CN1133204A - 失活的磺化芳族有机聚合物离子交换树脂床的再生方法 - Google Patents

失活的磺化芳族有机聚合物离子交换树脂床的再生方法 Download PDF

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CN1133204A
CN1133204A CN95105416A CN95105416A CN1133204A CN 1133204 A CN1133204 A CN 1133204A CN 95105416 A CN95105416 A CN 95105416A CN 95105416 A CN95105416 A CN 95105416A CN 1133204 A CN1133204 A CN 1133204A
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E·J·布雷斯曼
S·J·舍弗
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Abstract

提供了一种在高温下用无水酚使失活的具有化学结合的氨基有机硫醇基的磺化芳族有机离子交换树脂床(例如聚苯乙烯离子交换树脂床)再生的方法。

Description

失活的磺化芳族有机聚合物 离子交换树脂床的再生方法
参看同时提交的共同未决的申请RD-23146。
本发明涉及一种用来使失活的具有化学结合的氨基有机硫醇基的磺化芳族有机聚合物离子交换树脂复原的无水酚处理法。更具体地说，本发明提供了一种用无水酚在高温下处理失活的离子交换树脂的方法，以便使酚与失活的氨基有机硫醇基反应，同时从离子交换树脂中流出酚反应产物。
正如共同未决的申请RD-23146中所述，具有化学结合的氨基有机硫醇基的磺化芳族有机聚合物离子交换树脂可以用来催化酚与酮(例如丙酮)的缩合反应。但是，这种“含硫醇”的离子交换树脂与沾污了至少1ppm羟基丙酮的酚的长期接触会大大降低离子交换树脂的效率或使其“失活”。已经发现，羟基丙酮污染物与氨基有机硫醇基之间的接触会形成化学结合的物种。该物种会大大影响离子交换树脂有效地发挥它作为制造双酚的缩合催化剂的能力。
在共同未决的申请RD-23146中提到的含硫醇的离子交换树脂的另一应用是作为具有化学结合的氨基有机硫醇基的牺牲性离子交换树脂保护床。这种离子交换树脂保护床可以用来提供基本上不含羟基丙酮的纯化过的酚流出物，它延长了离子交换树脂缩合反应器床的寿命。
本发明以以下发现为基础，即通过用无水酚在高温下以间歇的或流动的方式处理树脂，可以使失活的离子交换树脂再生。已经发现，如果在70℃到120℃下用含水0-100ppm的基本上无水的酚处理一个失活的、具有已被化学改性的氨基有机硫醇基的磺化芳族有机聚合物离子交换树脂，则分离或洗脱的结果可得到分子量在约200-400范围内的酚反应产物。当高压液相色谱(HPLC)的结果表明在热的无水酚处理后的流出液中后文定义的三苯酚反应产物的含量少于1ppm时，可以确认离子交换树脂己基本再生。
一种使失活的磺化芳族有机聚合物离子交换树脂再生的方法，该树脂具有化学结合的氨基有机硫醇基团和由于在酚-酮缩合反应期间与羟基丙酮接触而被化学改性的氨基有机硫醇基团，所述的方法包括用含水量约为0到0.01％(重量)的无水酚在70至120℃下处理失活的磺化芳族有机聚合物离子交换树脂，直到形成一种酚反应混合物，所述酚反应混合物主要由酚和由于失活的磺化芳族有机聚合物离子交换树脂与无水酚接触而形成的三苯酚反应产物的混合物组成，其中用HPLC测得的三苯酚反应产物的含量小于约1ppm。
根据质谱数据，由无水酚和失活的离子交换树脂接触而形成的主要反应产物是结构式如下的三苯酚的异构体：
Figure A9510541600041
如后文所用的，有时用于氨基有机硫醇基的“含硫醇的”或“化学结合的”一词是指这些基团可以与磺化芳族有机聚合物(例如聚苯乙烯树脂)的骨架离子键合或共价键合。离子键合的氨基有机硫醇基的一个实例示于Pressman等的美国专利4,584,416中，该专利在本文中引用作为参考。Faler等的美国专利4,455,409中则提到了共价键合的氨基有机硫醇基。
适合用来实施本发明的是具有离子键合的下式所示的氨基有机硫醇基的磺化芳族有机聚合物，其中R是C(2-10)二价有机基团，R1是选自氢或C(1-8)烷基的一价基团。
式(1)的C(2-10)有机基团R包括二价的C(2-10)脂族基，例如1，2-亚乙基、1，3-亚丙基、1，4-亚丁基、1，5-亚戊基、1，6-亚己基；芳基，例如亚苯基、亚二甲苯基、亚甲代苯基、亚萘基等。R还包括进一步被卤素(例如氯、溴、氟等)取代的上面定义的脂族基或芳基。式(1)的R1基包括一价的烷基，例如甲基、乙基、丙基、丁基、戊基、己基、庚基和辛基。
可以在本发明中用来制造具有式(1)的离子键合的烷氨基有机硫醇基的离子交换催化剂的磺化芳族有机聚合物包括例如Rohm&Haas公司制造的Amberlite-118、Dow化学公司制造的Dowex50WX4及其它的磺化芳族有机聚合物，例如用二乙烯基苯交联的磺化聚苯乙烯。
本发明的离子交换树脂可以通过使磺化芳族有机聚合物和N-烷氨基有机硫醇单体进行反应来制备，后者可以是氢卤化物或相应的甲苯磺酸氢盐的形式。例如，一种合成N-烷氨基有机硫醇甲苯磺酸氢盐的方便方法包括先使溴氯烷烃和碱金属硫代硫酸盐在有机溶剂(例如含水甲醇)中于惰性气氛下回流反应。向所形成的反应混合物中加入合适的烷基胺，再回流。甲醇及过量的烷基胺可以从混合物中蒸馏除掉，加入异丙醇，通过共沸蒸馏除掉水。然后将异丙醇浆体过滤，使烷氨基有机硫代硫酸盐及副产物碱金属卤化物与水分离。
上述的烷氨基有机硫代硫酸盐和对甲苯磺酸一水合物及甲醇的混合物可以在氮气氛下回流，随后进行通常的有机萃取及后处理，得到溶在氯化烃溶剂中的所要的产物。然后加入适当的脂族烃溶剂使甲苯磺酸盐沉淀并过滤分离。
本发明的具有离子键合的N-烷氨基有机硫醇基的离子交换树脂催化剂可以通过使磺化芳族有机聚合物与N-烷氨基有机硫醇盐进行反应来制备，后者可以是如上所述的卤化物盐或甲苯磺酸盐的形式。干树脂形式的磺化芳族有机聚合物可以先用标准的中和法分析其磺酸含量，通常每4.70克干树脂含22.1毫摩尔磺酸基。将适量的氨基有机硫醇的氢卤化物或甲苯磺酸氢盐(通常为基础树脂上磺酸基的0.25当量)以水溶液的形式与基础树脂一起加热。将混合物在室温至70℃下加热4小时，同时缓慢搅拌，然后冷至室温。随后将所得的离子交换催化剂过滤，用水洗涤，然后用真空烘箱干燥。
离子交换催化剂的氮百分含量可以用Carlo Erba氮分析仪测定。根据此数据可以确定每克干催化剂中氮的毫克当量数，它表示总的磺酸位点中被式(1)的N-烷氨基有机硫醇基占据的分数。每克干催化剂中硫醇的毫克当量数可以用Ellman试剂测定(A.Fontant和C.Toniolo，The Chemistry of the Thiol Group，S.Patai编，JohnWiley & Sons公司，伦敦，1979，288-290页)。
为了使本领域技术人员能更好地实施本发明，给出以下实施例作为示例说明，但不是对本发明的限制。所有的份数均为重量份。
                      实施例
为了制备沾污的含硫醇的芳族有机聚合物，先由Rohm & Hass公司用4％二乙烯基苯(DVB)交联的聚苯乙烯磺酸型产品Amberlite118制成“原始的催化剂”。将Amberlite118用2-氨基乙硫醇处理，直到20％的酸位被中和。将7.5份1.75％的氨基乙硫醇盐酸盐(Aldrich化学公司)水溶液与1份Amberlite118磺酸树脂在氮气氛下缓慢地机械搅动数小时，以制备原始催化剂，所述水溶液是在室温下用氦吹洗过的水配制的。滤出催化剂，用水充分洗涤，在真空烘箱中干燥过夜(83℃，箱内真空度～20托)。
催化剂的硫醇含量通过对由磺酸树脂中解吸下的苯甲酰化等分试样作HPLC分析来确定。将200mg催化剂称入一只4英钱的小瓶中，加入磁搅拌子和3.5ml 1.5M的NaOH水溶液。搅拌4分钟后，加入过量的(4滴，约90mg)苯甲酰氯。将溶液搅拌40分钟。加入2.5ml含约200mg酚的1.5M NaOH水溶液或1ml含4滴正丙胺的水使多余的苯甲酰氯的作用骤停。再搅拌40分钟以后，将溶液过滤，用总量40ml的二氯甲烷和40ml水洗涤树脂。分离出滤液层，水层用40ml二氯甲烷洗涤。合并的有机层用无水MgSO4干燥，过滤，在旋转蒸发仪上蒸发。用一台带有100mm×4.6mm的5μm Hewlett-PackardODS Hypersil反相柱的HPl090液相色谱仪进行HPLC分析，在235nm、254nm和280nm处监测。注入含苯乙酮的10％腈溶液作为内标。
使原始催化剂在使用富含羟基丙酮(HA)的原料的连续式BPA反应中失活(进料＝8∶1(摩尔比)的酚/丙酮，还含有228ppm HA；重时空速(WHSV)＝20g进料·g-1·催化剂·小时-1；70℃，8小时)。原始催化剂和失活的催化剂的硫醇含量均列在表1中。将失活的树脂在含20％水的酚(酚∶水(重量比)＝80∶20)中进行间歇式处理基本上不能使树脂的硫醇含量增加，这里加入水是为了部分模拟BPA反应条件。用水含量小于约100ppm的无水酚作间歇式处理使硫醇含量大大增加。用无水酚作流动式处理使硫醇含量比用无水酚作间歇处理时又有额外增加。所得结果如下：
                     表1
         催化剂中氨基乙硫醇的含量
催化剂   辅助处理      毫克当量H2NCH2CH2SH/克
原始催化剂   -                  0.856
失活的       -                  0.367
失活的    间歇式含水酚          0.381
失活的    间歇式无水酚          0.530
失活的    流动式无水酚          0.609
用无水酚对失活的催化剂进行流动式处理时，将装在玻璃储器内的无水酚泵送流过与玻璃柱连接的热的不锈钢管，玻璃柱内装有17.3g失活的催化剂，WHSV＝6.5(向上流动)，温度保持在70℃。
间歇式处理失活的催化剂时，将5份纯化过的酚、1份失活的催化剂以及1份水(或不加水)一起在70℃下用磁搅拌器搅拌100小时。
由于无水酚的处理而造成的硫醇含量的提高伴随着分子量约为200至400的酚反应产物的流出；其主要组分的分子量约为320，由三个苯氧基单元和一个HA单元衍生形成。在有水存在时不发生同样的转变，因此在使用含水酚或者在通常的酚与羰基化合物缩合的反应条件下不发生这种转变。
虽然以上实施例只涉及可以用来实施本发明的很多方法中的几个，但是应该明白，本发明可用于处理更大范围内的具有化学结合的氨基有机硫醇基的磺化芳族有机聚合物离子交换树脂床的失活。

Claims (7)

1.一种使失活的磺化芳族有机聚合物离子交换树脂再生的方法，该树脂具有化学结合的氨基有机硫醇基团和由于在酚-酮缩合反应期间与羟基丙酮接触而被化学改性的氨基有机硫醇基团，所述的方法包括用含水量约为0到0.01％(重量)的无水酚在70至120℃下处理失活的磺化芳族有机聚合物离子交换树脂，直到形成一种酚反应混合物，所述酚反应混合物主要由酚和由于失活的磺化芳族有机聚合物离子交换树脂与无水酚接触而形成的三苯酚反应产物的混合物组成，其中用HPLC测得的酚反应产物的含量小于约1ppm。
2.根据权利要求1的方法，其中芳族有机离子交换树脂是聚苯乙烯。
3.根据权利要求1的方法，其中氨基有机硫醇基是离子键合的。
4.根据权利要求1的方法，其中氨基有机硫醇基是共价键合的。
5.根据权利要求1的方法，其中芳族有机离子交换树脂用流动处理法再生。
6.根据权利要求1的方法，其中芳族有机离子交换树脂用间歇处理法再生。
7.根据权利要求1的方法，其中氨基有机硫醇基是2-氨基乙硫醇基。
CN95105416A 1994-05-02 1995-05-02 失活的磺化芳族有机聚合物离子交换树脂床的再生方法 Pending CN1133204A (zh)

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US6620939B2 (en) * 2001-09-18 2003-09-16 General Electric Company Method for producing bisphenol catalysts and bisphenols
US6534686B1 (en) 2001-09-18 2003-03-18 General Electric Company Method for producing bisphenol catalysts and bisphenols
US6703530B2 (en) 2002-02-28 2004-03-09 General Electric Company Chemical reactor system and process
JP3862007B2 (ja) * 2002-05-31 2006-12-27 信越化学工業株式会社 スルホン化樹脂触媒の再活性化方法
US7112702B2 (en) * 2002-12-12 2006-09-26 General Electric Company Process for the synthesis of bisphenol
US7132575B2 (en) * 2003-07-01 2006-11-07 General Electric Company Process for the synthesis of bisphenol
WO2012036819A1 (en) * 2010-09-14 2012-03-22 Exxonmobil Chemical Patents Inc. Dehydrogenation process of cyclohexanone and phenol compositions
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