CN100453179C - 一种用于酯交换合成碳酸芳基酯的含锡复合催化剂 - Google Patents
一种用于酯交换合成碳酸芳基酯的含锡复合催化剂 Download PDFInfo
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Abstract
本发明涉及一种用于碳酸二烷基酯(如碳酸二甲酯)与单芳羟基化合物(如苯酚)酯交换合成碳酸单芳基酯(如甲基苯基碳酸酯)和碳酸二芳基酯(如碳酸二苯酯)的鼓形有机锡化合物催化剂和/或含锡复合催化剂。含锡复合催化剂由具有下列结构的化合物与羧酸或金属化合物中的至少一种组成;使用这些催化剂,在碳酸二烷基酯与单芳羟基化合物的摩尔比为1∶0.25~4,单芳羟基化合物与催化剂的摩尔比为1∶0.0005~0.03,酯交换反应温度120~220℃,酯交换反应压力0.1~0.5Mpa的条件下,能获得高产率高选择性的产物,并且易于提纯产物。
Description
技术领域
本发明涉及一种用于碳酸二烷基酯(如碳酸二甲酯)和单芳羟基化合物(如苯酚)酯交换合成碳酸单芳基酯(如甲基苯基碳酸酯)、碳酸二芳基酯(如碳酸二苯酯)的鼓形有机锡化合物催化剂和/或含锡复合催化剂。
背景技术
碳酸二芳基酯(特别是碳酸二苯酯)是一种重要的有机中间体,不仅用于合成医药、农药和其它产品,而且是制备聚碳酸酯的重要中间体,具有很高的产业价值。碳酸二芳基酯的合成方法主要有光气法、酯交换法和单芳羟基化合物氧化羰化法等三种方法。光气法由于原料剧毒、环境污染严重等问题正逐步被淘汰;单芳羟基化合物氧化羰化法合成效率不高,且催化剂昂贵。酯交换法采用一种单芳羟基化合物(例如苯酚、甲基苯酚、二甲基苯酚等)与一种碳酸二烷基酯(如碳酸二甲酯、碳酸二乙酯)进行酯交换反应生成碳酸二芳基酯。该方法是一种环境友好的方法,它避免了传统工艺中所使用的有害物质,如光气、亚甲基氯等。
JP 8188558,EP 0780361,JP 10032361介绍了一类钛、锡有机化合物催化剂。如钛酸四丁酯[Ti(OC4H9)4]、二丁基氧化锡[n-Bu2SnO]、钛酸四苯酯[Ti(OPh)4]等。该类催化剂性能高,目标产物的的产率可达50%以上,但催化剂与产品的分离回收较困难。
中国专利CN 1411909公开了一种用于酯交换合成甲基苯基碳酸酯的复合催化剂及其制备方法。该催化剂是由有机锡、有机钛和有机胺按一定摩尔比复配而成。其特点是三种组分的摩尔比为:1∶0.2~2∶0.001~0.5。反应温度为150~200℃,反应压力为常压,时间是6~30小时。苯酚转化率是15~50%,甲基苯基碳酸酯选择性>90%。此种催化剂综合了有机锡和有机钛催化剂的优点,在此基础上加入有机胺类,使得催化剂活性、选择性较高。
中国专利CN1036951介绍了一类有机锡化合物和金属化合物催化剂。有机锡化合物催化剂为SnO和/或XR2SnOSnR2Y(X和Y可以相同,也可以不同。它们各自表示OH、SCN等);金属化合物为选自Sc、Cr、Mo、W、Mn、Au、Ga、In、Bi、Te以及兰镧系元素中的任意一元素的化合物。但这些催化剂的活性低,甲基苯基碳酸酯和碳酸二苯酯的总收率低于20%。
US4554110报道了一种聚合的锡化合物,其分子式如下:
其中R、R1表示烃基。
该类催化剂用于酯交换反应时,只有在长的反应时间(≥24小时)条件下,才能获得高的碳酸二苯酯收率。
US4552704报道了RSn(O)OH催化碳酸二烷基酯与芳香羟基化合物合成芳基烷基碳酸酯和碳酸二芳基酯,但其仅使用了单一的RSn(O)OH作催化剂,没有复合催化剂的报道。
文献(Kumara Swamy K.C.,Said M.A.,Nagabrahmanandachari S.,PoojaryDamodara M.,Clearfield A.[J],J.Chem.Soc.Dalton Trans.1998,1645;Chandrasekhar V.,Day R.O.,Holmes R.R.[J],Inorg.Chem.,1985,24:1970;Chandrasekhar V.,Schmid C.G.,Burton S.D.,Holmes J.M.,Day R.O.,HolmesR.R.[J],Inorg.Chem.,1987,26:1050;Chandrasekhar V.,Nagendran S.,Bansal S.,Kozee M.A.,Powell D.R.[J],Angew.Chem.Int.Ed.Engl.,2000,39:1833;Day R.O.,Chandrasekhar V.,Kumara Swamy K.C.,Holmes J.M.,Burton S.D.,Holmes R.R.[J],Inorg.Chem.,1988,27:2887)仅报道了鼓形结构化合物的合成,没见将其用于催化碳酸二烷基酯与芳香羟基化合物酯交换合成芳基烷基碳酸酯和碳酸二芳基酯的报道。
发明内容
本发明所采用的有机锡化合物催化剂为具有独特鼓形结构的有机锡氧簇合物。这些有机锡化合物催化剂可以是(BuSn(O)O2CC5H4FeC5H5)6、(BuSn(O)O2CCH3)6、(BuSn(O)O2CCH2Cl)6、(BuSn(O)O2CCHCl2)6、(BuSn(O)O2CCCl3)6、(BuSn(O)O2CC6H4NO2)6、(C6H5Sn(O)O2CC6H11)6中的任意一种。
本发明所采用的含锡复合催化剂由具有下列结构的化合物与羧酸或金属化合物中的至少一种构成。
其中R1为取代或非取代的C1~C12烷基、烷氧基,取代或非取代的芳香基、芳香氧基。取代基R1可以是:甲基、乙基、丙基、丁基、戊基、己基、庚基、环戊基、环己基、苯基、苄基、甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、环戊氧基、环己氧基、苯氧基、苄氧基中的任意一种。
羧酸是一元或二元取代或非取代的脂肪酸、芳香酸,具体可以是:乙酸、环戊基甲酸、环己基甲酸、苯甲酸、取代苯甲酸、苯乙酸、二茂铁甲酸、氯乙酸、二氯乙酸、三氯乙酸、三氟乙酸中的任意一种。
金属化合物为主族、副族金属的氧化物、卤化物、乙酸盐、碳酸盐、硫酸盐等;具体可以是:镧系金属的氧化物、卤化物、乙酸盐、碳酸盐、硫酸盐,CuX(X=F、Cl、Br、I)、Cu2O、CuSO4、CuBr2、CuCl2、Cu(OAc)2、CuCO3、CuO、ZnO、ZnCl2、Zn(OAc)2、ZnCO3、ZnSO4、TiO2、TiOCl2、TiOSO4、V2O5、VOCl2、VOSO4、Cr2O3、CrCl3、Cr(OAc)3、Cr2(SO4)3、MnO、MnO2、MnCl2、MnSO4、FeO、Fe2O3、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、CoO、CoCl2、Co(OAc)2、CoSO4、NiO、Ni(OAc)2、NiSO4、ZrO2、ZrOCl2、ZrOSO4、Nb2O5、MoO3、WO3、Al2O3、AlCl3、Al2(SO4)3、Al(OAc)3、MgO、PbO、Pb3O4、Pb(OAc)2、PbCO3、PbSO4、PbCl2、SnO2、SnCl2、SnCl4中的任意一种。
本发明所述催化剂,其适用的酯交换反应式如下:
总方程式为:
(1)、(2)、(3)式以及总方程式中的R2代表以下基团中的任意一种或多种:H、CH3、CH3CH2、NO2、F、Cl、Br、CN、R3O。R3、R4代表C1~10的烷基,具体可以是:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基中的任意一种。
本发明所用催化剂适合的工艺条件为:碳酸二烷基酯与单芳羟基化合物的摩尔比为1∶0.25~4,单芳羟基化合物与催化剂的摩尔比为1∶0.0005~0.03。酯交换反应温度120~220℃,酯交换反应压力0.1~0.5MPa。反应过程中,副产的低碳醇与碳酸二烷基酯形成共沸物,用精馏塔及时分离。反应产物用气相色谱法分析。
具体实施方式
关于本发明的方法,用以下的实例加以说明,但本发明决不受这些实例的限制。
[实施例1]在氮气保护下,向配有搅拌器、精馏柱、冷凝器、加料泵的100ml反应釜中加入0.3mol苯酚和0.00339mol的鼓形催化剂(BuSn(O)O2CC5H4FeC5H5)6。当反应液温度上升到180℃后,开始加入碳酸二甲酯。0.15mol的碳酸二甲酯在3h内加完,然后继续反应5h。反应过程及时分离副产物甲醇与碳酸二甲酯形成的共沸物。碳酸二甲酯的转化率为50.5%,甲基苯基碳酸酯(MPC)的产率为34.0%,碳酸二苯酯(DPC)的产率为16.5%。
[实施例2]除由等摩尔的BuSn(O)OH与ClCH2COOH构成的复合催化剂代替实例1中的催化剂外,其它反应条件同实施例1,结果见表1。
[实施例3~9]除催化剂种类不同外,其余条件同实施例2。结果见表1。
[实施例10]由BuSn(O)OH与AlCl3构成的复合催化剂代替实例1中的催化剂,且BuSn(O)OH与AlCl3的摩尔比为5∶1,其它反应条件同实施例1,结果见表1。
[实施例11~16]除催化剂种类不同外,其余条件同实施例10。结果见表1。
表1催化剂对酯交换反应的影响
备注:MPC:甲基苯基碳酸酯;DPC:碳酸二苯酯。
[实施例17]在氮气保护下,向配有搅拌器、精馏柱、冷凝器、加料泵的100ml反应釜中加入0.2mol苯酚和0.002mol的由等摩尔的BuSn(O)OH与Cl3CCOOH构成的复合催化剂。当反应液温度上升到180℃后,开始加入碳酸二乙酯。0.1mol碳酸二乙酯在3h内加完,然后继续反应5h。反应过程及时分离副产物乙醇与碳酸二乙酯形成的共沸物。碳酸二乙酯的转化率为60.7%,乙基苯基碳酸酯的产率为39.0%,碳酸二苯酯的产率为20.5%,苯乙醚的收率为1.2%。
[实施例18]对硝基苯酚1mol、碳酸二甲酯3mol、0.01mol的由等摩尔的BuSn(O)OH与Cl3CCOOH构成的复合催化剂加入到反应釜中。反应温度205℃~220℃,反应表压2.5kgf/cm2,反应时间8h。对硝基苯酚的转化率为64.1%,对硝基苯基甲基碳酸酯的产率为55.2%,对二硝基二苯基碳酸酯的产率为10.7%。
Claims (2)
1.一种由碳酸二烷基酯与单芳羟基化合物通过酯交换法合成碳酸单芳基酯和碳酸二芳基酯的方法,其特征是使用鼓形有机锡化合物催化剂或含锡复合催化剂,碳酸二烷基酯与单芳羟基化合物的摩尔比为1∶0.25~4,单芳羟基化合物与催化剂的摩尔比为1∶0.0005~0.03,酯交换反应温度120~220℃,酯交换反应压力0.1~0.5Mpa;鼓形有机锡化合物催化剂为(BuSn(O)O2CC5H4FeC5H5)6;含锡复合催化剂由具有
结构的化合物与卤代羧酸或金属化合物组成,R1为甲基、乙基、丙基、丁基、戊基、己基或庚基,卤代羧酸为氯乙酸、二氯乙酸、三氯乙酸、三氟乙酸中的任意一种,金属化合物为CuSO4、CuBr2、CuCl2、Cu(OAc)2、CuCO3、CuO、V2O5、Cr2O3、CrCl3、Cr(OAc)3、Cr2(SO4)3、CoO、CoCl2、Co(OAc)2、CoSO4、NiO、Ni(OAc)2、NiSO4、MoO3、WO3、Al2O3、AlCl3、Al2(SO4)3、Al(OAc)3、PbO、Pb3O4、Pb(OAc)2、PbCO3、PbSO4、PbCl2、MoO3、Sb2O3、CeCl3中的任意一种;单芳羟基化合物具有如下结构
取代基R2是H、CH3、CH3CH2中的任意一种。
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US4552704A (en) * | 1983-12-27 | 1985-11-12 | General Electric Company | Process for the production of aromatic carbonates |
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Synthesis and structures of new mono- and multi-nuclearbenzyltin carboxylates and phosphinates: a novel dibenzyltinphosphinate stabilized by intramolecular hydrogen bonding. K.C.Kumara Swamy, et al.J.Chem.Soc.,Dalton Trans.. 1998 |
Synthesis and structures of new mono- and multi-nuclearbenzyltin carboxylates and phosphinates: a novel dibenzyltinphosphinate stabilized by intramolecular hydrogen bonding. K.C.Kumara Swamy, et al.J.Chem.Soc.,Dalton Trans.. 1998 * |
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