 MHz). The coated fillers were then mixed with biphenyl epoxy, phenol novolac (curing agent) and/or triphenylphosphine (catalyst), and subjected to DSC analyses in order to elucidate the chemical reaction between functional moieties in the plasma polymer coatings and the epoxy resin. For comparison, samples were also prepared with liquid monomers, biphenyl epoxy, phenol novolac and/or triphenylphosphine. In addition, silicon wafers were coated by plasma polymerization and analyzed by FT-IR. Only the samples with 1,3-diaminopropane and allylamine plasma-polymer-coated silica fillers showed heat of reaction peaks when they were mixed with biphenyl epoxy resin, while these samples as well as the sample with pyrrole plasma-polymer-coated silica fillers exhibited heat of reaction peaks when mixed with both biphenyl epoxy and phenol novolac (curing agent). However, all plasma polymer samples exhibited heat of reaction peaks when they were mixed with biphenyl epoxy, phenol novolac and triphenylphosphine. The samples with liquid monomers showed a similar behavior, but the peaks appeared in the lower temperature range.     

壬基酚生产工艺条件研究

研究了以苯酚、壬烯为原料 ,酸性阳离子交换树脂为催化剂 ,进行烷基化反应生产壬基酚的工艺条件。最佳反应条件是 :反应温度在催化剂使用初期为 90～ 95℃ ,原料酚烯物质的量比为 (15～ 2 0 )∶1,反应循环比为 (8～ 10 )∶1,反应压力对反应基本没有影响。     

磺酸树脂催化苯酚与正辛醇合成对辛基酚

以正辛醇和苯酚在磺酸树脂的作用下合成对辛基酚,利用单因素试验法,优选出反应的最佳工艺条件:反应温度135~140℃,反应时间20 h左右,催化剂用量约占原料苯酚的0.2,酚醇摩尔比1∶1.2。在此条件下,转化率可达80%,选择性可达80%左右。     

多段悬浮床反应气提生产双酚A的新工艺

研究开发了多段悬浮床反应气提生产双酚Ａ的新设备及工艺，解决了固定床树脂法生产工艺存在的问题。实现了双酚Ａ缩合液的高浓度，高收率，高选择性和高催化剂生产能力。采用正交实验设计法完成了工艺条件对缩合效果影响的显著性分析。