CN113999337A - 一种超大孔含氟超强酸催化树脂及其合成方法 - Google Patents
一种超大孔含氟超强酸催化树脂及其合成方法 Download PDFInfo
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Abstract
本发明是一种具有三维交联结构的超大孔含氟超强酸催化树脂,具有二氟甲基磺酸的超强酸性;由于具有稳定的三维交联结构,能长期耐受高温有机溶剂的溶胀,超大孔结构非常稳定,保持长期稳定的超强酸催化能力,在酯化、醚化、环氧基开环和酸催化重排等有机合成反应中,具有高效清洁和长期反复使用低成本的巨大优势。
Description
技术领域
本发明是一种超大孔含氟超级强酸催化剂树脂,应用于有机合成绿色高效催化的化工领域。
背景技术
超强酸是酸强度比98%浓硫酸更强的酸,是一种非常高效的催化剂;在大量有机合成反应中,诸如酯化、醚化、重排裂解或环氧基开环醚化等大量单元有机反应中,需要强酸催化,催化剂酸强度越大,收率越高,反应条件越温和。相比于硫酸等小分子液体强酸,现有的大孔强酸树脂能回收反复使用,虽然酸强度远弱于98%硫酸,,但清洁环保不腐蚀设备又成本低,具有很大的应用优势;
国内外常见的强酸催化是采用等效于对甲苯磺酸的大孔强酸树脂,诸如国产D001~D003大孔强酸树脂,或者采用浓硫酸催化;浓硫酸虽然酸强度很大,也很廉价,但液体酸的设备腐蚀严重,产品中的硫酸最后需要中和洗涤,既产生大量硫酸盐污染物,又需要分离产品硫酸盐而生产效率大幅降低。如果采用大孔强酸树脂催化,可以避免硫酸催化的设备腐蚀和废盐污染,但由于酸强度比硫酸弱10万倍以上,合成生产的催化效率也会大幅下降。最常见的稳定含氟超级强酸是三氟甲基磺酸,酸强度是浓硫酸的100倍以上,但三氟甲基磺酸是沸点仅仅169℃的液体酸,设备腐蚀严重,又容易挥发,也需要中和产生三氟甲基磺酸盐废盐污染。现有的强酸催化有机合成反应,非常需要一种大孔超强酸催化树脂,能高效催化,又绿色环保无残留,又不腐蚀设备,又能反复使用成本低。
常见化学稳定的强酸酸强度pKa依次降低如下:
(1)三氟甲磺酸:-13.8 没有氧化性,酸强度最强的含氟有机超强酸,酸容量≥6.66mmol/g;
(2)二氟甲基磺酸: -11.9 没有氧化性;
(3)杜邦Nafion树脂:-12.1 没有氧化性;酸容量≤1.2mmol/g,裸露酸容量≤0.6mmol/g;
(4)98%浓硫酸:-11.8 氧化性很强;
(5)对甲苯磺酸:-5.8 没有氧化性;
(6)大孔强酸树脂:-5.8 没有氧化性; 等效于对甲苯磺酸酸强度,远弱于硫酸的酸强度。
CN201610256925.1介绍了采用式D化学结构的含氟双烯交联单体、式E化学结构的五氟丙烯基硫醚单体和六氟丙烯聚合得到交联的大孔二氟甲基磺酸树脂,由于具有交联结构,催化孔道稳定不溶胀于有机溶剂。式E单体聚合后,经过氧化变为二氟甲基磺酸的超强酸,具有和Nafion树脂等效的超强酸性。但这种大孔含氟超强酸树脂,由于式D/式E化合物合成困难昂贵,污染严重,一直无法低成本量产;
其中:R1为H、叔丁基或氯等。
CN201410017118介绍了一种多孔全氟磺酸树脂的制备方法,是一种等效二氟甲基磺酸的含氟超强酸,由非常昂贵的具有式F化学结构的全氟磺酸单体和四氟乙烯聚合而成;
由于没有添加双烯交联单体,只是掺杂造孔剂聚合固化后脱除造孔剂,催化剂树脂没有交联结构,孔道结构不稳定,能被醇类、酮类或芳香烃溶剂等在≥100℃的强酸催化有机反应中,树脂孔道会溶胀而消失,比表面积大幅下降,失去超强酸催化能力。 而且由于全氟烷基链非常柔软,即使没有有机溶剂的溶胀,多孔结构的全氟烷基超强酸树脂非常容易变形,堵死孔道。
CN1337891A详细介绍了多孔全氟磺酸树脂催化剂的制备方法,采用SO2或CO2高压气体,和Nafion全氟磺酸树脂混合物加热到150~300℃,然后减压爆裂的方法制备多孔超强酸催化树脂,多孔的比表面积能够达到0.1~5M2/g,这么小的比较面积,大量二氟甲基磺酸没有裸露在催化孔道中,催化效率很差;由于母体树脂是采用式F化学结构全氟磺酸单体的Nafion全氟磺酸树脂,没有交联结构,在加热到≥100℃的有机溶剂中,这种多孔催化树脂的孔道会溶胀消失,失去催化性能。
郭琰辉介绍了采用二乙烯基苯和苯乙烯合成的大孔强酸树脂的合成《浙江化工》2015,V.46,No.2,P.28-30,能回收反复使用,也不腐蚀设备,但这是一种酸强度等效对甲苯磺酸的大孔强酸树脂,酸性较弱,催化能力不强。
理想的大孔超强酸催化树脂,既要具有三氟甲基磺酸(CF3SO3H)的超强酸性,离子酸量大于1.5mmol/g;又必须交联聚合,在高温有机反应中孔道稳定,合成容易廉价,能用得起。最好催化树脂的孔道能更大更稳定,物料穿过更迅速,从而大幅提高催化效率。现有的超强酸催化树脂都存在各种缺陷,全氟材料太柔软,没有交联结构的多孔超强酸催化树脂孔道不稳定,很容易变形堵死,催化寿命不长;而且全氟多孔催化树脂非常昂贵,难以大量使用。因此,本发明提供一种具有稳定交联的超大孔含氟超强酸催化树脂,能容易地廉价合成。
发明内容:
本发明是一种具有交联超大孔的含氟超强酸催化树脂,具有二氟甲基磺酸的超强酸性;由于具有接近式G化学结构的稳定交联结构,能长期耐受高温有机溶剂的溶胀,超大孔结构非常稳定,保持长期稳定的超强酸催化能力;
其中:n=5~20。
本发明的超大孔含氟超强酸催化树脂,采用式B化学结构的二(4-异丙烯基苯)砜为超大孔结构的双烯交联单体,需要经过聚合和氧化的两步反应过程:
(1)聚合反应:采用式B化学结构的双烯交联剂,在高压釜中混合六氟丙烯、式A化学结构的五氟丙烯基羟烷基硫醚、疏水溶剂、乳化剂、增粘剂和水,加入过氧化二酰基叔烷引发剂后,加热聚合为超大孔聚合物微球;
其中:R=甲基或氢;
(2)氧化反应:超大孔聚合物微球混合在含微量水的醇类溶剂中,保持在10~50℃通入氯气或溴素氧化聚合物微球羟乙基硫醚为羟烷基砜;在聚合物微球不再吸收氯气或溴素后,加入强碱性次氯酸钠,继续聚合物微球主链上的羟烷基砜氧化为二氟甲基磺酸盐。
聚合反应的疏水溶剂采用叔丁基苯、氟苯或纯苯等低自由基链转移的有机溶剂;疏水溶剂和五氟丙烯基羟烷基硫醚的质量比为1:1.5~2.5;
聚合反应的过氧化二酰基叔烷引发剂,采用疏水的式C化学结构的过氧化二酰基叔烷引发剂:
其中:R2为甲基或乙基。
聚合反应的聚合反应温度为10~80℃,优化反应温度为40~60℃;
聚合反应的乳化剂采用十二烷基苯磺酸钠,增稠剂是少量聚乙烯醇,加入水溶解透明为微粘稠的水溶液;
聚合反应的五氟丙烯基羟烷基硫醚和六氟丙烯的摩尔比是1:2~3;
氧化反应采用含水微量的醇类溶剂选用甲醇或乙醇。
由于式B化合物具有二苯基砜的刚性分子链结构,聚合的超大孔含氟超强酸树脂具有合适的刚性主链,不会变形堵死,能在各种有机溶剂强酸催化反应中保持稳定的超大孔结构,砜基的强吸电子效应,使苯基的a-碳不容易氧化,自由基聚合活性大幅增强。
通过调节六氟丙烯和式A结构的五氟丙烯基羟烷基硫醚的摩尔比,能保证超大孔含氟超强酸催化树脂的离子交换容量能达到1.4~2.0mmol/g,远大于Nafion超强酸树脂的0.8~1.0mmol/g;比表面积能达到20~40M2/g,比CN1337891A的爆裂多孔Naflion超强酸树脂的0.1~5M2/g大幅增加,二氟甲基磺酸能完全裸露参与强酸催化。
常用技术术语:
(1) 离子交换容量:每1000g催化树脂干重的磺酸基含量,等同于酸容量;
(2) 酸强度pKa: 强酸质子H+解离度的平衡常数,pKa值为负值越大,酸性越强;三氟甲基磺酸(CF3SO3H)pKa=-13.8,是最强的含氟有机超强酸;
(3) 双烯交联单体:具有2个聚合活性烯键的有机分子,能使聚合链交联固化为三维空间稳定的多孔结构。
附图说明
附图1:超大孔的超强酸催化树脂的聚合单元结构;
附图2.:超大孔聚合物微球的固定柱氧化系统;
1:三口瓶;
2:磁子;
3:平流泵;
4:超大孔含氟超强酸树脂;
5:层析柱;
6:下口阀门;
7:温度计。
具体实施方式:
为了更好地理解本发明,本发明举例以下实施例,但本发明不限于下面的实施例;
分离得到的超大孔含氟超强酸树脂的检测:采用扫描电镜测定孔径大小,采用筛分法确定粒径大小;
式A结构的五氟丙烯基羟烷基硫醚、二(4-异丙烯基苯)砜、疏水溶剂和式C结构的过氧化引发剂,在加入高压釜前都冷冻保持≤10℃。
实施例1:
(1)在2000ml的三角烧瓶中加入1000g纯水、5g十二烷基苯磺酸钠和30g聚乙烯醇颗粒,加热下搅拌溶解透明,冷却到≤10℃,然后倒入3000ml不锈钢高压釜中,加入五氟丙烯基羟乙基硫醚105g(0.5mol)、二(4-异丙烯基苯)砜9g(0.03mol)、160g叔丁苯和过氧化二酰基叔丁烷2g,密封后抽真空到≤20mmHg,然后计量加入150g六氟丙烯(1.0mol),缓慢搅拌保持在30~50r/分钟,加热升温到50℃,引发聚合,反应放热,内盘管通水冷却保持高压釜料温低于70℃,聚合反应2h后反应结束,冷却泄压,倒出来抽滤,收集白色聚合物微球。将白色球型颗粒倒入2000ml三口瓶中,加入1000ml纯水,加热共沸脱水,将叔丁苯完全共沸蒸出。冷却到室温后抽滤搜集脱溶白色聚合物微球。
(2)将脱溶的白色聚合物微球加入玻璃层析柱中,下阀门固定在2000ml三口瓶上;三口瓶中加入85%含水甲醇1200g,磁力搅拌下通入氯气5~10g/分钟,保持三口瓶料温≤30℃,将含氯气的甲醇水溶液用PTFE平流泵输送到层析柱上口,液面浸没聚合物微球,调节层析柱下流量和上口进入量平衡,湿氯气迅速氧化微球羟烷基硫醚为羟烷基砜基,直到层析柱下流液体开始出现氯气的黄绿色,三口瓶中停止通氯。
(3)更换新的2000ml三口瓶,加入活性氯≥8%的新鲜强碱性次氯酸钠水溶液1500g,保持在≤30℃下,用柱塞泵输送次氯酸钠水溶液到层析柱上口,液面浸没聚合物微球,层析柱上口进料和下口出料平衡,不断循环次氯酸钠水溶液,在循环氧化2h后,层析柱下口流出次氯酸钠活性氯含量和上口的活性氯含量无变化,氧化反应结束。
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到277g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.3~1.5mm,孔径大小为40nm~160nm,离子交换容量为1.8mmol/g,比表面积为28M2/g。
实施例2:
六氟丙烯通入180g(1.2mol),其他的具体投料及合成操作,和实施例1相同;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到308g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.4~1.5mm,孔径大小为40nm~180nm,离子交换容量为1.6mmol/g,比表面积为32M2/g
实施例3:
六氟丙烯通入225g(1.5mol),其他的具体投料及合成操作,和实施例1相同;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到355g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.4~1.5mm,孔径大小为40nm~220nm,离子交换容量为1.4mmol/g,比表面积为36M2/g。
实施例4:
过氧化引发剂采用过氧化二酰基叔戊烷,添加2g引发剂;其他的具体投料及合成操作,和实施例1相同;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到279g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.3~1.5mm,孔径大小为40nm~160nm,离子交换容量为1.8mmol/g,比表面积为30M2/g。
实施例5:
疏水溶剂采用300g氟苯,其他的具体投料及合成操作,和实施例1相同。由于氟苯沸点太低只有85℃,在高压釜密封后抽真空脱除空气时损失56g氟苯;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到276g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.3~1.5mm,孔径大小为30nm~150nm,离子交换容量为1.8mmol/g,比表面积为29M2/g。
实施例6:
式A化合物采用五氟丙烯基羟丙基硫醚112g(0.5mol),其他的具体投料及合成操作,和实施例1相同;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到272g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.4~1.6mm,孔径大小为30nm~160nm,离子交换容量为1.7mmol/g,比表面积为22M2/g。
实施例7:
式B化合物的二(4-异丙烯基苯)砜加入12g(0.04mol),其他的具体投料及合成操作,和实施例1相同;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到282g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.4~1.6mm,孔径大小为30nm~160nm,离子交换容量为1.7mmol/g,比表面积为34M2/g。
实施例8:
式B化合物的二(4-异丙烯基苯)砜加入12g(0.04mol),六氟丙烯加入180g(1.2mol),其他的具体投料及合成操作,和实施例1相同;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到312g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.4~1.6mm,孔径大小为30nm~160nm,离子交换容量为1.6mmol/g,比表面积为32M2/g。
实施例9
第一步聚合按照实施例1投料和合成操作,第二步氧化投料和合成操作如下改变:加入层析柱中氧化聚合物微球,三口瓶中加入95%乙醇1000g,用恒压漏斗滴加溴素5g/分钟,保持三口瓶料温≤30℃,将含溴素的乙醇水溶液用PTFE平流泵输送到层析柱上口,液面浸没聚合物微球,调节层析柱下流量和上口进入量平衡,湿溴素迅速氧化微球羟烷基硫醚为羟烷基砜基,直到层析柱下流液体开始出现溴素的红色,三口瓶中停止滴加溴素。其他的具体投料及合成操作,和实施例1相同;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到278g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.4~1.6mm,孔径大小为30nm~160nm,离子交换容量为1.8mmol/g,比表面积为26M2/g。
实施例10:
六氟丙烯加入180g(1.2mol),疏水溶剂叔丁基苯加入250g,其他的具体投料及合成操作,和实施例1相同;
层析柱用纯水冲洗到pH中性后,倒出聚合物微球,在80℃/20mmHg真空烘箱中减压烘干,得到309g白色聚合物微球,即为超大孔含氟超强酸催化树脂,粒径0.4~1.6mm,孔径大小为30nm~180nm,离子交换容量为1.6mmol/g,比表面积为36M2/g。
应用实施例1:
将实施例1制备的超大孔超强酸催化树脂催化甲醇和环氧丙烷合成丙二醇甲醚;
将酸化/洗涤到中性的200g超大孔超强酸催化树脂加入层析柱中,层析柱的下口阀门密封在3000ml三口瓶中;
3000ml三口瓶中加入1000g无水甲醇,加热沸腾,经过冷凝管回流到层析柱上口,浸没超大孔超强酸树脂液面,层析柱下口阀门调节流量平衡,甲醇回流三口瓶,洗涤除去树脂中的水分。在回流1h后,洗涤结束;将含水甲醇换掉,加入1800g无水甲醇,保持在30~40℃,将500g环氧丙烷常压下5g/分钟匀速加入三口瓶中磁力搅拌均匀,用平流泵5~10ml/分钟输送甲醇/环氧丙烷溶液到层析柱上口,浸没催化树脂液面,调节层析柱下口阀门流量平衡,反应放热,在环氧丙烷加入结束后,继续反应1h结束。GC检测产物,环氧丙烷转化率99%,丙二醇甲醚选择性98.2%。
应用实施例2:
将实施例1制备的超大孔超强酸催化树脂催化环氧氯丙烷连续重排为氯丙酮:
在内径30mm*长800mm的不锈钢层析柱中,加入400g酸化完全又洗净烘干无水的超大孔含氟超强酸树脂,90℃水浴加热层析柱夹套,保持催化树脂层温度80℃以上;
3000g环氧氯丙烷倒入5000ml三角瓶A中,平流泵从层析柱密封上口输送环氧氯丙烷10~20g/分钟,调节层析柱下口阀门流量6~10g/分钟,以保持不锈钢层析柱内压低于1.0MPa,层析柱出来的重排产物流入带回流冷凝器的5000ml三口瓶B中。前面300g重排产物倒回三角瓶A。反应结束后,GC分析:环氧氯丙烷转化率:99.3%,收率94.7%。
Claims (7)
1.一种超大孔含氟超强酸催化树脂及其合成方法,采用式B化学结构的二(4-异丙烯基苯)砜为超大孔结构的双烯交联单体,需要经过聚合和氧化的两步反应过程:
(1)聚合反应:采用式B化学结构的双烯交联剂,在高压釜中混合六氟丙烯、式A化学结构的五氟丙烯基羟烷基硫醚、疏水溶剂、乳化剂、增粘剂和水,加入过氧化二酰基叔烷引发剂后,加热聚合为超大孔聚合物微球;
其中:R=甲基或氢;
(2)氧化反应:超大孔聚合物微球混合在含微量水的醇类溶剂中,保持在10~50℃通入氯气或溴素氧化聚合物微球羟乙基硫醚为羟烷基砜;在聚合物微球不再吸收氯气或溴素后,加入强碱性次氯酸钠,将聚合物微球主链上的羟烷基砜继续氧化为二氟甲基磺酸盐。
2.根据权利要求1所述的聚合反应,其主要特征是疏水溶剂采用叔丁基苯,氟苯或纯苯等低自由基链转移的有机溶剂;疏水溶剂和五氟丙烯基羟烷基硫醚的质量比为1:1.5~2.5。
4.根据权利要求1所述的聚合反应,其主要特征是聚合反应温度为10~80℃,优化反应温度为40~60℃。
5.根据权利要求1所述的聚合反应,其主要特征是乳化剂采用十二烷基苯磺酸钠,增稠剂是少量聚乙烯醇,加入水溶解透明为微粘稠的水溶液。
6.根据权利要求1所述的聚合反应,其主要特征是五氟丙烯基羟烷基硫醚和六氟丙烯的摩尔比是1:2~3。
7.根据权利要求1所述的氧化反应,其主要特征是采用含水微量的醇类溶剂选用甲醇或乙醇。
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