CN116284727A - 一种基于离子化有机碱的双组份催化剂及其在聚醚制备中的应用 - Google Patents
一种基于离子化有机碱的双组份催化剂及其在聚醚制备中的应用 Download PDFInfo
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- CN116284727A CN116284727A CN202310307410.XA CN202310307410A CN116284727A CN 116284727 A CN116284727 A CN 116284727A CN 202310307410 A CN202310307410 A CN 202310307410A CN 116284727 A CN116284727 A CN 116284727A
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
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- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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Abstract
Description
技术领域
本发明属于催化聚合技术领域,具体涉及一种基于离子化有机碱的双组份催化剂及其在聚醚制备中的应用。
背景技术
聚醚材料由易旋转的醚键(-C-O-C-)构建而成,具有优异的柔顺性、亲水性、生物相容性、耐低温性、耐臭氧性等,广泛应用于医疗制药、航天航空、建材纺织等重要领域。脂肪族聚醚主要由环氧单体通过均聚或者同源单体共聚得到。以环氧乙烷(EO)和环氧丙烷(PO)开环聚合得到的脂肪族聚醚多元醇产品群,在基础研究、国计民生、高新技术等诸多领域取得了重要应用。聚环氧乙烷(PEO),又称聚氧化乙烯或聚乙二醇,是一种结晶性、热塑性的水溶性聚合物。在医药领域中,由于其水溶液具有无毒性以及良好的生物相容性,常被涂抹在药丸的外层,制成可控缓释药物。在轻工纺织方面,PEO水溶液可用作皮肤清洗剂,如洗涤剂、洗手皂等。在建材工业方面,高分子量的PEO可用作混凝土混合物的分散剂,或用作水泥浆料的添加剂。目前,各行各业对PEO的需求日益增加,从已开发的领域来看,其生产和应用前景广阔。聚环氧丙烷(PPO),又称聚氧化丙烯,常作液压流体、润滑剂、表面活性剂和聚氨酯泡沫塑料或橡胶的中间体。EO与PO的嵌段共聚物(商业名称Pluronic)也是一种非常重要的非离子型表面活性剂,被广泛地应用于日化领域当中。
聚醚丰富的结构以及由此带来的各种性质满足了不同领域的应用需求,进一步推动了相关领域的研究。其中,催化剂是调控聚合物结构性质的重要手段,因此开发新的催化剂以满足聚醚的精细化合成是必要的。工业上常采用碱金属醇盐催化引发环氧单体的开环聚合来制备聚醚材料。然而,碱金属醇盐在有机介质中溶解性差,这使得该反应需要在高温、高压以及强极性溶剂的条件下进行,以提高碱金属醇盐的催化活性和溶解性。但升高温度的同时也加剧了向溶剂和单体的链转移反应,导致聚合反应失控,分子量分布、分子量和产物结构与预期不符。在高温高压的条件下,该类聚合反应是气液相反应,压力对聚合速率也有很大的影响,压力过高或过低都会使产物颜色变深而影响产品质量。双氰金属催化剂(DMC)由于高催化活性而广为人知,是另一类工业级催化剂。但目前还存在许多局限性。DMC对PO的反应活性很高,但对EO的反应活性较低,难以生成一级羟基末端,另一方面,使用该催化剂的聚合反应存在诱导期,且实际生产中需对催化剂进行“活化”。此外,DMC对常规引发体系的适用性比较低,具有强络合能力的引发剂能够阻断聚合反应的进行。
工业上所用的金属类催化剂要在苛刻的条件下才能展现出催化效率高的优势,且通常对水氧十分敏感,不易于保存。此外,金属残留的问题是限制聚醚材料在医药、电子等领域应用的重要因素。近年来,有机小分子催化的开环聚合引起了广泛关注,展现出了媲美金属催化体系的催化效率和化学选择性。此外,有机催化剂还具有反应条件温和、水氧耐受性好、溶解性好、结构稳定等诸多优点。目前用于环氧单体的开环聚合的有机小分子催化剂主要有N-杂环烯、N-杂环卡宾、磷腈碱等中性有机强碱。这类催化剂通过活化羟基,形成烷氧阴离子,进而亲核进攻环氧单体使其开环,继而完成聚合物链增长。不足的是,在中性有机强碱催化体系中,增强有机碱的碱性虽然可以提高聚合效率,但同时也会伴随着显著的向单体链转移的副反应,造成分子量和高分子结构不可控。近些年,赵俊鹏课题组通过在有机碱活化引发剂/链末端的基础上,再加入Lewis酸三乙基硼活化单体,很好地解决上述聚合效率与可控性不兼容的问题(Macromolecules.2018,51(20):8286-8297)。该催化体系在碱的用量低至50ppm的条件下,依然能够高效可控地实现环氧乙烷的开环聚合,即使对于活性相对较低的环氧丙烷,催化剂的转化频率也可达到2720h-1,且在聚合过程中能够完全避免向单体的链转移副反应,得到分子量和分布都可控,结构特征明确的聚醚。
上述有机碱/三乙基硼的无金属催化体系虽然具有诸多优势,但其催化活性也与碱性高度相关。对于其中使用的非亲核性有机碱来说,越强的碱性往往要求其具有更为复杂的共轭结构,导致催化剂活性调节的范围和灵活度受限、催化剂合成工艺繁琐、成本增加、实用性降低,极大地限制了其在工业上的应用。脲/硫脲/方酰胺这类基于氢键作用的有机小分子催化剂在有机不对称催化领域中广受关注,在许多不对称有机合成反应(如Michael反应,Aldol反应,Mannich反应,Henry反应等)中展现出了高效的催化活性以及良好的对映选择性。近年来,这类有机小分子在高分子合成领域中常与强碱共同使用,能够高效可控地催化环酯的开环聚合。文献Jiang Z,et al.Ionic Organocatalyst with a UreaAnion and Tetra-n-butyl Ammonium Cation for Rapid,Selective,and VersatileRing-Opening Polymerization of Lactide.ACS Macro Letters.2019,8(7):759-765,通过四正丁基氢氧化铵与N,N-二取代硫脲/脲通过脱水反应制备了一系列离子化有机碱催化剂,在室温下实现了环酯单体高效、高选择性的开环聚合。同时,离子化有机碱种类丰富、价格低廉、结构易于设计,可以通过简单地变换两侧的取代基来实现催化活性的调节。但是仅凭离子化有机碱的氢键活化作用,不足以使环氧单体开环聚合。因此,一种合适、高效的催化体系及其用于合成聚醚的研究仍在继续。
发明内容
鉴于现有技术存在制备工艺繁琐、反应条件苛刻、生产成本高、反应体系调节不够灵活的不足,本发明的目的在于提供一种基于离子化有机碱的双组分催化剂及其在聚醚制备中的应用。本发明首次将离子化有机碱与路易斯酸(Lewis酸)组成双组份催化剂,其价格低廉、制备简便、结构和活性易灵活调节,在环氧单体开环聚合制备聚醚的反应中展现出高效性、化学选择性、可控性与普适性,得到一系列窄分布、分子量范围广、结构明确的聚醚高分子。
为了实现上述目的,本发明采用的技术方案是:
一种基于离子化有机碱的双组份催化剂在聚醚制备中的应用,包括以下步骤:
S1:将离子化有机碱与路易斯酸(Lewis酸)在惰性气氛中混合,得到双组份催化剂;
S2:在惰性气氛中,将环氧单体、质子引发剂与双组份催化剂混合进行聚合反应,即得聚醚类高分子。
进一步地,所述的离子化有机碱,具有如式I或式Ⅱ所示的结构:
式I中,
X表示O或S;
Z表示O、S、CRR或NR,其中R表示H或碳原子数为1~12的烃基;
Y表示N或P;
(Rn)4表示四个独立且碳原子数为1~12的烃基;
R1和R2为各自独立且碳原子数为1~10的烷基、乙烯基、酰基、磺酰基、苯基、取代苯基、萘基、取代萘基。
式Ⅱ中,
Y表示N或P;
(Rn)4表示四个独立且碳原子数为1~12的烃基;
R1和R2为各自独立且碳原子数为1~10的烷基、乙烯基、酰基、磺酰基、苯基、取代苯基、萘基、取代萘基。
进一步地,所述的路易斯酸为烷基硼化合物、烷基铝化合物、金属卤化物中的至少一种。
进一步地,所述的烷基硼化合物为B-异松蒎基-9-硼二环[3.3.1]壬烷、C1至C10的三烷基硼、三(五氟苯基)硼、三甲基环三硼氧烷、三苯基环三硼氧烷、硼酸三苯酯中的至少一种。
进一步地,所述的烷基铝化合物为三异丁基铝、C1至C10的三烷基铝、三苯基铝、三(五氟苯基)铝中的至少一种。
进一步地,所述的金属卤化物为氯化铝、氯化镁、氯化锂、氯化锌、碘化镁、溴化镁、碘化锌中的至少一种。
进一步地,所述的环氧单体为C0至C20的直链烷基环氧乙烷、氧化苯乙烯、环氧环己烷、4-乙烯基环氧环己烷、氧化柠檬烯、C1至C20的烃基缩水甘油醚、C1至C20的烃基缩水甘油酯中的至少一种。
进一步地,所述的C1至C20的烃基缩水甘油醚为C1至C16的直链烷基缩水甘油醚、异丙基缩水甘油醚、叔丁基缩水甘油醚、2-乙基己基缩水甘油醚、苯基缩水甘油醚、苄基缩水甘油醚、烯丙基缩水甘油醚、炔丙基缩水甘油醚中的至少一种。
进一步地,所述的C1至C20的烃基缩水甘油酯为C1至C10的直链烷基缩水甘油酯、甲基丙烯酸缩水甘油酯,直链脂肪酸缩水甘油酯、、叔碳酸缩水甘油酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、肉桂酸缩水甘油酯中的至少一种。
进一步地,所述的质子引发剂包含氨基、亚氨基、羟基、酚羟基、巯基、羧基、硫代羧基中的至少一种基团。
进一步地,所述的包含氨基、亚氨基的质子引发剂为C1至C10的直链烷基胺、异丙胺、叔丁胺、3-丁烯-1-胺、(S)-丁-2-胺、(R)-丁-2-胺、异丁胺、2-氨基丁烷、丁-3-炔-1-胺、N-乙基甲基胺、N-烯丙基甲胺、N-异丙基甲胺、二乙胺、N-甲基丙胺、C1至C10的直链烷基二胺、1,2-二氨基丙烷、N-甲基乙二胺中的至少一种。
进一步地,所述的包含羟基、酚羟基的质子引发剂为甲醇或C1至C18的直链烷基醇、异丙醇、2-丁醇、叔丁醇、C1至C10的1-苯基直链烷基醇、烯丙基醇或C4至C10的直链端烯1-醇、1-萘甲醇、顺丁烯二醇、乙二醇、1,4-丁二醇、对苯二甲醇、1,1,1-三羟甲基丙烷、甘油、季戊四醇、双季戊四醇、山梨醇、三季戊四醇中的至少一种。
进一步地,所述的包含巯基的质子引发剂为硫代乙醇或C3至C12的的直链硫醇,异戊硫醇,叔丁硫醇、乙二硫醇、2,3-丙二硫醇、1,1-丙二硫醇、1,6-己二硫醇、3,4-己二硫醇、四(3-巯基丙酸)季戊四醇酯、C7至C18的1-苯基直链烷基硫醇、1,3,5-苯三硫酚中的至少一种。
进一步地,所述的包含羧基的质子引发剂为甲酸或C2至C18的直链脂肪酸、异戊酸、丙烯酸、甲基丙烯酸、山梨酸、丙炔酸、苯甲酸或C7至C18的1-苯基直链烷基羧酸、草酸、十二烷二酸、顺丁烯二酸、反丁烯二酸、戊烯二酸、C6至C16的双不饱和二羧酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、1.3.5-苯三甲酸、丙三酸、丁烷四羧酸、胆酸、白桦醇酸、柠檬酸、葡萄糖酸、葡萄糖醛酸中的至少一种。
进一步地,所述的包含硫代羧基的质子引发剂为硫代乙酸、C3至C12的的直链硫代羧酸、硫代异戊酸、硫代特戊酸,硫代丙烯酸,硫代甲基丙烯酸,硫代苯甲酸或C8至C18的1-苯基直链烷基硫代羧酸,环己烷硫代甲酸,硫代烟酸,二硫代对苯二甲酸,二硫代草酸中的至少一种。
进一步地,所述的质子引发剂、离子化有机碱、路易斯酸三者的摩尔比为1:(0.005~10):(0.01~30)。
进一步地,所述聚合反应的反应时间为1~300h,反应温度为0~100℃。
进一步地,所述聚合反应的反应可在本体中进行,也可在溶剂中进行;所述溶剂为四氢呋喃、苯、甲苯、乙酸乙酯、环己烷、丙酮、2-甲基四氢呋喃、1,4-二氧六环、二氯甲烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、γ-丁内酯、丙烯碳酸酯、乙腈中的至少一种。
本发明相对于现有技术,具有以下优点和有益效果:
(1)针对现有中性有机碱存在活性调节的范围和灵活度受限、催化剂合成工艺繁琐、成本增加、实用性降低的不足。本发明使用的离子化有机碱原料易得、制备简便、结构丰富,具有价格低廉、结构稳定、活性易调节的优势,可以通过简单地变换离子化有机碱两侧的取代基来实现催化活性的调节,能够以较为简单的结构来实现较高碱性。
(2)本发明中首次将离子化有机碱与Lewis酸联用组成双组份催化剂,其活性不仅取决于离子化有机碱的主体结构和取代基,还受控于Lewis酸的种类、有机碱和Lewis酸的比例。对于位阻比较大、反应活性比较低的环氧单体,我们可以通过选择对称结构或碱性比较高的离子化有机碱、亲电性高的Lewis酸来催化聚合,也可以通过提高Lewis酸的比例来调节催化活性。因而该体系显著增大了催化活性调节和优化的窗口,可以针对不同环氧单体的结构和活性特征,对催化活性进行灵活的调节和优化。
(3)本发明中双组份催化剂与质子型引发剂互为独立组分,可以搭配不同的引发剂(如官能化引发剂、多官能引发剂、大分子引发剂)或单体使用,制备分子量及分布可控、结构丰富且明确的聚醚(具有端基官能化、侧基官能化、星状、接枝、嵌段、多嵌段等结构特征)。
(4)本发明的基于离子化有机碱的双组份催化剂能够高效可控地催化环氧单体的开环聚合,可以根据环氧单体的反应活性特征来设计催化剂结构。在较低的催化剂用量下,也能在数小时内转化完全。该反应能在室温无溶剂的条件下进行,极大地提升了操作的简便性、灵活性、安全性。
(5)本发明的基于离子化有机碱的双组份催化剂对环氧单体的开环聚合展现出优异的化学选择性、可控性与普适性,在聚合过程中能够完全规避向单体的破坏性链转移反应,所制备聚醚的端基和侧基的官能团结构能够保持完整,分子量及分布都可控。通过连续加料能够实现多种环氧单体嵌段聚合,提高了嵌段聚醚合成的效率、简便性、可控性,丰富了嵌段和多嵌段聚醚的结构。
本发明所使用的离子化有机碱、Lewis酸、质子引发剂、环氧单体各组分相对独立,可以灵活方便地组合使用满足多样化生产的需要。与不同的引发剂使用可以制备具有端基官能化、侧基官能化、星状、接枝、嵌段、多嵌段等结构特征的聚醚。温和的反应条件、离子化有机碱与Lewis酸的双重调控能够确保在聚合过程中引发剂的官能团结构不会发生变化,而且能够完全规避向单体的破坏性链转移反应。基于离子化有机碱的双组份催化剂可以通过多种手段(离子化有机碱中两侧取代基、四烃基铵/磷反离子、Lewis酸的种类、离子化有机碱与Lewis酸的比例)来调节催化活性,从而达到对环氧单体开环聚合的精准调控。基于离子化有机碱的双组份催化剂合成路线简便、原料来源广泛、价格低廉、性质稳定、活性易调节,在工业应用上具有不可比拟的优势。
附图说明
图1a为实施例3合成的聚醚的SEC曲线。
图1b为实施例3合成的聚醚的1H NMR谱图。
图2a为实施例9合成的聚醚的SEC曲线。
图2b为实施例9合成的聚醚的1H NMR谱图。
图3a为实施例11合成的聚醚的SEC曲线。
图3b为实施例11合成的聚醚的1H NMR谱图。
图4a为实施例12合成的聚醚的SEC曲线。
图4b为实施例12合成的聚醚的1H NMR谱图。
图5a为实施例16合成的聚醚的SEC曲线。
图5b为实施例16合成的聚醚的1H NMR谱图。
图6a为实施例24合成的聚醚的SEC曲线。
图6b为实施例24合成的聚醚的1H NMR谱图。
图7a为实施例28合成的聚醚的SEC曲线。
图7b为实施例28合成的聚醚的1H NMR谱图。
具体实施方式
下面结合具体实施例对本发明作进一步详细描述,但本发明的实施方式不限于此。凡基于本发明上述内容所实现的技术均属于本发明的范围。
以下实施例中:
单体的转化率、聚合物结构特征由Bruker AV400液体核磁共振仪测得,溶剂为氘代氯仿。
聚环氧乙烷的分子量及分子量分散度由体积排除色谱(SEC)测得,仪器采用Waters 1515型泵和HR-2、HR-4、HR-6系列色谱柱,以N,N-二甲基甲酰胺为流动相,柱温50℃,流速1mL/min;以一系列聚环氧乙烷标准样品作校准曲线。
其余聚合物的分子量及分散度的测试采用美国安捷伦(Agilent)1260Infinity型号的体积排除色谱仪测得,流动相为四氢呋喃,柱温35℃,流速1mL/min;以一系列聚苯乙烯或聚环氧乙烷标准样品作校准曲线。
以下实施例中配方所述份数均为摩尔份数。作为举例,摩尔份数可以为mol、mmol等,也可以是本领域常用的任意其他用量。
实施例1
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧乙烷(EO)的开环聚合。具体操作如下:
在惰性气氛中,将0.1份Sq1A3、0.3份Et3B、1份BEDO加入到Schlenk瓶中,然后将Schlenk瓶连接到真空线上,并用冰水降温,在0~4℃的条件下加入200份EO,在室温下反应4h后,加入0.1mL乙酸终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得理论数均分子量(Mn,th)为8.8kg/mol,SEC测得数均分子量(Mn,SEC)为9.2kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为9.1kg/mol,分子量分布为1.07。
实施例2
以离子化有机碱1,4-二环己基方酰胺四丁基铵(Sq5A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧乙烷(EO)的开环聚合。具体操作如下:
在惰性气氛中,将1份Sq5A3、10份Et3B、1份BEDO加入到Schlenk瓶中,然后加入2000份EO(加入环氧乙烷的操作步骤同实施例1),室温下反应24h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得理论数均分子量(Mn,th)为88.1kg/mol,SEC测得数均分子量(Mn,SEC)为90.7kg/mol,分子量分布为1.10。
实施例3
以离子化有机碱1,4-二叔丁基方酰胺四丁基铵(Sq10A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,甲基丙烯酸(MA)为质子引发剂,实施环氧丙烷(PO)的开环聚合。具体操作如下:
在惰性气氛中,将0.1份Sq10A3、0.3份Et3B、1份MA与100份PO混合,室温下反应6h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得PO的转化率为95%,理论数均分子量(Mn,th)为5.5kg/mol,SEC测得数均分子量(Mn,SEC)为6.8kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为5.5kg/mol,分子量分布为1.09。
以Sq10A3-Et3B为双组份催化剂,MA为引发剂,实施PO的开环聚合得到的粗产物的SEC曲线和1H NMR谱图分别如图1a和图1b所示。SEC曲线分布较窄,说明聚合过程符合活性聚合的特征,该催化剂具有优异的化学选择性。1H NMR谱图表明所得聚合物是由MA引发的PPO,结构明确。
实施例4
以离子化有机碱1,4-二苯基方酰胺四甲基铵(Sq1A1)、Lewis酸三乙基硼(Et3B)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧丙烷(PO)的开环聚合。具体操作如下:
在惰性气氛中,将1份Sq1A1、3份Et3B、1份BEDO与1000份PO混合,室温下反应12h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得PO的转化率为100%,理论数均分子量(Mn,th)为58.1kg/mol,SEC测得数均分子量(Mn,SEC)为60.4kg/mol,分子量分布为1.09。
实施例5
以离子化有机碱1,3-二苯基脲四丁基铵(U1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,丙三醇(GA)为质子引发剂,实施环氧乙烷(EO)的开环聚合。具体操作如下:
在惰性气氛中,将1份U1A3、3份Et3B、1份GA以及有机溶剂四氢呋喃加入Schlenk瓶中,然后加入2000份EO(加入环氧乙烷的操作步骤同实施例1),EO的浓度为3mol/L。室温下反应24h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得理论数均分子量(Mn,th)为88.1kg/mol,SEC测得数均分子量(Mn,SEC)为92.6kg/mol,分子量分布为1.10。
实施例6
以离子化有机碱为1-[3,5-二(三氟甲基)苯基]-3-苯基脲三甲基苄基铵(U2A2)、Lewis酸三乙基硼(Et3B)为双组份催化剂,苯甲酸(BA)为质子引发剂,实施环氧丙烷(PO)的开环聚合。
具体操作如下:
在惰性气氛中,将0.1份U2A2、0.3份Et3B、1份BA与100份PO混合,室温下反应24h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得PO的转化率为77%,理论数均分子量(Mn,th)为4.5kg/mol,SEC测得数均分子量(Mn,SEC)为5.1kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为4.0kg/mol,分子量分布为1.10。
实施例7
以离子化有机碱1-苯基3-环己基脲四丁基铵(U3A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,乙二硫醇(EDT)为质子引发剂,实施环氧丙烷(PO)的开环聚合。具体操作如下:
在惰性气氛中,将0.1份U3A3、0.3份Et3B、1份EDT与200份PO混合,室温下反应4h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得PO的转化率为92%,理论数均分子量(Mn,th)为11.1kg/mol,SEC测得数均分子量(Mn,SEC)为12.4kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为10.9kg/mol,分子量分布为1.08。
实施例8
以离子化有机碱1,3-二苯基脲四丁基磷(U1P1)、Lewis酸三乙基硼(Et3B)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧丙烷(PO)的开环聚合。具体操作如下:
在惰性气氛中,将0.1份U1P1、0.3份Et3B、1份BEDO、500份PO和有机溶剂2-甲基四氢呋喃混合,PO的浓度为5mol/L,室温下反应12h后终止反应,取少量粗产物进行SEC和1HNMR测试。
计算可得PO的转化率为92%,理论数均分子量(Mn,th)为26.7kg/mol,SEC测得数均分子量(Mn,SEC)为33.7kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为28.4kg/mol,分子量分布为1.10。
实施例9
以离子化有机碱1,3-二苯基硫脲四丁基铵(TU1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧丙烷(PO)的开环聚合。具体操作如下:
在惰性气氛中,将0.1份TU1A3、0.3份Et3B、1份BEDO和100份PO混合,室温下反应6h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得PO的转化率为98%,理论数均分子量(Mn,th)为5.7kg/mol,SEC测得数均分子量(Mn,SEC)为7.4kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为5.2kg/mol,分子量分布为1.09。
以TU1A3-Et3B为双组份催化剂,BEDO为引发剂,实施PO的开环聚合得到的粗产物的SEC曲线和1H NMR谱图分别如图2a和图2b所示。可以看到1H NMR谱图上没有出现向单体转移产生的不饱和烯丙基C=C双键特征峰,说明在反应过程中没有发生向单体的链转移副反应,说明了该类催化剂对聚醚的合成具有良好的化学选择性。
实施例10
以离子化有机碱为1-[3,5-二(三氟甲基)苯基]-3-苯基硫脲四丁基铵(TU2A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧丙烷(PO)的开环聚合。具体操作如下:
在惰性气氛中,加入0.1份TU2A3、0.3份Et3B、1份BEDO与100份PO混合,在0℃下反应72h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得PO的转化率为47%,理论数均分子量(Mn,th)为2.7kg/mol,SEC测得数均分子量(Mn,SEC)为3.0kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为2.9kg/mol,分子量分布为1.07。
实施例11
以离子化有机碱1,3-二(4-甲基苯磺酰基)脲四丁基铵(SU1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂、季戊四醇(PT)为质子引发剂,实施环氧乙烷(EO)的开环聚合。具体操作如下:
在惰性气氛中,将0.1份SU1A3、0.6份Et3B、1份PT加入到Schlenk瓶中,然后加入100份EO(加入环氧乙烷的操作步骤同实施例1),室温下反应6h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得理论数均分子量(Mn,th)为4.4kg/mol,SEC测得数均分子量(Mn,SEC)为4.0kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为3.9kg/mol,分子量分布为1.09。
以SU1A3-Et3B为双组份催化剂,PT为引发剂,实施EO的开环聚合得到的粗产物的SEC曲线和1H NMR谱图分别如图3a和图3b所示。可以看到Mn,SEC、Mn,th基本一致,分子量分布比较窄,1H NMR谱图也证实了产物是由PT引发得到的星型聚醚。
实施例12
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂、硫代乙酸(TA)为质子引发剂,实施环氧乙烷(EO)的开环聚合。具体操作如下:
在惰性气氛中,将0.01份Sq1A3、0.03份Et3B、1份TA加入到Schlenk瓶中,然后加入50份EO(加入环氧乙烷的操作步骤同实施例1),室温下反应24h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得理论数均分子量(Mn,th)为2.2kg/mol,SEC测得数均分子量(Mn,SEC)为2.6kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为2.2kg/mol,分子量分布为1.07。
以Sq1A3-Et3B为双组份催化剂,TA为引发剂,实施EO的开环聚合得到的粗产物的SEC曲线和1H NMR谱图分别如图4a和图4b所示。可以看到所得产物是由TA引发的PEO,具有窄分布的特征,使用硫代羧酸类引发剂也能引发聚合,进一步地说明了该催化剂的普适性。
实施例13
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三异丁基铝(iBu3Al)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧乙烷(EO)的开环聚合。
将Lewis酸替换为iBu3Al,其他操作同实施例1。
计算可得理论数均分子量(Mn,th)为8.8kg/mol,SEC测得数均分子量(Mn,SEC)为9.6kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为9.0kg/mol,分子量分布为1.12。
实施例14
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三正丁基硼(nBu3B)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧乙烷(EO)的开环聚合。
将Lewis酸替换为nBu3B,其他操作同实施例1。
计算可得理论数均分子量(Mn,th)为8.8kg/mol,SEC测得数均分子量(Mn,SEC)为9.7kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为9.4kg/mol,分子量分布为1.08。
实施例15
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis碘化锌(ZnI2)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施环氧乙烷(EO)的开环聚合。
将Lewis酸替换为ZnI2,其他操作同实施例1。
计算可得理论数均分子量(Mn,th)为8.8kg/mol,SEC测得数均分子量(Mn,SEC)为10.2kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为9.9kg/mol,分子量分布为1.12。
实施例16
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸氯化锂(LiCl)为双组份催化剂,苯甲醇(BA)为质子引发剂,实施右旋丁酸缩水甘油酯(RGB)的开环聚合。具体操作如下:
在惰性气氛中,将1份Sq1A3、3份LiCl、1份BEDO与100份RGB混合,在室温下反24h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得转化率为96%,理论数均分子量(Mn,th)为13.8kg/mol,SEC测得数均分子量(Mn,SEC)为13.0kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为14.6kg/mol,分子量分布为1.09。
以Sq1A3-LiCl为双组份催化剂,BA为引发剂,实施RGB的开环聚合得到的粗产物的SEC曲线和1H NMR谱图分别如图5a和图5b所示。可以看出对于大位阻单取代环氧化合物,该催化剂依然能够保持较高的催化活性,从1H NMR谱图上来看RGB的侧基官能团能够完整保留,进一步地说明了催化剂优异的化学选择性以及高催化活性。
实施例17
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,顺丁烯二醇(BEDO)为质子引发剂,实施烯丙基缩水甘油醚(AGE)的开环聚合。具体操作如下:
在惰性气氛中,将0.1份Sq1A3、0.3份Et3B、1份BEDO与100份AGE混合,在室温下反应12h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得AGE的转化率为94%,理论数均分子量(Mn,th)为10.7kg/mol,SEC测得数均分子量(Mn,SEC)为13.4kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为11.2kg/mol,分子量分布为1.10。
实施例18
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,对二苯甲醇(BDM)为质子引发剂,实施环氧丁烷(BO)的开环聚合。具体操作如下:
在惰性气氛中,将1份Sq1A3、3份Et3B、1份BDM、1000份BO和有机溶剂甲苯混合,BO的浓度为5mol/L,室温下反应12h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得BO的转化率为89%,理论数均分子量(Mn,th)为64.2kg/mol,SEC测得数均分子量(Mn,SEC)为71.8kg/mol,分子量分布为1.12。
实施例19
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,对二苯甲醇(BDM)为质子引发剂,实施环氧丁烷(BO)的开环聚合。具体操作如下:
在惰性气氛中,将0.005份Sq1A3、0.01份Et3B、1份BDM与20份BO混合,100℃反应4h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得BO的转化率为100%,理论数均分子量(Mn,th)为1.7kg/mol,SEC测得数均分子量(Mn,SEC)为2.1kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为1.7kg/mol,分子量分布为1.12。
实施例20
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,对二苯甲醇(BDM)为质子引发剂,实施环氧丁烷(BO)的开环聚合。具体操作如下:
在惰性气氛中,将0.005份Sq1A3、0.01份Et3B、1份BDM与20份BO混合,室温下反应300h后终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得BO的转化率为100%,理论数均分子量(Mn,th)为1.7kg/mol,SEC测得数均分子量(Mn,SEC)为2.3kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为1.9kg/mol,分子量分布为1.10。
实施例21
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,N-异丙基甲胺为质子引发剂,实施环氧丁烷(BO)的开环聚合。具体操作如下:
将引发剂由对二苯甲醇替换为N-异丙基甲胺,其他操作同实施例18。
计算可得BO的转化率为100%,理论数均分子量(Mn,th)为1.7kg/mol,SEC测得数均分子量(Mn,SEC)为2.3kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为1.8kg/mol,分子量分布为1.07。
实施例22
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,己二胺(HMDA)为质子引发剂,实施环氧丁烷(BO)的开环聚合。具体操作如下:
将引发剂由对二苯甲醇替换为HMDA,其他操作同实施例19。
计算可得BO的转化率为100%,理论数均分子量(Mn,th)为1.7kg/mol,SEC测得数均分子量(Mn,SEC)为2.2kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为1.8kg/mol,分子量分布为1.14。
实施例23
以离子化有机碱1-苯基-4-环己基方酰胺四丁基铵(Sq11A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,对二苯甲醇(BDM)为质子引发剂,实施环氧乙烷(EO)与环氧丙烷(PO)的嵌段聚合,制备PEO-b-PPO-b-PEO三嵌段聚醚二醇。具体操作如下:
在惰性气氛中,将0.1份Sq11A3、0.3份Et3B、1份BDM与400份PO在Schlenk瓶中混合,室温下反应12h后取少量产物进行SEC和1H NMR测试。
计算可得PO的转化率为100%,理论数均分子量(Mn,th)为23.2kg/mol,SEC测得数均分子量(Mn,SEC)为25.7kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为24.3kg/mol,分子量分布为1.08。
然后将该Schlenk瓶连接到真空线上,加入400份EO在室温下反应24h后(加入环氧乙烷的操作步骤同实施例1),加入0.1mL乙酸终止反应,取少量粗产物进行SEC和1HNMR测试。
计算可得三嵌段聚醚二醇(PPO-b-PEO-b-PPO)理论数均分子量(Mn,th)为40.8kg/mol,SEC测得数均分子量(Mn,SEC)为43.6kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为42.9kg/mol,分子量分布为1.09
实施例24
以离子化有机碱1-苯基-4-环己基方酰胺四丁基铵(Sq11A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,对二苯甲醇(BDM)为质子引发剂,实施环氧乙烷(EO)与环氧丙烷(PO)的嵌段聚合,制备PPO-b-PEO-b-PPO三嵌段聚醚二醇。具体操作如下:
在惰性气氛中,将0.1份Sq11A3、0.3份Et3B、1份BDM与400份EO在Schlenk瓶中混合,室温下反应6h后取少量产物进行SEC和1H NMR测试。
计算可得理论数均分子量(Mn,th)为17.6kg/mol,SEC测得数均分子量(Mn,SEC)为22.4kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为19.2kg/mol,分子量分布为1.07。
然后将该Schlenk瓶连接到真空线上,加入400份PO,在室温下反应6h后,加入0.1mL乙酸终止反应,取少量粗产物进行SEC和1H NMR测试。
计算可得PO的转化率为96%,理论数均分子量(Mn,th)为40.8kg/mol,SEC测得数均分子量(Mn,SEC)为44.4kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为47.6kg/mol,分子量分布为1.06。
以Sq11A3-Et3B为双组份催化剂,BDM为引发剂,实施环氧乙烷(EO)与环氧丙烷(PO)的嵌段聚合得到的粗产物的SEC曲线和1H NMR谱图分别如图6a和图6b所示,可以看出高分子量聚合物依然能够保持窄分布,且Mn,SEC与Mn,th基本能够保持一致,依然没有发生向单体的链转移的副反应,体现了基于离子化有机碱的双组份催化剂对环氧聚合具有高选择性以及普适性。EO与PO在连续嵌段共聚中能够完全转化,1H NMR谱图也证实了产物是结构明确的PPO-b-PEO-b-PPO三嵌段聚醚二醇。
实施例25
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,1-萘甲醇(NtA)为质子引发剂,实施环氧乙烷(EO)与环氧丙烷(PO)的嵌段聚合,制备PPO-b-PEO嵌段聚醚。具体操作如下:
在惰性气氛中,将1份Sq1A3、3份Et3B、1份NtA、1000份PO与有机溶剂四氢呋喃混合,PO的浓度为3mol/L,室温下反应6h后取少量产物进行SEC和1H NMR测试。
计算可得PO的转化率为100%,理论数均分子量(Mn,th)为58.1kg/mol,SEC测得数均分子量(Mn,SEC)为62.7kg/mol,分子量分布为1.09。
然后加入2000份EO,在室温下反应24h后终止反应,取少量粗产物进行SEC和1HNMR测试。
计算理论数均分子量(Mn,th)为146.2kg/mol,SEC测得数均分子量(Mn,SEC)为164.4kg/mol,分子量分布为1.17。
实施例26
以离子化有机碱1,4-二苯基方酰胺四丁基铵(Sq1A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,1-萘甲醇(NtA)为引发剂,实施环氧丙烷(PO)与烯丙基缩水甘油醚(AGE)的嵌段聚合,制备PPO-b-PAGE嵌段聚醚。具体操作如下:
在惰性气氛中,先加入1000份PO,室温下反应6h后,取少量产物进行SEC和1HNMR测试,再加入1000份AGE,室温下反应12h后终止反应,取少量产物进行SEC和1HNMR测试,其他操作同实施例21。
PO的转化率为100%,聚环氧丙烷(PPO)的理论数均分子量(Mn,th)为58.1kg/mol,SEC测得数均分子量(Mn,SEC)为62.4kg/mol,分子量分布为1.07。
AGE的转化率为88%,嵌段聚醚(PPO-b-PAGE)理论数均分子量(Mn,th)为158.5kg/mol,SEC测得数均分子量(Mn,SEC)为177.9kg/mol,分子量分布为1.19。
实施例27
以离子化有机碱1,4-二环己基方酰胺四丁基铵(Sq5A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,对二苯甲醇(BDM)为质子引发剂,实施叔丁基缩水甘油醚(BGE)与烯丙基缩水甘油醚(AGE)的嵌段聚合,制备PBGE-b-PAGE-b-PBGE三嵌段聚醚二醇。具体操作如下:
在惰性气氛中,在惰性气氛中,将10份Sq5A3、30份Et3B、1份BDM、400份AGE与有机溶剂丙烯碳酸酯混合,AGE的浓度为3mol/L,室温下反应12h后取少量产物进行SEC和1H NMR测试。
AGE的转化率为47%,PAGE的理论数均分子量(Mn,th)为21.4kg/mol,SEC测得数均分子量(Mn,SEC)为25.4kg/mol,1H NMR计算得出的数均分子量(Mn,NMR)为23.8kg/mol,分子量分布为1.12。
然后加入400份BGE,在室温下反应300h后终止反应,取少量产物进行SEC和1HNMR测试。
BGE的转化率为72%,PBGE-b-PAGE-b-PBGE理论数均分子量(Mn,th)为58.8kg/mol,SEC测得数均分子量(Mn,SEC)为64.5kg/mol,分子量分布为1.19。
实施例28
以离子化有机碱1,4-二环己基方酰胺四丁基铵(Sq5A3)、Lewis酸三乙基硼(Et3B)为双组份催化剂,对二苯甲醇(BDM)为质子引发剂,实施叔丁基缩水甘油醚(BGE)与烯丙基缩水甘油醚(AGE)的嵌段聚合,制备PAGE-b-PBGE-b-PAGE三嵌段聚醚二醇。具体操作如下:
在惰性气氛中,先加入400份BGE,有机溶剂换为二氯甲烷,室温下反应1h后,取少量产物进行SEC和1H NMR测试,再加入400份AGE,室温下反应1h后终止反应,取少量产物进行SEC和1H NMR测试,其他操作同实施例26。
BGE的转化率为100%,PBGE的理论数均分子量(Mn,th)为52.1kg/mol,SEC测得数均分子量(Mn,SEC)为62.1kg/mol,分子量分布为1.07。
AGE的转化率为100%,PAGE-b-PBGE-b-PAGE的理论数均分子量(Mn,th)为98.1kg/mol,SEC测得数均分子量(Mn,SEC)为88.4kg/mol,分子量分布为1.06。
以Sq5A3-Et3B为双组份催化剂,BDM为引发剂,实施叔丁基缩水甘油醚(BGE)与烯丙基缩水甘油醚(AGE)的嵌段聚合得到的粗产物的SEC曲线和纯化产物的1H NMR谱图分别如图7a和图7b所示。可以看到高分子量聚醚依然能够保持窄分布,且AGE开环聚合后侧基的不饱和双键能够完整保留,对于大位阻取代环氧催化剂仍保持较高的催化活性,进一步地说明了该催化剂具有优异的化学选择性与高效性。
以上实施例仅为本发明较优的实施方式,仅用于解释本发明,而非限制本发明,本领域技术人员在未脱离本发明精神实质下所作的改变、替换、修饰等均应属于本发明的保护范围。
Claims (10)
1.一种基于离子化有机碱的双组分催化剂在聚醚制备中的应用,其特征在于,包括以下步骤:
S1:将离子化有机碱与路易斯酸在惰性气氛中混合,得到双组分催化剂;
S2:在惰性气氛中,将环氧单体、质子引发剂与双组份催化剂混合进行聚合反应,即得聚醚类高分子。
3.根据权利要求1所述的一种基于离子化有机碱的双组分催化剂在聚醚制备中的应用,其特征在于,所述的路易斯酸为烷基硼化合物、烷基铝化合物、金属卤化物中的至少一种。
4.根据权利要求3所述的一种基于离子化有机碱的双组分催化剂在聚醚制备中的应用,其特征在于,所述的烷基硼化合物为B-异松蒎基-9-硼二环[3.3.1]壬烷、C1至C10的三烷基硼、三(五氟苯基)硼、三甲基环三硼氧烷、三苯基环三硼氧烷、硼酸三苯酯中的至少一种;所述的烷基铝化合物为三异丁基铝、C1至C10的三烷基铝、三苯基铝、三(五氟苯基)铝中的至少一种;所述的金属卤化物为氯化铝、氯化镁、氯化锂、氯化锌、碘化镁、溴化镁、碘化
锌中的至少一种。
5.根据权利要求1所述的一种基于离子化有机碱的双组分催化剂在聚醚制备中的应用,其特征在于,所述的环氧单体为C0至C20的直链烷基环氧乙烷、氧化苯乙烯、环氧环己烷、4-乙烯基环氧环己烷、氧化柠檬烯、C1至C20的烃基缩水甘油醚、C1至C20的烃基缩水甘油酯中的至少一种。
6.根据权利要求1所述的一种基于离子化有机碱的双组分催化剂在聚醚制备中的应用,其特征在于,所述的质子引发剂包含氨基、亚氨基、羟基、酚羟基、巯基、羧基、硫代羧基中的至少一种基团。
7.根据权利要求1所述的一种基于离子化有机碱的双组分催化剂在聚醚制备中的应用,其特征在于,质子引发剂、离子化有机碱、路易斯酸三者的摩尔比为1:(0.005~10):(0.01~30)。
8.根据权利要求1所述的一种基于离子化有机碱的双组分催化剂在聚醚制备中的应用,其特征在于,所述聚合反应的反应时间为1~300h,反应温度为0~100℃。
9.根据权利要求1所述的一种基于离子化有机碱的双组分催化剂在聚醚制备中的应用,其特征在于,所述聚合反应可在本体中进行,也可在溶剂中进行;所述溶剂为四氢呋喃、苯、甲苯、乙酸乙酯、环己烷、丙酮、2-甲基四氢呋喃、1,4-二氧六环、二氯甲烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、γ-丁内酯、丙烯碳酸酯、乙腈中的至少一种。
10.一种由权利要求1-9任一项所述的基于离子化有机碱的双组分催化剂在聚醚制备中的应用所制备得到的聚醚高分子。
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