CN109225323B - 磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸阴离子复合杂化体及其合成与应用 - Google Patents
磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸阴离子复合杂化体及其合成与应用 Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
本发明公开了一种磺酸基官能化有机/无机双阳离子‑钒掺杂多酸阴离子复合杂化体及其合成与应用。所述复合杂化体是将磺酸基官能化有机/无机双阳离子通过静电作用力包覆在纳米尺度的钒掺杂杂多酸阴离子表面,形成以杂多酸阴离子为内核的类核壳结构;其中,所述有机阳离子为双磺酸基官能化的线性结构季铵,所述无机阳离子为二价铜离子。该复合杂化体同时具有Brønsted酸性、Lewis酸性、两亲性和氧化催化活性,可以其为非均相催化剂,氯酸钠为氧化剂,水为反应溶剂,将8‑羟基喹啉一步氧化为2,3‑吡啶二羧酸。此合成方法具有催化体系反应活性高、选择性好,反应条件温和、产物易分离、纯度高,催化体系可循环使用、原料易得等特点。
Description
技术领域
本发明属于化工产品及催化材料制备技术领域,具体涉及一种磺酸基官能化有机/无机双阳离子-钒掺杂多酸阴离子复合杂化体及其合成与其在清洁合成2,3-吡啶二羧酸中的应用。
背景技术
2,3-吡啶二羧酸俗称喹啉酸,是合成农药、医药、染料等功能精细化学品的重要中间体,如除草剂、灭草烟、抗生素喹诺酮以及具有光电磁特性的功能配合物等。其合成方法根据原料的不同分为:(2)吡啶衍生物氧化法。如以2,3-二醛基吡啶、2-甲基-3-羧基吡啶为原料,通过底物的活性侧链或取代基氧化,引入1个或2个羧基,但其存在原料价格高,反应选择性低,设备成本高等不足。(1)喹啉氧化法——直接以喹啉作为氧化底物。由于喹啉环具有较强的芳香性,其开环氧化反应需要在较强烈条件下进行,故需选用强氧化剂,并存在氧化剂用量大、催化体系复杂、成本高、容易失活,反应条件相对苛刻等不足。(3)喹啉衍生物氧化法——以喹啉环上具有给电子取代基的喹啉衍生物(如8-羟基喹啉)为氧化底物。给电子基的引入提高了喹啉开环氧化活性,降低了氧化反应条件,提高了反应的转化率和产率。
发展基于环境友好型氧化剂是当前研究的主要方向,如Hankinson(Hawkinson AT et al., Preparation of quinolinic acid[P].US,2371691,1945-3-20.)、William(William et al., Method for the preparation of pyridine-2,3dicarboxylic acids[P], US , 61212563, 1989-03-28.)、Geertrudes(Geertrudes, et al., Process forpreparation of dicarboxylic acids[P].US,5917049,1999-6-29.)等发展了基于过氧化氢为氧化剂,硝酸/硝酸铜或硝酸铁为催化体系的喹啉一步开环氧化方法,优化反应条件下2,3-吡啶二羧酸的产率为70%,但由于使用低浓度过氧化氢,制约了该方法的工业化。Furukawa(Process for the preparation of 2,3-pyridinecar-boxylicacids[P].US,20020062025,2002-5-23.)及Hara小组(Production of heterocyclic carboxylic acid[P]. JP, 0310661,1991-4-26.)以次氯酸钠为氧化剂,发展了基于酸性和碱性反应条件下,三氯化钌为催化体系的喹啉一步开环氧化方法,将2,3-吡啶二羧酸的产率提高到80%。国内盛洁君(2,3-吡啶二羧酸的合成[J].石油化工,2009,38(8):889~892.)、刘冬杰小组(喹啉酸的生产方法[P].中国专利,102399182,2010-04-04.)则以氯酸钠作为氧化剂,钌盐/铜盐作为复合催化体系,将2,3-吡啶二羧酸的产率提高到90%以上。从提高催化体系的氧化活性出发,研究者将同时具有酸性和氧化催化活性的杂多酸,引入至氧化催化体系中,如段湘生等(喹啉酸的合成研究[J].精细化工中间体,2006(02):18-20.)报道的方法,2,3-吡啶二羧酸的纯度可达到98%以上。
本发明从调控催化体系的氧化催化活性,改善水溶性氧化剂与水溶性氧化底物的两相间反应,同时提高氧化反应的转化率与选择性这三方面入手,通过引入绿色催化剂杂多酸,在分子水平构建多功能化杂多酸离子杂化体,以其作为绿色非均相催化体系,建立以氯酸性水溶剂为氧化剂,8-羟基喹啉为氧化底物的2,3-吡啶二羧酸的绿色、高效合成新工艺,具有重要的理论价值和良好的工业应用前景。
发明内容
本发明的目的在于提供一种磺酸基官能化有机/无机双阳离子-钒掺杂多酸阴离子复合杂化体及其合成与应用。
为实现上述目的,本发明采用如下技术方案:
本发明第一个目的是保护一种磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸阴离子复合杂化体,其是将磺酸基官能化有机/无机双阳离子通过静电作用力包覆在纳米尺度的钒掺杂杂多酸阴离子表面,形成以杂多酸阴离子为内核的类核壳结构复合杂化体,所得复合杂化体杂化体同时具有Brønsted/Lewis酸性、氧化催化活性及良好的两亲活性,且催化活性的大小能够灵活地通过有机或无机阳离子数目、杂多酸阴离子结构中的钒离子数目加以调控;
其中,所述有机阳离子来源于线性结构的二丙基磺酸基五甲基二乙烯基三铵、二丁基磺酸基五甲基二乙烯基三铵,或二丙基磺酸基四甲基乙二铵、二丁基磺酸基四甲基乙二铵;
所述无机阳离子为二价铜离子;
所述钒掺杂杂多酸阴离子为Dawson构型的钒掺杂磷杂多酸阴离子[P2Mo17VO62]7-、[P2Mo16V2O62]8-或[P2Mo15V3O62]9-。
1mol复合杂化体中含有机阳离子1~3 mol,无机阳离子1~3.5 mol。
具体地,所述磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸阴离子复合杂化体为:[二丙基或丁基磺酸基五甲基二乙烯基三铵] 2 [Cu+2] [1钒17钼磷酸根盐]、[二丙基或丁基磺酸基四甲基乙二铵] 2.5 [Cu+2] [1钒17钼磷酸根盐]、2[二丙基或丁基磺酸基四甲基乙二铵] 1.5 [Cu+2] [1钒17钼磷酸根盐]、2[二丙基或丁基磺酸基五甲基二乙烯基三铵][Cu+2] [2钒16钼磷酸根盐]、[二丙基或丁基磺酸基四甲基乙二铵] 3 [Cu+2] [2钒16钼磷酸根盐]、2[二丙基或丁基磺酸基四甲基乙二铵] 2 [Cu+2] [2钒16钼磷酸根盐]、3[二丙基或丁基磺酸基四甲基乙二铵] [Cu+2] [2钒16钼磷酸根盐]、2[二丙基或丁基磺酸基五甲基二乙烯基三铵] 1.5 [Cu+2] [3钒15钼磷酸根盐]、1[二丙基或丁基磺酸基四甲基乙二铵]3.5 [Cu+2] [3钒15钼磷酸根盐]、2[二丙基或丁基磺酸基四甲基乙二铵] 2.5 [Cu+2] [3钒15钼磷酸根盐]、3[二丙基或丁基磺酸基四甲基乙二铵] 1.5 [Cu+2] [3钒15钼磷酸根盐]。其化学式简写为:[C17H52N3 +O6S2]1[Cu+2]2[P2Mo17VO62 -7]或[C15H48N3 +O6S2]1[Cu+2]2[P2Mo17VO62 -7](1)、[C14H34N2 +O6S2]1[Cu+2]2.5[P2Mo17VO62 -7]或[C12H30N2 +O6S2]1[Cu+2]2.5[P2Mo17VO62 -7](2)、[C14H34N2 +O6S2]2[Cu+2]1.5[P2Mo17VO62 -7]或[C12H30N2 +O6S2]2[Cu+2]1.5[P2Mo17VO62 -7](3)、[C17H52N3 +O6S2]2[Cu+2]1[P2Mo16V2O62 -8]或[C15H48N3 +O6S2]2[Cu+2]2[P2Mo16V2O62 -8](4)、[C14H34N2 +O6S2]1[Cu+2]3[P2Mo16V2O62 -8]或[C12H30N2 +O6S2]1[Cu+2]3[P2Mo16V2O62 -8](5)、[C14H34N2 +O6S2]2[Cu+2]2P2Mo16V2O62 -8]或[C12H30N2 +O6S2]2[Cu+2]2[P2Mo16V2O62 -8](6)、[C14H34N2 +O6S2]3[Cu+2]1[P2Mo16V2O62 -8]或[C12H30N2 +O6S2]3[Cu+2]1[P2Mo16V2O62 -8](7)、[C17H52N3 +O6S2]2[Cu+2]1.5[P2Mo15V3O62 -9]或[C15H48N3 +O6S2]2[Cu+2]1.5[P2Mo15V3O62 -9](8)、[C14H34N2 +O6S2]1[Cu+2]3.5[P2Mo15V3O62 -9]或[C12H30N2 +O6S2]1[Cu+2]3.5[P2Mo15V3O62 -9](9)、[C14H34N2 +O6S2]2[Cu+2]2.5[P2Mo15V3O62 -9]或[C12H30N2 +O6S2]2[Cu+2]2.5[P2Mo15V3O62 -9](10)、[C14H34N2 +O6S2]3[Cu+2]1.5[P2Mo15V3O62 -9]或[C12H30N2 +O6S2]3[Cu+2]1.5[P2Mo15V3O62 -9](11)。该11种复合杂化体的结构式如下:
本发明第二个目的是保护所述复合杂化体的合成方法,其包括以下步骤:
1)在配有磁力搅拌的反应瓶中,加入乙腈、1,4-丁烷磺酸内酯或1,3-丙烷磺酸内酯,充分搅拌后升温至50℃,滴加五甲基二乙基三胺或四甲基乙二胺,保温反应48h;反应物依次经过滤、乙醚洗涤、真空干燥,得到中间体季铵盐(L1、L2或L3、L4);
2)将步骤1)所得中间体季铵盐充分溶于去离子水后,滴加氯化铜水溶液,充分搅拌30min后,滴加钒掺杂杂多酸H7[P2Mo17VO62]、H8[P2Mo16V2O62]或H9[P2Mo15V3O62]的水溶液,然后室温下反应12 h;所得反应物经过滤、去离子水淋洗、真空干燥至恒重,得到所述复合杂化体。
步骤1)中1,4-丁烷磺酸内酯或1,3-丙烷磺酸内酯与五甲基二乙基三胺或四甲基乙二胺的摩尔比为2.05:1。
步骤2)中,当采用H7[P2Mo17VO62]为钒掺杂杂多酸时,所用季铵盐L1或L2与钒掺杂杂多酸、氯化铜的摩尔比为1:1:2;所用季铵盐L3或L4与钒掺杂杂多酸、氯化铜的摩尔比为1:1:2.5或2:1:1.5;
当采用H8[P2Mo16V2O62]为钒掺杂杂多酸时,所用季铵盐L1或L2与钒掺杂杂多酸、氯化铜的摩尔比为2:1:1;所用季铵盐L3或L4与钒掺杂杂多酸、氯化铜的摩尔比为1:1:3、2:1:2或3:1:1;
当采用H9[P2Mo15V3O62]为钒掺杂杂多酸时,所用季铵盐L1或L2与钒掺杂杂多酸、氯化铜的摩尔比为2:1:1.5;所用季铵盐L3或L4与钒掺杂杂多酸、氯化铜的摩尔比为1:1:3.5、2:1:3.5或3:1:3.5。
本发明以五甲基二乙烯基三胺或四甲基乙二胺为母体,以1,3-丙烷磺酸内酯或1,4-丁烷磺酸内酯为磺酸基官能化侧链引入单元,先经季铵化在母体叔胺的两个N原子上引入碳数为3或4的磺酸基官能化侧链;再分别以1个[P2Mo17VO62]7-、[P2Mo16V2O62]8-或[P2Mo15V3O62]9-,与1~3个磺酸基双官能化季铵两性盐,1~3.5个二价铜离子相配。所得复合杂化体结构中,有机/无机双阳离子通过静电作用力包覆在杂多酸阴离子的表面,形成了以杂多酸阴离子为核心的类核壳结构。磺酸基官能团在赋予离子杂化体强Brønsted酸性的同时,与母体直链季铵结构共同使所得复合杂化体表现出良好的两亲性。二价铜离子、杂多酸阴离子中的钒离子则分别赋予了复合杂化体Lewis酸性和氧化催化活性。
本发明第三个目的是保护所述磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸阴离子复合杂化体的应用,即以所述复合杂化体作为非均相催化剂,氯酸钠为氧化剂,无离子水为反应溶剂,将8-羟基喹啉一步氧化为2,3-吡啶二羧酸。
其具体应用方法为:在配有磁力搅拌的反应瓶中,依次加入无离子水、复合杂化体,室温下充分混合后升温至45℃,然后加入8-羟基喹啉,升温至90℃,并分3次加入氯酸钠,再在回流状态下反应10h;所得反应物经冷却、抽滤、去离子水淋洗,分出复合杂化体,然后将滤液降温至10℃以下,并缓慢滴加浓盐酸以调节其pH值为1以下,充分析出产物;所得产物抽滤、去离子水淋洗、真空干燥,即得外观为类白色细小颗粒的目标产物2,3-吡啶二羧酸;其中,所用复合杂化体与8-羟基喹啉、氯酸钠的摩尔比为0.0025:1:3.0。
所得磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸阴离子离子杂化体的再生方法为:将使用后的离子杂化体用去离子水充分洗涤后,真空干燥至恒重。
本发明提供的2,3-吡啶二羧酸的合成方法具有催化体系活性高、选择性好、反应条件温和、产品收率高、杂化体可循环使用,以及易于工业化实施等特点。
本发明从杂多酸结构在分子水平的设计出发,提出一种磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸阴离子复合杂化体,其是将官能化有机阳离子、二价铜离子通过静电相互作用包覆在尺寸在纳米级的杂多酸阴离子表面,形成以杂多酸阴离子为核的类核壳结构。其中,钒离子的引入赋予了复合杂化体氧化催化活性,而多个磺酸基的引入则使复合杂化体表现出强Brønsted酸性,并且氧化催化活性和酸性大小可通过钒离子的数目、阳离子的数目加以调控;铜离子的引入还赋予了复合杂化体Lewis酸性,且其可起到调控杂化体形貌的作用,构建具有纳米尺度结构的复合杂化体;有机阳离子的磺酸基官能化长链胺类结构,赋予了复合杂化体良好的两亲性,这一方面可有效促进底物与水溶性氧化剂的两相间反应,另一方面能够及时地将生成的水溶性2,3-吡啶二羧酸从杂化体表面移出,避免了产物进一步发生脱羧等副反应。
本发明的有益效果在于:
1. 本发明复合杂化体结构中的磺酸基官能团、二价铜离子、钒离子及磺酸基官能化的长链季铵结构,使该杂化体同时表现Brønsted/Lewis双酸性、表面两亲性和氧化催化活性,从而有利于底物8-羟基喹啉与氯酸钠水溶液的反应,并且这些性质可通过有机/无机阳离子的数目、钒离子的数目加以调控。
2. 以本发明所得复合杂化体作为非均相催化剂,以氯酸钠为氧化剂,水为反应溶剂,可见8-羟基喹啉经一步氧化合成2,3-吡啶二羧酸,其具有催化活性高、选择性好、反应后处理简便、产物纯度高、产率良好等优势;
3. 本发明所得复合杂化体在氧化反应后,经洗涤、真空干燥至恒重,即可再生循环使用,且其循环使用5次,催化活性基本保持不变。
附图说明
图1为本发明所得磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸复合杂化体1~11的结构示意图;
图2为本发明所得磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸复合杂化体的合成路线;
图3-1为本发明所得磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸复合杂化体1的热重图;
图3-2为本发明所得磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸复合杂化体4的热重图;
图3-3为本发明所得磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸复合杂化体5的热重图;
图4-1为本发明所得磺酸基官能化有机/无机阳离子-钒掺杂杂多酸复合杂化体1的红外光谱图;
图4-2为本发明所得磺酸基官能化有机/无机阳离子-钒掺杂杂多酸复合杂化体4的红外光谱图;
图4-3为本发明所得磺酸基官能化有机/无机阳离子-钒掺杂杂多酸复合杂化体5的红外光谱图;
图5-1为本发明所得磺酸基官能化有机/无机阳离子-钒掺杂杂多酸复合杂化体1的XRD图;
图5-2为本发明所得磺酸基官能化有机/无机阳离子-钒掺杂杂多酸复合杂化体4的XRD图;
图5-3为本发明所得磺酸基官能化有机/无机阳离子-钒掺杂杂多酸复合杂化体5的XRD图;
图6-1为本发明所得磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸复合杂化体1的扫描电镜图;
图6-2为本发明所得磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸复合杂化体5的扫描电镜图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1:季铵盐L1的合成
在配有氮气保护和磁力搅拌的反应瓶中,加入30ml乙腈、1,3-丙烷磺酸内酯2.05mol,充分搅拌后升温至50℃,缓慢滴加1mol五甲基二乙基三胺,加毕保温反应48h;然后依次经抽滤、乙醚淋洗、真空干燥,得到产物季铵盐L1,外观类白色固体,产率97.0%。
实施例2:季铵盐L2的合成
将1,3-丙烷磺酸内酯用1,4-丁烷磺酸内酯替换,其他同实施例1,得到季铵盐L2,外观类白色固体,产率96.0%。
实施例3:季铵盐L3的合成
将五甲基二乙基三胺用四甲基乙二胺替换,其他同实施例1,得到季铵盐L3,外观类白色固体,产率97.0%。
实施例4:季铵盐L4的合成
将五甲基二乙基三胺用四甲基乙二胺替换,其他同实施例2,得到季铵盐L4,外观类白色固体,产率96.0%。
实施例5:复合杂化体[C17H52N3 +O6S2]1[Cu+2]2[P2Mo17VO62 -7]或 [C15H48N3 +O6S2]1[Cu+2]2[P2Mo17VO62 -7](1)的合成
在配有磁力搅拌的反应器中加入50mmol H7[P2Mo17VO62],用最少量去离子水完全溶解后,依次滴加15ml溶有100mmol氯化铜的去离子水溶液,15ml溶有50mol季铵盐L1或L2的去离子水溶液,加毕于室温下搅拌12h。所得反应混合物经抽滤或离心,去离子水洗涤后,于60℃下真空干燥至恒重,得到目标化合物,其产率为90%。
FT-IR(KBr),ν/cm-1:3426(O-H伸缩振动),2924(饱和-CH伸缩振动),1183(-SO3伸缩振动),1060(P-O伸缩振动),958(V-O不对称伸缩振动),867,787(Mo-O-Mo伸缩振动)。
杂化体元素分析,[C17H52N3 +O6S2]1[Cu+2]2[P2Mo17VO62 -7]
C17H52N3P2Mo17O68S2V1Cu2:实测值(计算值),%:C 6. 12(6.15);H 1. 53 (1.58);N1.25 (1.27);S 1.91(1.93)。杂化体XRD显示,没出现H7[P2Mo17VO62]杂多酸特征峰,表明杂化体以非晶态形式存在。
杂化体元素分析,[C15H48N3 +O6S2]1[Cu+2]2[P2Mo17VO62 -7]
C15H48N3P2Mo17O68S2 V1 Cu2:实测值(计算值),%:C 5.45(5.47);H 1.42 (1.47);N1.25(1.28);S 1.92(1.95)。杂化体XRD显示,没出现H7[P2Mo17VO62]杂多酸特征峰,表明杂化体以非晶态形式存在。
实施例6:复合杂化体[C17H52N3 +O6S2]2[Cu+2]1[P2Mo16V2O62 -8]或[C15H48N3 +O6S2]2[Cu+2]1[P2Mo16V2O62 -8] (4)的合成
在配有磁力搅拌的反应器中加入50mmol H8[P2Mo16V2O62],用最少量去离子水完全溶解后,依次滴加15ml溶有50mmol氯化铜的去离子水溶液,15ml溶有100mol季铵盐L1或L2的去离子水溶液,加毕于室温下搅拌12h。所得反应混合物经抽滤或离心,去离子水洗涤后,于60℃下真空干燥至恒重,得到目标化合物,其产率92%。
FT-IR(KBr),ν/cm-1:3422(O-H伸缩振动),2925(饱和-CH伸缩振动),1183(-SO3伸缩振动),1060(P-O伸缩振动),958(Mo=O、V=O伸缩振动),866、787cm-1(Mo-O-Mo桥的伸缩振动)。
杂化体元素分析,[C17H52N3 +O6S2]2[Cu+2]1[P2Mo16V2O62 -8]
C34H104N6P2Mo16O78S4V2Cu1:实测值(计算值),%:C 10.92(10.93);H 2.77 (2.81);N2. 88 (2.25);S 3.40(3.42)。杂化体XRD显示,没出现H8[P2Mo16V2O62]杂多酸特征峰,表明杂化体以非晶态形式存在。
杂化体元素分析,[C15H48N3 +O6S2]2[Cu+2]1[P2Mo16V2O62 -8]
C30H96N6P2Mo16O78S4V2Cu1:实测值(计算值),%:C 9.76(9.79);H 2.60 (2.63);N2.27 (2.28);S 3.46(3.49)。杂化体XRD显示,没出现H8[P2Mo16V2O62]杂多酸特征峰,表明杂化体以非晶态形式存在。
实施例7:离子杂化体[C14H34N2 +O6S2]1[Cu+2]3[P2Mo16V2O62 -8]或[C12H30N2 +O6S2]1 [Cu+2]3[P2Mo16V2O62 -8] (5)的合成
在配有磁力搅拌的反应器中加入50mmol H8[P2Mo16V2O62],用最少量去离子水完全溶解后,依次滴加15ml溶有150mmol氯化铜的去离子水溶液,15ml溶有50mol季铵盐L3或L4的去离子水溶液,加毕于室温下搅拌12h。所得反应混合物经抽滤或离心,去离子水洗涤后,于60℃下真空干燥至恒重,得到目标化合物,其产率为91%。
FT-IR(KBr),ν/cm-1:3421(-OH伸缩振动),2922(饱和-CH伸缩振动),1189(-SO3伸缩振动),1060(P-O伸缩振动),959(Mo=O、V=O伸缩振动),870、790(Mo-O-Mo桥的伸缩振动)。
杂化体元素分析,[C14H34N2 +O6S2]1[Cu+2]3[P2Mo16V2O62 -8]
C14H34N2P2Mo16O68S2V2Cu3:实测值(计算值),%:C 5. 15( 5. 14);H 1. 08 ( 1.05);N 0. 84( 0. 86);S 1. 93( 1. 96)。杂化体XRD显示,没出现H8[P2Mo16V2O62]杂多酸特征峰,表明杂化体以非晶态形式存在。
杂化体元素分析,[C12H30N2 +O6S2]1 [Cu+2]3[P2Mo16V2O62 -8]
C12H30N2P2Mo16O68S2V2Cu3:实测值(计算值),%:C 4.42(4.44);H 0.90 (0.93);N0.84 (0.86);S 1.96(1.98)。杂化体XRD显示,没出现H8[P2Mo16V2O62]杂多酸特征峰,表明杂化体以非晶态形式存在。
通过图6-1与图6-2对比可见,复合杂化体结构中铜离子的引入对杂化体形貌表现出显著影响,铜离子的数目由1个增加至3个,杂化体的形貌可由无规堆积变化相对规整的片状结构。
应用例1;2,3-吡啶二羧酸的合成
在配有氮气保护和磁力搅拌的反应釜中,加入制备的复合杂化体1~11、去离子水,充分搅拌后升温至45℃,然后加入8-羟基喹啉,加毕升温至90℃,分三次加入氯酸钠,加毕反应体系在回流状态下反应10h(复合杂化体与8-羟基喹啉、氯酸钠的摩尔比为0.0025:1:3.0)。将体系冷却,抽滤,去离子水淋洗,分出复合杂化体,所得滤液降温至10℃以下,并缓慢滴加浓盐酸以调节体系pH值为1以下,充分析出产物。所得产物抽滤、去离子水淋洗、真空干燥,得到外观为类白色细小颗粒的目标产物2,3-吡啶二羧酸,产物熔点187℃。11种复合杂化体的产率见表1。
表1 11种复合杂化体的产率
由表1可见,复合杂化体10产率最高、复合杂化体1产率最低。
分离出的复合杂化体(杂化体10)经再生后循环使用,其再生方法是将复合杂化体用去离子水充分洗涤后,真空干燥至恒重。
第一次循环使用2,3-吡啶二羧酸的产率为85%,第二次循环使用2,3-吡啶二羧酸的产率为86%,第三次循环使用2,3-吡啶二羧酸的产率为84%、第四次循环使用2,3-吡啶二羧酸的产率为84%,第五次循环使用2,3-吡啶二羧酸的产率为84%。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (5)
1.一种磺酸基官能化有机/无机双阳离子-钒掺杂杂多酸阴离子复合杂化体在催化氧化合成2,3-吡啶二羧酸中的应用,其特征在于:以所述复合杂化体作为非均相催化剂,氯酸钠为氧化剂,无离子水为反应溶剂,将8-羟基喹啉一步氧化为2,3-吡啶二羧酸;
所述复合杂化体是由磺酸基官能化有机/无机双阳离子通过静电作用力包覆在纳米尺度的钒掺杂杂多酸阴离子表面,形成以杂多酸阴离子为内核的类核壳结构复合杂化体,所得复合杂化体同时具有Brønsted/Lewis酸性、氧化催化活性及良好的两亲活性,且催化活性的大小能够灵活地通过有机或无机阳离子数目、杂多酸阴离子结构中的钒离子数目加以调控;
其中,所述有机阳离子来源于线性结构的二丙基磺酸基五甲基二乙烯基三铵、二丁基磺酸基五甲基二乙烯基三铵,或二丙基磺酸基四甲基乙二铵、二丁基磺酸基四甲基乙二铵;有机阳离子的数目分别为1个、2个或3个;
所述无机阳离子为二价铜离子;无机阳离子的数目分别为1个、1.5个、2个、2.5个、3个或3.5个;
所述钒掺杂杂多酸阴离子为Dawson构型的钒掺杂杂多酸阴离子[P2Mo17VO62]7-、[P2Mo16V2O62]8-或[P2Mo15V3O62]9-。
2.根据权利要求1所述的应用,其特征在于:所述复合杂化体的制备包括以下步骤:
1)在配有磁力搅拌的反应瓶中,加入乙腈、1,4-丁烷磺酸内酯或1,3-丙烷磺酸内酯,充分搅拌后升温至50℃,滴加五甲基二乙基三胺或四甲基乙二胺,保温反应48h;反应物依次经过滤、乙醚洗涤、真空干燥,得到中间体季铵盐;
2)将步骤1)所得中间体季铵盐充分溶于去离子水后,滴加氯化铜水溶液,充分搅拌30min后,滴加钒掺杂杂多酸H7[P2Mo17VO62]、H8[P2Mo16V2O62]或H9[P2Mo15V3O62]的水溶液,然后室温下反应12 h;所得反应物经过滤、去离子水淋洗、真空干燥至恒重,得到所述复合杂化体。
3.根据权利要求2所述的应用,其特征在于:步骤1)中1,4-丁烷磺酸内酯或1,3-丙烷磺酸内酯与五甲基二乙基三胺或四甲基乙二胺的摩尔比为2.05:1。
4.根据权利要求2所述的应用,其特征在于:步骤2)中,当采用H7[P2Mo17VO62]为钒掺杂杂多酸时,所用季铵盐与钒掺杂杂多酸、氯化铜的摩尔比为(1~2):1:(1.5~2.5);
当采用H8[P2Mo16V2O62]为钒掺杂杂多酸时,所用季铵盐与钒掺杂杂多酸、氯化铜的摩尔比为(1~3):1:(1~3);
当采用H9[P2Mo15V3O62]为钒掺杂杂多酸时,所用季铵盐与钒掺杂杂多酸、氯化铜的摩尔比为(1~3):1:(1.5~3.5)。
5.根据权利要求1所述的应用,其特征在于:具体应用方法为:在配有磁力搅拌的反应瓶中,依次加入无离子水、复合杂化体,室温下充分混合后升温至45℃,然后加入8-羟基喹啉,升温至90℃,并分3次加入氯酸钠,体系在回流状态下反应10h;所得反应物经冷却、抽滤,将滤液降温至10℃以下,并缓慢滴加浓盐酸以调节其pH值为1以下,充分析出产物;所得产物抽滤、去离子水淋洗、真空干燥,即得目标产物2,3-吡啶二羧酸;
其中,所用复合复合杂化体与8-羟基喹啉、氯酸钠的摩尔比为0.0025:1:3.0。
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