CN102482308A - 二氧化碳/环氧化合物共聚反应的催化系统 - Google Patents
二氧化碳/环氧化合物共聚反应的催化系统 Download PDFInfo
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- CN102482308A CN102482308A CN201080027027XA CN201080027027A CN102482308A CN 102482308 A CN102482308 A CN 102482308A CN 201080027027X A CN201080027027X A CN 201080027027XA CN 201080027027 A CN201080027027 A CN 201080027027A CN 102482308 A CN102482308 A CN 102482308A
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Abstract
本发明涉及一种包括用钴(III)或铬(III)作为催化剂使环氧化合物和CO2进行共聚的过程的制备聚碳酸酯的方法,其中配体包含至少3个铵阳离子,中心金属具有-1形式电荷,两个阳离子铵基团的共轭阴离子为酸碱同共轭。根据本发明,当生产所述聚碳酸酯时可减少起始诱导时间,且有可能提高催化剂的活性和所得聚合物的分子量。
Description
技术领域
本发明涉及一种使用由含有铵盐的配体制得的钴或铬络合物作为催化剂共聚环氧化合物和CO2来制备聚碳酸酯的方法。
背景技术
脂肪族聚碳酸酯是一种可生物降解的共聚物,是一种用于包装或涂层的材料。考虑到不使用任何对人体有害的化合物光气,且CO2以低成本获取,由环氧化合物和CO2来制备聚碳酸酯的方法是非常环保的。
20世纪60年代以来,已开发出各类催化剂用于由环氧化合物和CO2制备聚碳酸酯。近来,本发明人已公开了从包括季铵盐的萨伦(Salen)[萨伦:([H2萨伦=N,N′-双(3,5-二烷基亚水杨基)-1,2-乙二亚胺]-型配体合成的高活性和高选择性的催化剂[Bun-Yeoul Lee,韩国专利No.10-0853358(注册日:2008年8月13日);Bun-Yeoul Lee,Sujith S,Eun-Kyung Noh,Jae-Ki Min,韩国专利申请No.10-2008-0015454(申请日:2008年2月20日);Bun-Yeoul Lee,Sujith S,Eun-Kyung Noh,Jae-KiMin,PCT/KR2008/002453(申请日:2008年4月30日);Eun Kyung Noh,Sung Jae Na,Sujith S,Sang-Wook Kim,和Bun Yeoul Lee*,J.Am Chem.Soc.2007,129,8082-8083(2007.07.04);Sujith S,Jae Ki Min,Jong EonSeong,Sung Jea Na,和Bun Yeoul Lee,Angew.Chem.Int.Ed.,2008,47,7306-7309.(2008.09.08)]。由本发明人公开的催化剂显示出高活性和高选择性,可用于制备高分子量共聚物,由于在高温下聚合而适于商业应用。此外,由于配体包括季铵盐,它具有聚合反应后易回收及再利用催化剂的好处。
此外,本发明人在所述专利的一组催化剂中仔细分析了显示出特别高活性和高选择性的催化剂的结构,从而证明该结构是独特的、之前未知的,其中萨伦-配体的氮原子不与金属原子配位(coordinate),但氧原子与金属原子(例1)配位。因此,根据提交的韩国专利申请No.10-2008-0074435(申请日:2008年7月30日)结果,本发明涉及一种新型的催化系统。
[例1]
X=2,4-二硝基苯酚盐
通过对例1化合物的NMR研究披露了二硝基苯酚盐(DNP)的状态。更具体地,化合物中所含四个DNPs中两个总是与钴配位,它们中的另外两个处于流变(fluxional)的配位和非配位状态之间,其中根据温度、溶剂和配体取代基(R、R1、R2)的变化,配位状态的程度可以不同。下图显示了室温下在THF溶剂中根据催化剂结构的DNP状态,该介质与聚合反应介质非常相似。在化合物1′中,流变运动(fluxional motion)随时间变化较大,从而在NMR谱中未观察到流变(fluxional)DNP的信号。在络合物2′和3′中,流变DNPs大多数保持在非配位状态,但在络合物2′中其保持非配位状态的时间更长。也就是说,两个流变DNPs保持非配位状态的程度的顺序为(即与钴的结合亲和力)为1′>3′>2′。然而,在CO2/环氧丙烷共聚中观察到的活性(TOF)的顺序反之为2′>3′>1′。这意味着,如果两个流变DNPs与钴的结合亲和力高,则活性降低。
上述结构的化合物显示出高活性的原因可解释为下述特点,两个阴离子DNP配体易于在配位和非配位状态之间流变运动。下图显示了CO2/环氧化合物共聚的聚合物链的生长机制。在这种机制中,碳酸盐阴离子对配位的环氧化合物的攻击是至关重要的。阴离子的流变特点使碳酸盐阴离子能够从后侧攻击配位的环氧化合物。如下图所示的链生长机制中,如果配位的碳酸盐阴离子可以很容易地转移到非配位状态,则预期其具有高活性。
使用所述络合物催化的CO2/环氧化合物共聚中,聚合溶液的[水]/[催化剂]比率在实现催化剂的活性中起着重要的作用。虽然试图从环氧化合物和CO2中彻底去除水,尤其是当[环氧化合物]/[催化剂]的比率很高如100,000时,所述[水]/[催化剂]的比率是不容忽视的。在这种100,000的高[环氧化合物]/[催化剂]比率下,环氧化合物和CO2中残留的少量水显著影响着[水]/[催化剂]比率。只有当聚合反应在[环氧化合物]/[催化剂]为诸如100,000的高比率条件下进行时,可得到高活性(TON)。因此,作为具有商业价值的催化剂,催化剂应对水不太敏感。在具有所述结构的催化剂的情况下,观察到根据聚合溶液的干燥程度,诱导时间差异较大。例如,当聚合反应是在干燥的冬季进行,聚合反应诱导时间约为1-2小时,而当聚合反应是在湿热的夏季进行,聚合反应甚至为12小时。聚合反应一旦开始,之后的活性(TOF)就不会发生变化。在1H NMR光谱实验中,观察到络合物中的DNP攻击环氧丙烷。当有意加入水时,这种攻击率显著下降。通过氢与水键合从而稳定了两个流变阴离子,因此亲核攻击率下降。
下表1显示了使用例1的络合物2,通过混合环氧丙烷(PO)和环氧环己烷(CyO),与CO2三聚反应的结果。如表1所示,观察到诱导时间可以从45分钟到9小时10分钟变化。此外,观察到分子量随着诱导时间的增加而降低。这种不规则、有时较长的诱导时间可成为使用这种催化剂的商业化进程发展中的障碍。此外,为了持续制备高分子聚合物,必然要求商业化。
[表1]P0CHO-C02三聚反应结果
发明内容
技术问题
本发明的目的是解决共聚CO2和环氧化合物制备聚碳酸酯中,上述催化剂系统的诱导时间不规则和时间过长,获得的是低分子量聚合物且催化剂的活性降低的问题。
技术方案
为了实现上述目的,本发明提供了一种制备聚碳酸酯的方法,其包括使用钴(III)或铬(III)络合物(式1)作为催化剂共聚环氧化合物和CO2的步骤,其中配体包含至少3个铵阳离子,中心金属具有-1形式电荷,两个阳离子铵基团的共轭阴离子为酸碱同共轭。
[式1]
[L1L2L3L4M]-[X1...H...X2]- aZ- b
其中,M为钴(III)或铬(III);
L1-L4为阴离子X型配体,L1-L4为相同或各自不同的,也可通过相互连接形成双齿配体、三齿配体或四齿配体,L1-L4中至少一个包括季铵盐,L1-L4中包含的铵阳离子总数为1+a+b,因此所述络合物整体呈中性;
a或b为整数;优选a或b为0-15的整数,但不限于此,且满足1+a+b。
L1-L4中除包括季铵盐阳离子的配体之外的配体,或X1和X2各自独立地为卤素阴离子或HCO3 -,或者含或不含卤原子、氮原子、氧原子、硅原子、硫原子和磷原子中的一个或多个且碳原子数6-20的芳氧基阴离子,碳原子数1-20的羧基阴离子;碳原子数1-20的烷氧基阴离子;碳原子数1-20的碳酸盐阴离子;碳原子数1-20的烷基磺酸盐阴离子;碳原子数1-20的酰胺阴离子;碳原子数1-20的甲酰胺阴离子;碳原子数1-20的磺酰胺阴离子;或碳原子数1-20的氨基甲酸酯阴离子,
Z为BF4 -、C1O4 -、NO3 -或PF6 -。
所述X-型配体详细描述于Gary O.Spessard和Gary L.Miessler,金属有机化学(Organometallic Chemistry),第46页,Prentice Hall中。所述X-型配体为阴离子配体如氢、氯或甲基,认为X-阴离子与金属元素M+阳离子共轭,且所述X-型配体的结合影响金属的氧化状态。
本发明的实施方案提供了一种制备聚碳酸酯的方法,包括使用下述式2所表示的催化剂共聚环氧化合物和CO2的步骤。
[式2]
其中,L5、L6、X3或X4各自独立地为卤素阴离子或HCO3 -,或者含或不含卤原子、氮原子、氧原子、硅原子、硫原子和磷原子中的一个或多个且碳原子数6-20的芳氧基阴离子,碳原子数1-20的羧基阴离子;碳原子数1-20的烷氧基阴离子;碳原子数1-20的碳酸盐阴离子;碳原子数1-20的烷基磺酸盐阴离子;碳原子数1-20的酰胺阴离子;碳原子数1-20的甲酰胺阴离子;碳原子数1-20的磺酰胺阴离子;或碳原子数1-20的氨基甲酸酯阴离子,
C为1或0,
Z为BF4 -、ClO4 -、NO3 -或PF6 -,
R12和R14可选自甲基、乙基、异丙基或氢,R11和R13为-[CH{(CH2)3N+Bu3}2]或-[CMe{(CH2)3N+Bu3}2],
Q为用于连接两个氮原子的结合的双自由基,所述Q为(C6~C30)亚芳基、(C1~C20)亚烷基、(C2~C20)亚烯基、(C2~C20)亚炔基、(C3~C20)亚环烷基或结合的(C3~C20)亚环烷基,或所述亚芳基、亚烷基、亚烯基、亚炔基、亚环烷基或结合的亚环烷基可被选自下组的取代基所取代:卤原子、(C1~C7)烷基、(C6~C30)芳基或硝基,或包含选自氧、硫和氮的一个或多个杂原子。
更具体地,在式2中,Q为反式-1,2-环己烯基或乙烯基;X为2,4-二硝基苯酚盐、4-硝基苯酚盐、2,4,5-三氯苯酚盐、2,4,6-三氯苯酚盐或五氟苯酚盐;Z为BF4 -。
更优选地,本发明提供一种制备聚碳酸酯的方法,包括使用下述式3的催化剂共聚环氧化合物和CO2的步骤。
[式3]
其中,L7、L8、X5或X6各自独立地为卤素阴离子或HCO3 -,或者含或不含卤原子、氮原子、氧原子、硅原子、硫原子和磷原子中的一个或多个且碳原子数6-20的芳氧基阴离子,碳原子数1-20的羧基阴离子;碳原子数1-20的烷氧基阴离子;碳原子数1-20的碳酸盐阴离子;碳原子数1-20的烷基磺酸盐阴离子;碳原子数1-20的酰胺阴离子;碳原子数1-20甲酰胺阴离子;碳原子数1-20的磺酰胺阴离子;或碳原子数1-20的氨基甲酸酯阴离子,
Z为BF4 -、ClO4 -、NO3 -或PF6 -,
R12和R14可选自甲基、乙基、异丙基或氢,R11和R13为-[CH{(CH2)3N+Bu3}2]或-[CMe{(CH2)3N+Bu3}2],
Q为用于连接两个氮原子的结合的双自由基,所述Q为(C6~C30)亚芳基、(C1~C20)亚烷基、(C2~C20)亚烯基、(C2~C20)亚炔基、(C3~C20)亚环烷基或结合的(C3~C20)亚环烷基,或所述亚芳基、亚烷基、亚烯基、亚炔基、亚环烷基或结合的亚环烷基可被选自下组的取代基所取代:卤原子、(C1~C7)烷基、(C6~C30)芳基或硝基,或包含选自氧、硫和氮的一个或多个杂原子。
更具体地,在式3中,Q为反式-1,2-环己烯基或乙烯基;X为2,4-二硝基苯酚盐、4-硝基苯酚盐、2,4,5-三氯苯酚盐、2,4,6-三氯苯酚盐或五氟苯酚盐;Z为BF4 -。
本发明的络合物是通过生产催化剂的方法制备的,包括合成带有铵盐的配体,使金属醋酸盐(所述金属为钴或铬)与带有铵盐的配体发生反应,去除生成的醋酸而得到钴(II)络合物,在足量酸(HX)的存在下以氧作为氧化剂进行氧化而获得钴(III)化合物,然后用60~100mol%的NAX进行阴离子交换反应。所述带有铵盐的配体按照本发明人公开的方法(Bull.Korean Chem.Soc.2009,30,745)进行制备。
在酸(HX)中,X为卤素阴离子或HCO3 -,或者含或不含卤原子、氮原子、氧原子、硅原子、硫原子和磷原子中的一个或多个且碳原子数6-20的芳氧基阴离子,碳原子数1-20的羧基阴离子;碳原子数1-20的烷氧基阴离子;碳原子数1-20的碳酸盐阴离子;碳原子数1-20的烷基磺酸盐阴离子;碳原子数1-20的酰胺阴离子;碳原子数1-20的甲酰胺阴离子;碳原子数1-20的磺酰胺阴离子;或碳原子数1-20的氨基甲酸酯阴离子。
本发明提供一种制备聚碳酸酯的方法,包括用选自式1-3的钴络合物作为催化剂共聚环氧化合物和CO2的步骤。
所述环氧化合物可选自下组:被或未被卤素或烷氧基取代的(C2~C20)环氧烷烃(alkyleneoxide);被或未被卤素或烷氧基取代的(C4~C20)环氧环烷烃(cycloalkyleneoxide);以及被或未被卤素、烷氧基、烷基或芳基取代的(C8~C20)环氧苯乙烷。所述烷氧基(alkoxy)具体为烷基氧基(alkyloxy)、芳氧基、芳基烷氧基(aralkyloxy)等,所述芳氧基为苯氧基、联二苯氧基、萘氧基等。所述烷氧基、烷基和芳基可含卤原子或烷氧基取代基。
所述环氧化合物为例如环氧乙烷、环氧丙烷、环氧丁烷、环氧戊烷、环氧己烷、环氧辛烷、环氧癸烷、环氧十二烷、环氧十四烷、环氧十六烷、环氧十八烷、环氧丁烯(butadiene monoxide)、1,2-环氧-7-辛烯、环氧氟丙烷、环氧氯丙烷、环氧溴丙烷、异丙基缩水甘油醚、丁基缩水甘油醚、叔丁基缩水甘油醚、2-乙基己基缩水甘油醚、烯丙基缩水甘油醚、环氧环戊烷、环氧环己烷、环氧环辛烷、环氧环十二烷、α-环氧蒎烷、2,3-环氧降冰片烷(2,3-epoxidnobonene)、柠檬烯氧化物(limonene oxide)、氧桥氯甲桥萘(dieldrine)、2,3-环氧丙基苯、环氧苯乙烷、苯基环氧丙烷、环氧芪、氯代环氧芪、二氯代环氧芪、1,2-环氧-3-苯氧基丙烷、苄氧甲基环氧乙烷、缩水甘油基-甲基苯基醚、氯苯基-2,3-环氧丙基醚、环氧丙基-甲氧基苯基醚、联苯缩水甘油醚、缩水甘油基萘基醚等。
所述环氧化合物可用于使用有机溶剂作为反应介质的聚合反应,且所述溶剂为,例如脂肪烃类如戊烷、辛烷、癸烷、环己烷等,芳烃如苯、甲苯和二甲苯等,卤化烃类如氯甲烷、二氯甲烷、氯仿、四氯化碳、1,1-二氯乙烷、1,2-二氯乙烷、氯乙烷、三氯乙烷、1-氯丙烷、2-氯丙烷、1-氯丁烷、2-氯丁烷、1-氯-2-甲基丙烷、氯苯和溴苯等,其可单独使用或两种或两种以上组合使用。更优选地,使用单体本身作为溶剂可进行本体聚合反应(bulk polymerization)。
环氧化合物与催化剂的摩尔比率,即环氧化合物:催化剂在1,000-1,000,000是有益的,优选50,000-200,000。
在所述共聚步骤中,CO2的压力为大气压力-100bar,优选5bar-30bar。
共聚中的聚合反应温度为20℃-120℃,优选50℃-90℃。
作为聚合聚碳酸酯的方法,可进行分批聚合、半分批(semibatch)聚合或连续聚合。在分批聚合或半分批聚合的情况下,反应时间为1-24小时,优选1.5-4小时。连续聚合反应中催化剂的平均保留时间也优选为1.5-4小时。
根据本发明,可制备出数均分子量(Mn)5,000-1,000,000且分子量分布(即,Mw/Mn)为1.05-4.0的聚碳酸酯。上述Mn表示以聚苯乙烯标准物在GPC上测定的数均分子量。所述分子量分布值(Mw/Mn)为在GPC上测定的重均分子量(Mw)和数均分子量(Mn)之间的比值。
获得的聚碳酸酯聚合物包括80%或以上的碳酸盐连接,更多为95%或以上的碳酸盐连接。根据本发明制备的聚碳酸酯易于降解,燃烧时无残留物和烟尘,是用于例如包装、绝缘体或涂料的有益材料。
有益效果
如上所述,常规催化剂显示出高活性的原因是由于两种阴离子配体的配位和非配位状态之间的流变特点。此外,如果流变阴离子配体可以很容易地从金属中心去配位,也就是说,当与金属中心较少相互作用时,活性增强。本发明涉及通过使用酸碱同共轭,例如[DNP...H...DNP]-(参考表2和表3)取代流变阴离子配体以减弱阴离子与金属中心的相互作用,从而增加活性。如果催化剂活性增加,通常分子量增加(参考表2和表3)。此外,用酸碱同共轭(参考表2和表3)取代两种阴离子可降低对水的敏感性。如上所述,在现有催化剂的情况下,诱导时间根据聚合溶液的干燥程度而有很大变化;其被解释为流变阴离子与水形成氢键而降低了阴离子对环氧丙烷的亲核攻击。酸碱同共轭的情况下,其中已存在氢键且对水的敏感度较差,从而诱导时间的变化相对较小。
如果DNP与水形成氢键,其亲核性降低,从而降低了与PO反应速率,然而在同共轭的情况下,它本身形成氢键,相反提高了对PO的亲核攻击率。图1是1H NMR谱,显示下述式4的化合物6和环氧丙烷之间反应。可观察到,与环氧丙烷发生同共轭反应,生成迈森海默盐(Meisenheimer salt)阴离子(带有*标记的信号(signal))以及醇化合物2,4-(NO2)2C6H3-OCH2CH(Me)OH和2,4-(NO2)2C6H3-OCH(Me)CH2OH(带有x标记的信号),配位的DNP(带有^标记的信号)是存在的。当化合物3和6与环氧丙烷的反应活性通过计算最初30分钟反应的环氧丙烷的量来计量时,可看出化合物6比化合物3快两倍,而这些结果与化合物6的活性高于化合物3的结果是相同的。此外,在化合物4的情况下,与环氧丙烷的反应活性通过加入50当量的水而大大降低,然而从图1可见,在50当量的水存在下,化合物6与环氧丙烷的反应活性不降低。这一结果解释了化合物6对水的敏感度小于化合物3的原因。
[式4]
[式5]
[反应式1]
酸碱同共轭中氢键的强度比一般氢键的强度高得多。参考Shan,S.-o.和Loh,S.和Herschlag,D,科学(Science)1996,272,97,其报道了在PKa值相同的酸和碱之间形成氢键的情况下,氢键强度异常大,从而使酶的活性最大化。此外,(18-Crown-6-k6O)2,4-二硝基苯酚钾2,4-二硝基苯酚同共轭的x-射线单晶结构报道于Barnes,J.C.和Weakley,T.J.R.,Acta Cryst.2003,E59,m160,通过氢键连接的氧氧键的长度是2.453(4)这种键的长度支持很强的氢键。(Paola Gilli,P.;Bertolasi,V.;Ferretti,V.;和Gilli,V.J.Am.Chem.Sec.1994,116,909.)。此外,参考Magonski,J.和Pawlak,Z和Jasinski,T,J.Chem.Soc.Faraday Trans.1993,89,119,形成同共轭的平衡常数为100左右,且有机溶剂中的两种成分作为同共轭存在,如式4所示。在实践中,在thf-d8溶剂中测得的化合物6的1H MR谱中,可清楚地看到带有*标记的配位DNP信号以及带有^标记的同共轭[DNP...H...DNP]-信号。
附图说明
图1是dmso-d6中的1H MR谱,表示化合物4和环氧丙烷之间的反应。带有*标记的信号是通过DNP阴离子的反应生成的迈森海默盐的阴离子,带有x标记的信号是2,4-(NO2)2C6H3-OCH2CH(Me)OH和2,4-(NO2)2C6H3-OCH(Me)CH2OH,带有^标记的信号是DNP。
图2是在thf-d8溶剂中测得的化合物4的1H NMR谱。带有*标记的信号是配位的DNP信号,带有^标记的信号是同共轭信号。
具体实施方式
下面将参考以下实施例详细描述本发明,但本发明的范围不限于此。
[制备例1]60mol%二硝基苯酚钠(NaDNP)的合成
将市售二硝基苯酚(10.0g,54.3mmol)溶解于250mL二氯甲烷中,并用无水硫酸镁除去水。减压下,通过过滤除去溶剂。所述无水二硝基苯酚(10.0g,54.3mmol)溶于无水THF(300mL)后,缓慢加入NaH(0.782g,32.6mmol)。加入所有NaH后,搅拌溶液3小时。减压下除去溶剂,获得60mol%二硝基苯酚钠。
[制备例2]100mol%二硝基苯酚钠的合成
将无水二硝基苯酚(10.0g,54.3mmol)溶于无水THF(300mL)中,然后缓慢加入NaH(1.30g,54.3mmol)。将该溶液搅拌3小时后减压下除去溶剂,获得100mol%二硝基苯酚钠。
[实施例]
[式4]
[实施例1]化合物4的合成
根据公开的文献(Bull.Korean Chem.Soc.2009,30,745)合成配体。在手套箱(glove box)中,配体(0.376g,0.230mmol)和Co(OAc)2(0.041g,0.230mmol)被定量加入50mL圆底烧瓶中后,加入乙醇(17mL),所得溶液搅拌3小时。加入乙醚(20mL)形成固体沉淀,并用玻璃过滤器过滤,然后用乙醚(10mL)洗涤三次。减压下彻底去除所得橙色固体中的溶剂。向含有上述制得的钴(II)化合物(0.200g,0.117mmol)的烧瓶中加入2,4-二硝基苯酚(0.022g,0.117mmol),并加入二氯甲烷(5mL)。氧气气氛下搅拌该溶液3小时后,加入上述制备的60mol%二硝基苯酚钠(0.121g,0.585mmol)并搅动12小时。用玻璃过滤器过滤该溶液后,减压下除去溶剂而获得红棕色固体(0.284g,0.111mmol)。产率95%。1H NMR(dmso-d6,40℃):d 8.62(br,3H,(NO2)2C6H3O),8.03(br,3H,(NO2)2C6H3O),7.87(br,1H,CH=N),7.41-7.22(br,2H,m-H),6.71(br,3H,(NO2)2C6H3O),3.62(br,1H,环己基-CH),3.08(br,16H,NCH2),2.62(s,3H,CH3),2.09(1H,环己基-CH),1.89(1H,环己基-CH),1.72-1.09(br,37H),0.87(br,18H,CH3)ppm。
[实施例2]化合物5的合成
使用4-硝基苯酚采用与化合物4相同的制备方法合成化合物5。O2-氧化反应的速率很慢,所以反应进行了3天。使用按照生产上述60mol%4-硝基苯酚钠的方法制得的60mol%4-硝基苯酚钠进行阴离子交换反应。产率95%。1H NMR(dmso-d6,40℃):d 7.96(br,4H,(NO2)C6H4O),7.77(br,1H,CH=N),7.49(br,1H,(NO2)C6H4O),7.10(br,1H,m-H),7.02(br,2H,m-H,(NO2)C6H4O),6.56(br,4H,(NO2)C6H4O),3.97(br,1H,环己基-CH),2.96(br,16H,NCH2),2.61(s,3H,CH3),2.09(1H,环己基-CH),1.89(1H,环己基-CH),1.55-1.05(br,37H),0.87(br,18H,CH3)ppm。
[实施例3]化合物6的合成
使用2,4,5-三氯苯酚采用与化合物4相同的制备方法合成该化合物。O2-氧化反应的速率很慢,所以反应进行了3天。使用按照生产上述60mol%2,4,5-三氯苯酚钠的方法制得的60mol%2,4,5-三氯苯酚钠进行阴离子交换反应。产率95%。1H NMR(dmso-d6,40℃):d 8.34(s,1H,C6H2Cl3O),7.70(s,1H,CH=N),7.39(s,2H,C6H2Cl3O),7.09(s,1H,m-H),6.97(s,1H,m-H),6.85(s,2H,C6H2Cl3O),6.69(s,1H,C6H2Cl3O),4.13(br,1H,环己基-CH),2.99(br,16H,NCH2),2.63(s,3H,CH3),2.10(br,1H,环己基-CH2),1.84(br,1H,环己基-CH2),1.57-1.05(br,37H),0.84(br,18H,CH3)ppm。
[实施例4]化合物7的合成
使用2,4,6-三氯苯酚采用与化合物4相同的制备方法合成化合物7。O2-氧化反应的速率很慢,所以反应进行了3天。使用按照生产上述60mol%2,4,6-三氯苯酚钠的方法制得的60mol%2,4,6-三氯苯酚钠进行阴离子交换反应。产率98%。1H NMR(dmso-d6,40℃):d 7.92(br,1H,CH=N),7.44(br,1H,m-H),7.31(br,1H,m-H),7.20(br,6H,C6H3Cl3O),3.60(br,1H,环己基-CH),3.10(br,16H,NCH2),2.65(s,3H,CH3),2.01(br,1H,环己基-CH2),1.83(br,1H,环己基-CH2),1.66-1.15(br,37H),0.88(br,18H,CH3)ppm。
[实施例5]化合物8的合成
使用五氟苯酚采用与化合物4相同的制备方法合成化合物8。O2-氧化反应的速率很慢,所以反应进行了3天。使用按照生产上述60mol%五氟苯酚钠的方法制得的60mol%五氟苯酚钠进行阴离子交换反应。产率97%。1H NMR(dmso-d6,40℃):d 7.85(br,1H,CH=N),7.18(br,1H,m-H),7.10(br,1H,m-H),4.03(br,1H,环己基-CH),3.09(br,16H,NCH2),2.46(br,3H,CH3),2.09(br,1H,环己基-CH2),1.87(br,1H,环己基-CH2),1.70-1.15(br,37H),0.88(br,18H,CH3)ppm。
[实施例6-10]CO
2
/环氧丙烷共聚
在上面实施例1-5(0.0027mmol,单体/催化剂=50,000)中制得化合物4-8和环氧丙烷(7.71g,135mmol)被加入至弹式反应器(bombreactor)中后,组装该反应器。将所述反应器浸在温度控制在80℃的油浴中,然后搅拌约15分钟使溶液温度达到浴温。在20bar的压力下通入CO2气体。可以观察到,随着聚合反应的发生,CO2压力下降。压力降至7bar(30min反应)时除去CO2气体,终止反应。进一步向所得粘溶液中加入单体10g以降低粘度,然后使溶液通过硅胶垫(400mg,Merck,粒径为0.040-0.063mm(230-400目))得到无色溶液。通过减压下除去所述单体获得白色固体聚合物。通过测定重量来计算TON(周转次数)和TOF(周转频率),使用GPC测定上述得到的聚合物的分子量。通过分析1H NMR谱,计算聚合物形成与碳酸丙烯的选择性。下表2显示了聚合的结果。
[表2]CO2/实施例6-10的环氧丙烷的聚合结果
a单体/催化剂-100,000
[对比例]
[式5]
[对比例1]化合物3的合成
采用如制备化合物4的制备方法生成钴(III)化合物后,用上述获得的100mol%二硝基苯酚钠(5当量)进行阴离子交换反应。产率94%。1H NMR(dmso-d6,40℃):d 8.59(br,2H,(NO2)2C6H3O),7.89(br,1H,CH=N),7.79(br,2H,(NO2)2C6H3O),7.41-7.18(br,2H,m-H),6.32(br,2H,(NO2)2C6H3O),3.62(br,1H,环己基-CH),3.08(br,16H,NCH2),2.62(s,3H,CH3),2.08(1H,环己基-CH),1.82(1H,环己基-CH),1.69-1.05(br,37H),0.83(br,18H,CH3)ppm。
[对比例2]化合物9的合成
采用如制备化合物5的制备方法生成钴(III)化合物后,用上述获得的100mol%4-硝基苯酚钠(5当量)进行阴离子交换反应。产率98%。1H NMR(dmso-d6,40℃):d 7.75(br,2H,C6H4NO2O),7.66(br,1H,CH=N),7.37(br,2H,C6H4NO2O),6.98(br,1H,m-H),6.91(br,3H,m-H,C6H4NO2O),6.21(br,2H,C6H4NO2O),3.85(br,1H,环己基-CH),2.86(br,16H,NCH2),2.50(s,3H,CH3),1.98(br,1H,环己基-CH2),1.78(br,1H,环己基-CH2),1.56-0.90(br,37H),0.72(br,18H,CH3)ppm。
[对比例3]化合物10的合成
采用如制备化合物6的制备方法生成钴(III)化合物后,用上述获得的100mol%2,4,5-三氯苯酚钠(5当量)进行阴离子交换反应。产率94%。1H NMR(dmso-d6,40℃):d 8.34(s,1H,C6H2Cl3O),7.70(s,1H,CH=N),7.11(s,1.5H,C6H2Cl3O),7.09(s,1H,m-H),6.97(s,1H,m-H),6.69(s,1H,C6H2Cl3O),6.39(s,1.5H,C6H2Cl3O),4.13(br,1H,环己基-CH2),1.84(br,1H,环己基-CH2),1.57-1.05(br,37H),0.84(br,18H,CH3)ppm。
[对比例4]化合物11的合成
采用如制备化合物6的制备方法生成钴(III)化合物后,用上述获得的100mol%2,4,6-三氯苯酚钠(5当量)进行阴离子交换反应。产率99%。1H NMR(dmso-d6,40℃):d 7.99(br,1H,CH=N),7.46(br,1H,m-H),7.31(br,1H,m-H),6.91(br,5H,C6H2Cl3O),3.55(br,1H,环己基-CH2),3.08(br,16H,NCH2),2.62(s,3H,CH3),2.00(br,1H,环己基-CH2),1.80(br,1H,环己基-CH2),1.70-1.15(br,37H),0.87(br,18H,CH3)ppm。
[对比例5]化合物12的合成
采用如制备化合物6的制备方法生成钴(III)化合物后,用上述获得的100mol%五氟苯酚钠(5当量)进行阴离子交换反应。产率97%。1H NMR(dmso-d6,40℃):d 7.85(br,1H,CH=N),7.18(br,1H,m-H),7.10(br,1H,m-H),4.03(br,1H,环己基-CH),3.09(br,16H,NCH2),2.46(br,3H,CH3),2.07(br,1H,环己基-CH2),1.89(br,1H,环己基-CH2),1.70-1.15(br,37H),0.88(br,18H,CH3)ppm。
[对比例6-10]CO
2
/环氧丙烷共聚
使用式5的催化剂进行聚合反应。下表3显示了聚合的结果。
[表3]对比例6-10的CO2/环氧丙烷共聚结果
a单体/催化剂=100,000;
b诱导时间不同,观察到值为60~600分钟。
工业实用性
根据本发明,可制备得到数均分子量(Mn)为5,000-1,000,000以及分子量分布(即,Mw/Mn)为1.05-4.0的聚碳酸酯。上述Mn表示使用聚苯乙烯标准物在GPC上测定的数均分子量。所述分子量分布值(Mw/Mn)为在GPC上测定的重均分子量(Mw)和数均分子量(Mn)之间的比值。
获得的聚碳酸酯聚合物包括80%或以上的碳酸盐连接,更多为95%或以上的碳酸盐连接。根据本发明制备的聚碳酸酯易于降解,燃烧时无残留物和烟尘,是用于例如包装、绝缘体或涂料的有益材料。
Claims (7)
1.具有下述式1结构的络合物:
[式1]
[L1L2L3L4M]-[X1...H...X2]- aZ- b
其中,M为钴(III)或铬(III);
L1-L4为阴离子X型配体,L1-L4为相同或各自不同的,也可通过相互连接形成双齿配体、三齿配体或四齿配体,L1-L4中至少一个包括季铵盐,L1-L4中包含的铵阳离子总数为1+a+b,因此所述络合物整体呈中性;
a或b为整数;
L1-L4中除包括季铵盐阳离子的配体之外的配体,或X1和X2各自独立地为卤素阴离子或HCO3 -,或者含或不含卤原子、氮原子、氧原子、硅原子、硫原子和磷原子中的一个或多个且碳原子数6-20的芳氧基阴离子,碳原子数1-20的羧基阴离子;碳原子数1-20的烷氧基阴离子;碳原子数1-20的碳酸盐阴离子;碳原子数1-20的烷基磺酸盐阴离子;碳原子数1-20的酰胺阴离子;碳原子数1-20的甲酰胺阴离子;碳原子数1-20的磺酰胺阴离子;或碳原子数1-20的氨基甲酸酯阴离子,
Z为BF4 -、ClO4 -、NO3 -或PF6 -。
2.如权利要求1所述的络合物,其中所述络合物结构具有下述式2的结构:
[式2]
其中,L5、L6、X3或X4各自独立地为卤素阴离子或HCO3 -,或者含或不含卤原子、氮原子、氧原子、硅原子、硫原子和磷原子中的一个或多个且碳原子数6-20的芳氧基阴离子,碳原子数1-20的羧基阴离子;碳原子数1-20的烷氧基阴离子;碳原子数1-20的碳酸盐阴离子;碳原子数1-20的烷基磺酸盐阴离子;碳原子数1-20酰胺阴离子;碳原子数1-20的甲酰胺阴离子;碳原子数1-20的磺酰胺阴离子;或碳原子数1-20的氨基甲酸酯阴离子,
C为1或0,
Z为BF4 -、ClO4 -、NO3 -或PF6 -,
R12和R14可选自甲基、乙基、异丙基或氢,R11和R13为-[CH{(CH2)3N+Bu3}2]或-[CMe{(CH2)3N+Bu3}2],
Q为用于连接两个氮原子的结合的双自由基。
3.如权利要求2所述的络合物,其中式1中的Q为(C6~C30)亚芳基、(C1~C20)亚烷基、(C2~C20)亚烯基、(C2~C20)亚炔基、(C3~C20)亚环烷基或结合的(C3~C20)亚环烷基,或所述亚芳基、亚烷基、亚烯基、亚炔基、亚环烷基或结合的亚环烷基可被选自下组的取代基所取代:卤原子、(C1~C7)烷基、(C6~C30)芳基或硝基,或包含选自氧、硫和氮的一个或多个杂原子。
4.如权利要求2所述的络合物,其中Q为反式-1,2-环己烯基或乙烯基;X为2,4-二硝基苯酚盐、4-硝基苯酚盐、2,4,5-三氯苯酚盐、2,4,6-三氯苯酚盐或五氟苯酚盐;Z为BF4 -。
6.使用权利要求1-5任一项所述的络合物作为催化剂制备聚碳酸酯的方法,包括:
共聚环氧化合物和CO2的步骤,其中化合物可选自下组:被或未被卤素或烷氧基取代的(C2~C20)环氧烷烃;被或未被卤素或烷氧基取代的(C4~C20)环氧环烷烃;被或未被卤素、烷氧基、烷基或芳基取代的(C8~C20)环氧苯乙烷。
7.制备下述式1的络合物(所述L1、L2和X与下述式1的相同)的方法,包括:
使L1或L2的配体与金属醋酸盐(所述金属为钴或铬)反应以使所述金属与配体结合的步骤;及
所述金属与配体结合后,在氧存在下加入酸(HX),并氧化所述金属使阴离子X配位到所述金属上的步骤;以及
用带有阴离子X的金属盐(所述金属为锂、钠、钾)进行离子交换的步骤:
[式1]
[L1L2L3L4M]-[X1...H...X2]- aZ- b
其中,M为钴(III)或铬(III);
L1-L4为阴离子X型配体,L1-L4为相同或各自不同的,也能够通过相互连接形成双齿配体、三齿配体或四齿配体,L1-L4中的至少一个包括季铵盐,L1-L4中包含的铵阳离子总数为1+a+b,因此所述络合物整体呈中性;
a或b为整数;
L1-L4中除包括季铵盐阳离子的配体之外的配体,或X1和X2各自独立地为卤素阴离子或HCO3 -,或者含或不含卤原子、氮原子、氧原子、硅原子、硫原子和磷原子中一个或多个且碳原子数6-20的芳氧基阴离子,碳原子数1-20的羧基阴离子;碳原子数1-20的烷氧基阴离子;碳原子数1-20的碳酸盐阴离子;碳原子数1-20的烷基磺酸盐阴离子;碳原子数1-20的酰胺阴离子;碳原子数1-20的甲酰胺阴离子;碳原子数1-20的磺酰胺阴离子;或碳原子数1-20的氨基甲酸酯阴离子,
Z为BF4 -、ClO4 -、NO3 -或PF6 -。
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TW201114774A (en) | 2011-05-01 |
KR20100136310A (ko) | 2010-12-28 |
CA2764932A1 (en) | 2010-12-23 |
EP2443131A2 (en) | 2012-04-25 |
KR101221404B1 (ko) | 2013-01-11 |
JP5639163B2 (ja) | 2014-12-10 |
US20100324260A1 (en) | 2010-12-23 |
US20150175743A1 (en) | 2015-06-25 |
EP2443131B1 (en) | 2014-05-21 |
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