CN103896742A - 一种阳离子交换树脂固载离子液体催化合成双酚f的方法 - Google Patents

一种阳离子交换树脂固载离子液体催化合成双酚f的方法 Download PDF

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CN103896742A
CN103896742A CN201410033044.4A CN201410033044A CN103896742A CN 103896742 A CN103896742 A CN 103896742A CN 201410033044 A CN201410033044 A CN 201410033044A CN 103896742 A CN103896742 A CN 103896742A
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刘跃进
肖丹
李勇飞
吴志民
王庆
聂真
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Abstract

本发明公开了一种以阳离子交换树脂固载离子液体为催化剂，苯酚、甲醛为原料，经缩合反应制备双酚F的方法。所采用的催化剂是以咪唑类离子液体、强酸性阳离子交换树脂为原料，通过化学键合法制备得催化剂前驱体，再与

Description

一种阳离子交换树脂固载离子液体催化合成双酚F的方法
技术领域
本发明涉及一种催化合成双酚F的方法。 
背景技术
双酚F，化学名为二羟基二苯基甲烷，有2，2′、2，4′、4，4′-三种同分异构体，是一种重要的化工中间体。由于其化学结构特点，适合于制备低粘度环氧树脂，其成品在耐热性、耐湿性、绝缘性、加工性及注塑浇铸等性能方面均优于双酚A环氧树脂，尤其是其便于注塑浇铸流动、可以少加甚至不加稀释剂的特点，特别适合于大型风电叶片环氧树脂的加工成型，也大大减少了环境污染，改善了加工环境。 
专利JP58177928、JP08268943、JP08268943、JP08198790报道了以无机酸、有机酸为催化剂合成双酚F的方法。无机酸催化收率高，但对设备腐蚀性严重、副反应多；有机酸催化反应条件温和，对设备的腐蚀性较轻，但副反应多、酚醛比高、产率低。专利JP11269113和专利CN101987812A分别报道了沸石分子筛、介孔分子筛催化合成双酚F的方法，此类方法产物分离和催化剂回收比较容易，但酚醛比和反应温度较高，反应难于控制，原料消耗较大。 
专利CN102584541A报道了一种用咪唑类离子液体催化合成双酚F的方法，该方法具有不使用其它溶剂、缩短反应时间、无挥发、可回收重复使用等优点，是一种新型高效绿色环保的双酚F制备方法，离子液体催化合成双酚F收率较高，但存在4，4′-双酚F含量少，离子液体成本、用量和反应温度都偏高，离子液体的分离回收也还存在一定损失。 
为了达到既高效利用离子液体绿色环保的催化活性，又解决离子液体分离回收和用量偏大问题的目的，本发明提出一种阳离子交换树脂固载离子液体催化合成双酚F的新方法。该方法具有离子交换树脂磺酸基团与离子液体咪唑环活性碳原子双功能复合高效催化合成双酚F、载体廉价易得、离子液体用量少、 催化剂便于分离回收、绿色环保等优点，便于工业应用。 
发明内容
本发明目的在于提供一种阳离子交换树脂固载离子液体催化合成双酚F的新方法。 
本发明的技术方案是： 
1、将苯酚和阳离子交换树脂固载
Figure BSA0000100755130000021
酸性离子液体催化剂加入反应器，充分搅拌混合均匀状态下缓慢滴加甲醛溶液，所加催化剂与甲醛的质量比为1～6∶1，苯酚与甲醛的摩尔比为4～20∶1，反应温度为40～90℃，氮气保护，反应1～5h，反应结束后冷却至室温，抽滤回收催化剂，滤液减压蒸馏回收苯酚，冷却后即得双酚F产品。 
2、所述的阳离子交换树脂固载
Figure BSA0000100755130000022
酸性离子液体，具有离子液体咪唑环活性碳原子与离子交换树脂磺酸基团的复合催化活性，其结构式如下： 
Figure BSA0000100755130000023
式中强酸性阳离子交换树脂是指带有强酸性磺酸基(-SO3H)的苯乙烯系强酸性阳离子交换树脂)，
Figure BSA0000100755130000024
酸性离子液体是指1-(3-三甲氧基硅基)丙基-3-甲基咪唑或者1-(2羟基)乙基-3-甲基咪唑离子液体，
Figure BSA0000100755130000025
酸性离子液体中X-为硫酸氢根、硝酸根、磷酸二氢根、碳酸氢根、醋酸根、硼酸根、草酸根和六氟磷酸根离子中的一种。 
3、所述的阳离子交换树脂固载
Figure BSA0000100755130000026
酸性离子液体的制备方法为： 
(1)载体前处理 
将强酸性阳离子交换树脂用饱和氯化钠溶液浸泡12～24h，去离子水洗净后用质量浓度为3～5％的NaOH溶液浸泡4～8h，洗至中性，再用4～6％HCl浸泡4～8h，去离子水冲洗，抽滤，40～50℃干燥，得氢型强酸性阳离子交换树脂载体。 
(2)N-侧链含-Si(MeO)3、-OH的两种咪唑类离子液体的制备 
用(3-氯丙基)三甲氧基硅烷对咪唑环N-侧链进行修饰：将等摩尔量的(3-氯丙基)三甲氧基硅烷和1-甲基咪唑在N2保护下，60～110℃回流24～60h，冷却、洗涤、干燥，得N-侧链含-Si(MeO)3的1-(3-三甲氧基硅基)丙基-3-甲基咪唑氯化物离子液体； 
用2-氯乙醇对咪唑环N-侧链进行修饰：将等摩尔量的2-氯乙醇和1-甲基咪唑在N2保护下，60～110℃回流24～60h，冷却、洗涤、干燥，得N-侧链含-OH的1-(2-羟基)乙基-3-甲基咪唑氯化物离子液体。 
(3)离子液体的固载 
将强酸性阳离子交换树脂与适量甲苯充分混合后，分别加入与载体质量比为0.2～1.2∶1的上述两种离子液体，在35～50℃下搅拌反应48～60h，抽滤、洗涤、干燥，得到以两种不同化学键键合的催化剂前驱体。 
(4)催化剂的酸化 
将催化剂前驱体分散在乙腈中，冰水浴下滴加
Figure BSA0000100755130000031
酸，
Figure BSA0000100755130000032
酸为硫酸、硝酸、磷酸、碳酸、醋酸、硼酸、草酸或者六氟磷酸中的一种，
Figure BSA0000100755130000033
酸与催化剂前驱体中离子液体的摩尔比为0.9～1.2∶1，滴加完毕升至室温，搅拌反应12～30h，抽滤，洗涤，真空干燥，得到一种强酸性阳离子交换树脂固载 
Figure BSA0000100755130000034
酸性离子液体催化剂。 
本发明具有如下的技术效果，以阳离子交换树脂固载
Figure BSA0000100755130000035
酸性离子液体为催化剂催化合成双酚F，不仅能保留离子液体原有的特性，又能发挥载体材料的酸性，实现磺酸基团和
Figure BSA0000100755130000036
酸性咪唑类离子液体的复合催化，与单独的离子液体催化相比大大减少了离子液体用量。本发明制备的这种阳离子交换树脂固载酸性离子液体催化剂具有稳定性好，催化剂易分离重复使用，载体廉价易得等优点，且在低温条件下复合催化合成双酚F效果佳，双酚F收率达70％以上，4,4′-双酚F选择性高达50％以上。 
附图说明
图1为强酸性阳离子交换树脂固载1-(3-三甲氧基硅基)丙基-3-甲基咪唑氯化物离子液体的FT-IR图谱。 
图2为强酸性阳离子交换树脂固载1-(2羟基)乙基-3-甲基咪唑氯化物离子液体的FT-IR图谱。 
具体实施方式
实施例1 
(1)载体前处理：将强酸性阳离子交换树脂用饱和氯化钠溶液浸泡24h，去离子水洗净后用质量浓度为4％的NaOH溶液浸泡6h，洗至中性，再用5％HCl浸泡8h，去离子水冲洗，抽滤，45℃干燥，得氢型强酸性阳离子交换树脂载体(IER)； 
(2)1-(3-三甲氧基硅基)丙基-3-甲基咪唑氯化物离子液体的制备：在三口烧瓶中加入等摩尔量的(3-氯丙基)三甲氧基硅烷和1-甲基咪唑，在N2保护下，70℃回流反应48h，将反应液用乙酸乙酯洗涤，除去未反应的原料组分，80℃干燥8h，得到黄色油状产品，即1-(3-三甲氧基硅基)丙基-3-甲基咪唑氯化物离子液体([Pmim]Cl)； 
(3)离子液体的固载：取10g真空干燥处理的载体强酸性阳离子交换树脂分散在装有40ml甲苯的三口烧瓶中，再加入10gl-(3-三甲氧基硅基)丙基-3-甲基咪唑氯化物离子液体([Pmim]Cl)，40℃下回流48h，抽滤，用二氯甲烷洗去未键合到阳离子交换树脂上的离子液体，70℃干燥，得催化剂前驱体。 
(4)催化剂的酸化：将10g催化剂前驱体分散在40ml乙腈中，冰水浴下滴加浓0.018mol质量浓度为98％的H2SO4，滴加完毕升至室温反应24h，抽滤，用二氯甲烷洗涤，70℃干燥，得到一种强酸性阳离子交换树脂固载1-(3-三甲氧基硅基)丙基-3-甲基咪唑氯化物离子液体催化剂(IER-ILs-Si)催化剂，其结构式为： 
Figure BSA0000100755130000051
附图1所示：1500-1700cm-1是C＝C、C=N的伸缩振动频率；IER图谱中1380cm-1处是树脂中磺酸的SO2反对称伸缩峰，固载后此峰明显减弱，说明离子液体与树脂上的磺酸基团发生化学键合；ILs-Si中1100cm-1是Si-O-C的反对称伸缩振动频率，是单峰，而IER-ILs-Si中1000-1200cm-1分裂为双峰，是Si-O-C和Si-O-S振动频率，说明离子液体和树脂以共价键的方式键合。 
(5)催化合成双酚F：取2.7g催化剂和11.29g苯酚加入三口烧瓶中，在反应温度50℃下搅拌15min，充分混合后滴加1.22g甲醛溶液，滴加完毕开始计时，反应3h取样分析，反应结束后，冷却，用乙酸乙酯洗涤反应液，过滤回收催化剂，滤液减压蒸馏回收苯酚，冷却即得双酚F产品，双酚F收率为65％，4,4′-双酚F选择性为48％。 
实施例2 
(1)载体前处理同实施例1； 
(2)1-(2-羟基)乙基-3-甲基咪唑氯化物离子液体([C2OHmim]Cl)的制备：除原料为2-氯乙醇和1-甲基咪唑、80℃回流外，其余同实施例1； 
(3)离子液体的固载：除离子液体为1-(2-羟基)乙基-3-甲基咪唑氯化物外，其余同实施例1； 
(4)催化剂的酸化：除催化剂前驱体为强酸性阳离子交换树脂固载1-(2羟基)乙基-3-甲基咪唑氯化物离子液体、滴加浓0.031mol质量浓度为98％的H2SO4外，其余同实施例1，得到一种强酸性阳离子交换树脂固载1-(2羟基)乙基-3-甲基咪唑氯化物离子液体(IER-ILs-OH)催化剂，其结构式为： 
附图2所示：1500-1700cm-1是C=C、C=N的振动频率；IER图谱中1380cm-1处是磺酸的SO2反对称伸缩峰，固载后此峰明显减弱，说明离子液体与树脂上的磺酸基团发生化学键合；磺酸在1180，1130cm-1处有强吸收峰，分裂为两个谱带，而磺酸酯只有1175cm-1处有强峰而且强度明显增强，位置稳定，与IER-ILs-OH曲线一致。 
(5)催化合成双酚F：除催化剂为强酸性阳离子交换树脂固载1-(2-羟基)乙基-3-甲基咪唑氯化物离子液体(IER-ILs-OH)催化剂，其余合成步骤与参数同实施例1，双酚F收率为69％，4，4′-双酚F选择性为51％。 
实施例3 
同实施例2，但将催化剂用量改为0.45g，使催化剂用量与甲醛质量比为1∶1，得双酚F收率为35％，4，4′-双酚F选择性为43％。 
实施例4 
同实施例2，但将苯酚用量改为5.65g，使苯酚与甲醛的摩尔比为4∶1，得双酚F收率为63％，4，4′-双酚F选择性为49.1％。 
实施例5 
同实施例2，但将苯酚用量改为28.23g，使苯酚与甲醛的摩尔比为20∶1，得双酚F收率为73％，4,4′-双酚F选择性为48.2％。 
实施例6 
同实施例2，但反应温度为40℃，得双酚F收率为58％，4,4′-双酚F选择 性为46％。 
实施例7 
同实施例2，但反应温度为90℃，得双酚F收率为60％，4,4′-双酚F选择性为38％。 
实施例8 
催化剂制备与双酚F催化合成同实施例2，所不同的是催化剂酸化滴加的是冰乙酸(0.031mol，99.5％)，得双酚F收率为42％，4,4′-双酚F选择性为45％。 
实施例9 
同实施例2，不同的是直接用处理过的但没有固载离子液体的强酸性阳离子交换树脂做催化剂，得双酚F收率为23％，4,4′-双酚F选择性为40％。 
实施例10 
同实施例2，不同的是直接用3.4g[C6min][CH3COO]离子液体做催化剂，反应温度90℃，得双酚F收率为35％，4,4′-双酚F选择性为39％。 

Claims (3)

1.一种阳离子交换树脂固载离子液体催化合成双酚F的方法，其特征在于：将苯酚和强酸性阳离子交换树脂固载
Figure RE-FSB0000125390200000012
酸性离子液体催化剂加入反应器，充分搅拌混合均匀状态下缓慢滴加甲醛溶液，所加催化剂与甲醛的质量比为1～6∶1，苯酚与甲醛的摩尔比为4～20∶1，反应温度为40～90℃，氮气保护，反应1～5h，反应结束后冷却至室温，抽滤回收催化剂，滤液减压蒸馏回收苯酚，冷却后即得双酚F产品。 
2.根据权利要求1所述的一种阳离子交换树脂固载
Figure FSA0000100755120000013
酸性离子液体催化合成双酚F的方法，其特征在于：所述的阳离子交换树脂固载
Figure FSA0000100755120000014
酸性离子液体，具有离子液体咪唑环活性碳原子与离子交换树脂磺酸基团的复合催化活性，其结构式如下： 
Figure FSA0000100755120000015
式中强酸性阳离子交换树脂是指带有强酸性磺酸基(-SO3H)的苯乙烯系强酸性阳离子交换树脂，
Figure FSA0000100755120000016
酸性离子液体是指1-(3-三甲氧基硅基)丙基-3-甲基咪唑或者1-(2-羟基)乙基-3-甲基咪唑离子液体，
Figure 2014100330444100001FSA0000100755120000016
酸性离子液体中X-为硫酸氢根、硝酸根、磷酸二氢根、碳酸氢根、醋酸根、硼酸根、草酸根和六氟磷酸根离子中的一种。 
3.根据权利要求2所述的一种阳离子交换树脂固载酸性离子液体催化合成双酚F的方法，其特征在于：阳离子交换树脂固载
Figure FSA0000100755120000018
酸性离子液体的制备方法为： 
(1)载体前处理 
将强酸性阳离子交换树脂用饱和氯化钠溶液浸泡12～24h，去离子水洗净后 用质量浓度为3～5％的NaOH溶液浸泡4～8h，洗至中性，再用4～6％HCl浸泡4～8h，去离子水冲洗，抽滤，40～50℃干燥，得氢型强酸性阳离子交换树脂载体。 
(2)N-侧链含-Si(MeO)3、-OH的两种咪唑类离子液体的制备 
用(3-氯丙基)三甲氧基硅烷对咪唑环N-侧链进行修饰：将等摩尔量的(3-氯丙基)三甲氧基硅烷和1-甲基咪唑在N2保护下，60～110℃回流24～60h，冷却、洗涤、干燥，得N-侧链含-Si(MeO)3的1-(3-三甲氧基硅基)丙基-3-甲基咪唑氯化物离子液体； 
用2-氯乙醇对咪唑环N-侧链进行修饰：将等摩尔量的2-氯乙醇和1-甲基咪唑在N2保护下，60～110℃回流24～60h，冷却、洗涤、干燥，得N-侧链含-OH的1-(2-羟基)乙基-3-甲基咪唑氯化物离子液体。 
(3)离子液体的固载 
将强酸性阳离子交换树脂与适量甲苯充分混合后，分别加入与载体质量比为0.2～1.2∶1的上述两种离子液体，在35～50℃下搅拌反应48～60h，抽滤、洗涤、干燥，得到两种不同化学键合的催化剂前驱体。 
(4)催化剂的酸化 
将催化剂前驱体分散在乙腈中，冰水浴下滴加
Figure FSA0000100755120000021
酸，
Figure FSA0000100755120000022
酸为硫酸、硝酸、磷酸、碳酸、醋酸、硼酸、草酸或者六氟磷酸中的一种，
Figure FSA0000100755120000023
酸与催化剂前驱体中离子液体的摩尔比为0.9～1.2∶1，滴加完毕升至室温，搅拌反应12～30h，抽滤，洗涤，干燥，得到一种强酸性阳离子交换树脂固载
Figure FSA0000100755120000024
酸性离子液体催化剂。 
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