CN110354908A - 聚醚基官能化钒掺杂杂多酸聚离子液体、合成方法及其在制备环己内酯上的应用 - Google Patents
聚醚基官能化钒掺杂杂多酸聚离子液体、合成方法及其在制备环己内酯上的应用 Download PDFInfo
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- 125000004429 atom Chemical group 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D309/30—Oxygen atoms, e.g. delta-lactones
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—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
- 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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- C08G65/32—Polymers modified by chemical after-treatment
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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Abstract
本发明涉及一种聚醚基官能化钒掺杂杂多酸聚离子液体、合成方法及其在制备环己内酯上的应用。本发明所述的聚醚官能化钒掺杂杂多酸聚离子液体结构具有:聚醚官能化季铵有机阳离子,Keggin构型杂多酸阴离子[PMo11VO40]‑4或[PMo10V2O40]‑5或[P2Mo9V3O40]‑6或Dawson构型钒掺杂杂多酸阴离子[P2MO17VO62 ‑7]或[P2MO16V2O62 ‑8]或[P2MO16V3O62 ‑9];并将该聚离子液体作为催化剂,由环己烯、环戊烯接力氧化合成环己内酯、环戊内酯的方法,具有原料价廉、易得,合成路线简单,催化体系活性高,选择性好,催化体系便于循环使用等特点。
Description
技术领域
本发明属于化工产品及其制备技术领域,具体涉及系列聚醚官能化钒掺杂杂多酸聚离子液体的设计合成;以合成的聚醚官能化钒掺杂杂多酸聚离子液体为非均相催化体系,工业级过氧化氢为氧化剂,由环己烯、环戊烯接力氧化制备环己内酯、环戊内酯的方法。
背景技术
随着石化产业的发展,以环己烯、环戊烯为代表的环烯烃实现了商业供给,由于此类化合物结构中同时存在碳碳双键和α-氢两个活性反应位点,通过直接氧化可构建一系列高附加值含氧化合物,如从环己烯出发,双键经环氧化可制备环氧化环己烷、氧化羟化合成环己二醇;α-氢位点氧化可合成环己烯酮、环己烯醇,以及环己醇、环己酮、羟基环己酮等一系列精细化学品合成中间体。分子氧作为来源作为广泛和廉价的氧化剂,在烯烃氧化中得到了普遍应用,研究者发展出了基于过渡金属[王娟娟.催化空气氧化环己烯制环己烯酮[J].陕西师范大学学报(自然科学版),2008,36:73-74]、纳米粒子[Hughes M D,Xu Y J,etal.Tunable gold catalysts for selective hydrocarbon oxidation under mildconditions[J].Nature,2005,437(7062)1132-1135]、仿生物酶[Kameyama H,Nanumi F,Hattori T,et al.Oxidation of cyclohexene with molecular oxygen catalyzed bycobaltporphyrin complexes mmobilized on montmorillonite[J]Journal ofMolecular Catalysis A:Chemical,2006258:172-177]等高效催化体系,有效提高了氧化反应选择性,但仍存在诸如反应条件的相对苛刻,催化剂制备复杂、成本高、稳定性差等不足。
目前环己内酯、环戊内酯的合成的主要方法是Baeyer-Villiger氧化(以下简写为BV),该方法以有机过氧酸为氧化剂,通过在底物酮的羰基碳和其邻位的亚甲基间插入一个氧原子,而生成对应的内酯产物。BV氧化具有合成路线简捷、原子经济等突出优点。不足是产生化学计量量的副产有机羧酸,有机过氧化酸成本高、存在安全问题等。过氧化氢做为一种绿色氧化剂,具有活性氧含量高,唯一副产物为水的特点,符合绿色化学的思想,以其为氧化剂当前BV氧化的研究方向。本发明通过烯烃先选择性氧化生成环己酮或环戊酮,其在继续进行Baeyer-Villiger氧化,生成终产物己内酯或戊内酯,实现烯烃氧化与BV氧化的接力。催化体系引入物化性质及催化活性可设计调节的功能化聚杂多酸离子液体,探索建立直接以环己烯、环戊烯为原料,工业级过氧化氢为绿色氧化剂,环己内酯或环戊内酯的合成新工艺,具有理论上的创新性和良好的工业应用前景。
发明内容
本发明的目的之一是从杂多酸分子结构的可设性出发,以聚醚官能化季铵有机阳离子,钒掺杂Keggin构型和Dawson构型杂多酸阴离子为构建单元,提出了一种兼具氧化催化活性和良好两亲性的聚醚官能化钒掺杂杂多酸聚离子液体及其制备方法,聚离子液体结构中具有:聚醚官能化季铵有机阳离子,Keggin构型杂多酸阴离子[PMo11VO40]-4或[PMo10V2O40]-5或[P2Mo9V3O40]-6或Dawson构型钒掺杂杂多酸阴离子[P2MO17VO62 -7]或[P2MO16V2O62 -8]或[P2MO16V3O62 -9];其中聚醚官能化季铵有机阳离子与杂多酸阴离子以静电作用力结合,形成了以有机阳离子为网络、杂多酸阴离子为结点的三维网状立体结构。聚醚官能化季铵有机离子,赋予了聚离子液体良好表面两亲性,并可通过聚合度、烷基化试剂的选择进行灵活的设计和调节,从而可有效地促进底物烯烃和中间体环酮与过氧化氢两相间反应的进行,同时也能够及时将生成的疏水性质的产物及时从聚离子液体体表面移出,避免了进一步氧化反应的发生;钒掺杂杂多酸阴离子则使聚离子液体,同时具有氧化催化活性和酸活性,两者的活性大小可方便地通过聚合度、钒离子的数目灵活调节;由于杂多酸阴离子大小在纳米尺度,聚醚官能化季铵阳离子在其表面的包覆与缠绕,形成了大小在纳米级的微孔至介孔的内腔为疏水性的多孔结构。
为实现上述目的,本发明采用如下技术方案:
所述聚醚官能化钒掺杂杂多酸聚离子液体以环氧氯丙烷、乙二醇或1,2-丙二醇或1,3-丙二醇或1,4-丁二醇,三甲胺或三乙胺或三乙醇胺,Keggin构型钒掺杂杂多酸H4[PMo11VO40]或H5[PMo10V2O40]或H6[P2Mo9V3O40],Dawson构型钒掺杂杂多酸H7[P2Mo1VO62]或H8[P2Mo16V2O62]或H9[P2Mo15V3O62]为起始原料。
进一步地,所述聚醚官能化钒掺杂杂多酸聚离子液体包括[N,N,N-三甲基-N-羟乙基聚醚季铵]或[N,N,N–三甲基-N-羟异丙基聚醚季铵]或[N,N,,NN–三甲基-N-羟正丙基聚醚季铵]或[N,N,N–三甲基-N-羟正丁基聚醚季铵][1钒11钼磷酸根]盐或[2钒10钼磷酸根]盐或[3钒9钼磷酸根]盐或[1钒17钼磷酸根]盐或[2钒16钼磷酸根]盐或[3钒15钼磷酸根]盐;[N,N,N–三乙基-N-羟乙基聚醚季铵]或[N,N,N–三乙基-N-羟异丙基聚醚季铵]或[N,N,N–三乙基-N-羟丙基聚醚季铵]或[N,N,N–三乙基-N-羟正丁基聚醚季铵][1钒11钼磷酸根]盐或[2钒10钼磷酸根]盐或[3钒9钼磷酸根]盐或[1钒17钼磷酸根]盐或[2钒16钼磷酸根]盐或[3钒15钼磷酸根]盐;[N,N,N–三羟乙基-N-羟乙基聚醚季铵]或[N,N,N–三羟乙基-N-羟异丙基聚醚季铵]或[N,N,N–三羟乙基-N-羟丙基聚醚季铵]或[N,N,N–三羟乙基-N-羟丁基聚醚季铵][1钒11钼磷酸根]盐或[2钒10钼磷酸根]盐或[3钒9钼磷酸根]盐或[1钒17钼磷酸根]盐或[2钒16钼磷酸根]盐或[3钒15钼磷酸根]盐。相对应化学式依次为:[C8H20O3N+]4n[PMo11VO40 -4]n(PEPIL-1)、[C8H20O3N+]5n[PMo10V2O40 -5]n(PEPIL-2)、[C8H20O3N+]6n[PMo9V3O40 -6]n(PEPIL-3)、[C8H20O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-4)[C8H20O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-5)、[C8H20O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-6)或[C9H22O3N+]4n[PMo11VO40 -4]n(PEPIL-7)、[C9H22O3N+]5n[PMo10V2O40 -5]n(PEPIL-8)、[C9H22O3N+]6n[PMo9V3O40 -6]n(PEPIL-9)、[C9H22O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-10)、[C9H22O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-11)、[C9H22O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-12)或[C9H22O3N+]4n[PMo11VO40 -4]n(PEPIL-13)、[C9H22O3N+]5n[PMo10V2O40 -5]n(PEPIL-14)、[C9H22O3N+]6n[PMo9V3O40 -6]n(PEPIL-15)、[C9H22O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-16)、[C9H22O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-17)、[C9H22O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-18)或[C10H24O3N+]4n[PMo11VO40 -4]n(PEPIL-19)、[C10H24O3N+]5n[PMo10V2O40 -5]n(PEPIL-20)、[C10H24O3N+]6n[PMo9V3O40 -6]n(PEPIL-21)、[C10H24O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-22)、[C10H24O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-23)、[C10H24O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-24)或[C11H26O3N+]4n[PMo11VO40 -4]n(PEPIL-25)、[C11H26O3N+]5n[PMo10V2O40 -5]n(PEPIL-26)、[C11H26O3N+]6n[PMo9V3O40 -6]n(PEPIL-27)、[C11H26O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-28)[C11H26O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-29)、[C11H26O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-30)或[C12H28O3N+]4n[PMo11VO40 -4]n(PEPIL-31)、[C12H26O3N+]5n[PMo10V2O40 -5]n(PEPIL-32)、[C12H28O3N+]6n[PMo9V3O40 -6]n(PEPIL-33)、[C12H26O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-34)、[C12H26O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-35)、[C12H26O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-36)或[C12H28O3N+]4n[PMo11VO40 -4]n(PEPIL-37)、[C12H28O3N+]5n[PMo10V2O40 -5]n(PEPIL-38)、[C12H28O3N+]6n[PMo9V3O40 -6]n(PEPIL-39)、[C12H28O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-40)、[C12H28O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-41)、[C12H28O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-42)或[C13H30O3N+]4n[PMo11VO40 -4]n(PEPIL-43)、[C13H30O3N+]5n[PMo10V2O40 -5]n(PEPIL-44)、[C13H30O3N+]6n[PMo9V3O40 -6]n(PEPIL-45)、[C13H30O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-46)[C13H30O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-47)、[C13H30O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-48)或[C11H26O6N+]4n[PMo11VO40 -4]n(PEPIL-49)、[C11H26O6N+]5n[PMo10V2O40 -5]n(PEPIL-50)、[C11H26O6N+]6n[PMo9V3O40 -6]n(PEPIL-51)、[C11H26O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-52)[C11H26O6N+]8n[P2Mo16V2O62 -8]n(PEPIL-53)、[C11H26O6N+]9n[P2Mo15V3O62 -9]n(PEPIL-54)或[C12H28O6N+]4n[PMo11VO40 -4]n(PEPIL-55)、[C12H28O6N+]5n[PMo10V2O40 -5]n(PEPIL-56)、[C12H28O6N+]6n[PMo9V3O40 -6]n(PEPIL-57)、[C12H28O6N+]7n[P2Mo17V1O62 -7]n(PEPIL-58)、[C12H28O6N+]8n[P2Mo16V2O62 -8]n(PEPIL-59)、[C12H28O6N+]9n[P2Mo15V3O62 -9]n(PEPIL-60)或[C12H28O6N+]4n[PMo11VO40 -4]n(PEPIL-61)、[C12H28O6N+]5n[PMo10V2O40 -5]n(PEPIL-62)、[C12H28O6N+]6n[PMo9V3O40 -6]n(PEPIL-63)、[C12H28O6N+]7n[P2Mo17V1O62 -7]n(PEPIL-64)、[C12H28O6N+]8n[P2Mo16V2O62 -8]n(PEPIL-65)、[C12H28O6N+]9n[P2Mo15V3O62 -9]n(PEPIL-66)或[C13H30O6N+]4n[PMo11VO40 -4]n(PEPIL-67)、[C13H30O6N+]5n[PMo10V2O40 -5]n(PEPIL-68)、[C13H30O6N+]6n[PMo9V3O40 -6]n(PEPIL-69)、[C13H30O6N+]7n[P2Mo17V1O62 -7]n(PEPIL-70)、[C13H30O6N+]8n[P2Mo16V2O62 -8]n(PEPIL-71)、[C13H30O6N+]9n[P2Mo15V3O62 -9]n(PEPIL-72);该72种聚离子液体具有以下结构式:
聚醚官能化钒掺杂杂多酸聚离子液体结构上具有以下特点:环氧氯丙烷与乙二醇或1,2-丙二醇或1.3-丙二醇或1,4-丁二醇经开环聚合,得到羟基封端氯代聚醚,氯代聚醚与三甲胺或三乙胺或三乙醇胺经季铵化反应得到聚醚官能化季铵盐,季铵盐与钒掺杂Keggin型杂多酸H4[PMo11VO40]或H5[PMo10V2O40]或H6[P2Mo9V3O40],Dawson构型钒掺杂杂多酸H7[P2Mo1VO62]或H8[P2Mo16V2O62]或H9[P2Mo15V3O62]在水相中经离子交换,分子自组装,构建了以聚醚官能化季铵有机阳离子为网络,杂多酸阴离子为结点的多孔三维网状结构超分子体系。聚离子液体结构中的聚醚官能团季铵阳离子、多酸阴离子赋予了聚离子液体可调节和设计的氧化催化活性、良好的表面两亲活性和酸催化活性。
进一步地,聚醚官能化钒掺杂多酸聚离子液体PEPIL-1-72的合成包括以下步骤:
步骤S101:在配有磁力搅拌的反应瓶中,依次加入15mL二氯乙烷、0.35~0.86mL乙二醇或1,2-丙二醇或1,3-丙二醇或丁二醇,1.5mL三氟化硼乙醚络合物,冷至0~5℃,滴加25mL环氧氯丙烷,加毕保温反应6h。加15-30mL水终止反应。水洗、静置分相、旋蒸,得到无色粘稠状的端羟基聚醚,产率89~93%。
步骤S102:氮气保护下,在配有磁力搅拌的反应瓶中,将上述步骤S101所得的任一种聚醚溶于无水乙醇,升温至45℃滴加三甲胺或三乙胺或三乙醇胺的醇溶液,加毕保温反应12h。抽滤,乙醇淋洗、真空干燥至恒重。聚醚与三甲胺或三乙胺或三乙醇胺的摩尔比为1:n*1.05:(n为聚醚的聚合度)。
步骤S103:在配有磁力搅拌的反应瓶中,将上述步骤S102所得的任一种聚醚季铵盐溶于去离子水,室温下滴加H4PMo11VO40或H5PMo10V2O40或H6PMo9V3O40或H7P2Mo17V1O62或H8P2Mo16V2O62或H9P2Mo15V3O62水溶液,加毕室温下反应12h。抽滤,去离子水淋洗、真空干燥至恒重。聚醚季铵盐与杂多酸的摩尔比为1:n/4或1:n/5或1:n/6或1:n/7或1:/或1:n/9(n为聚醚的聚合度)。
本发明的目的之二是,提供一种应用上述聚醚官能化钒掺杂杂多酸聚离子液体为非均相催化体系,工业级过氧化氢为氧化剂,环戊烯或环己烯接力氧化为环戊内酯或环己内酯的方法。此合成方法具有原料价廉、易得,合成路线原子经济,催化体系活性高,选择性好,催化体系便于循环使用等特点。
为解决上述技术问题,本发明提供的技术方案是:
一种应用上述的聚醚官能化钒掺杂杂多酸聚离子液体为催化体系,工业级过氧化氢为氧化剂,由环己烯或环戊烯连续氧化制备环己内酯、环戊内酯的方法,包括以下步骤:
步骤S200:在配有磁力的反应瓶中,按摩尔比n(环烯):n(过氧化氢):n(聚离子液体)=1:8:0.0006,依次加入聚离子液体、环烯(环己烯或环戊烯),升温至50℃,先滴加为总质量的一半的过氧化氢水溶液(质量比35%),加毕保温反应4h。静置分相,分去下层水相,减压蒸馏除去未反应的环烯烃,混合升温至70℃,滴加剩余的过氧化氢水溶液(质量比35%),加毕保温反应4h。无水乙醚(3×10mL)萃取,静置分相、过滤,有机相经无水硫酸镁干燥、抽滤、离心、旋蒸得到目标产物,产率为23~49%。
聚离子液体的再生与循环使用步骤:
步骤S301:将步骤S200中离心得到的杂多酸聚离子液体,依次用无水乙醚、去离子水充分洗涤后,真空干燥至恒重,即完成聚离子液体的再生。
S302:将步骤S301所得的再生杂多酸聚离子杂化体、环烯加入反应釜中,升温到至50℃,先滴加为总质量的一半的过氧化氢水溶液(质量比35%),加毕保温反应4h。静置分相,分去下层水相,减压蒸馏除去未反应的环烯烃,升温至70℃,滴加剩余的过氧化氢水溶液(质量比35%),加毕保温反应4h。无水乙醚(3×10mL)萃取,静置分相、过滤,有机相无水硫酸镁干燥、抽滤、旋蒸得到目标产物,产率为31~48%。
其中投料比n(环烯):n(过氧化氢):n(聚离子液体)=1:8:0.0006。
本发明从环氧氯丙烷,乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇,三甲胺、三乙胺、三乙醇胺,H4[PMo11VO40]、H5[PMo10V2O40]、H6[P2Mo9V3O40]、H7[P2Mo17VO62]、H8[P2Mo16V2O62]、H9[P2Mo16V3O62]出发,经开环聚合、季铵化、分子自组装,构建了72种聚醚官能化钒掺杂杂多酸聚离子液体,聚离子液体同时表现出氧化催化活性、酸性和良好的表面两亲活性。三种性质可灵活地通过杂多酸阴离子的数目、种类、钒离子数目、有机阳离子的聚合度加以调控。
以上述合成的聚醚官能化钒掺杂杂多酸聚离子液体为催化剂,工业级过氧化氢为氧化剂(质量比35%),由环己烯、环戊烯连续接力氧化合成了环己内酯、环戊内酯。本发明从聚离子液体结构的可设计性出发,设计合成了72种聚醚官能化钒掺杂杂多酸聚离子液体,聚离子液体将氧化催化活性、酸性与两亲活性三者有机结合。以合成的聚醚官能化杂多酸聚离子液体为非均相催化体系,工业级过氧化氢为氧化剂,由环己烯、环戊烯接力氧化合成了环己内酯、环戊内酯。聚离子液体经离心、洗涤、真空干燥后即可再生循环使用,循环使用5次,目标化合物的产率基本保持不变。
本发明的有益效果在于:
1.聚醚官能化钒掺杂杂多酸聚离子液体结构中,聚醚官能化聚季铵有机离子与杂多酸阴离子以静电相互作用结合,形成了有机阳离子为网络、杂多酸阴离子为结点的三维网状超分子结构,杂多酸阴离子、钒离子、聚醚官能化季铵有机阳离子,赋予了聚离子液体氧化催化活性、酸性催化活和优良的表面两亲活性,不但可有效地促进环烯烃、环酮与过氧化氢水溶液的两相间反应的进行,同时有利于氧化产物能够及时从聚离子液体表面的催化活性中心分离,从而避免了产物进一步氧化的发生。
2.聚醚官能化钒掺杂杂多酸聚离子液体作为非均相催化剂,工业级过氧化氢为氧化剂,由环己烯、环戊烯接力氧化合成了环己内酯、环戊内酯。
3.聚离子液化体经离心分离、洗涤、真空干燥至恒重,即可再生循环使用,循环使用5次催化活性基本保持不变。
附图说明
图1为本发明所述的聚醚官能化钒掺杂杂多酸聚离子液体前体季铵盐合成路线及结构示意的图示。
图2为本发明所述的聚醚官能化钒掺杂杂多酸聚离子液体的合成路线及结构示意图
图3为聚醚官能化钒掺杂杂多酸聚离子液体PEPIL-7的XRD图;
图4为聚醚官能化钒掺杂杂多酸聚离子液体PEPIL-8的XRD图;
图5为聚醚官能化钒掺杂杂多酸聚离子液体PEPIL-9的XRD图;
图6为聚醚官能化钒掺杂杂多酸聚离子液体PEPIL-10的XRD图;
图7为聚醚官能化钒掺杂杂多酸聚离子液体PEPIL-11的XRD图;
图8为聚醚官能化钒掺杂杂多酸聚离子液体PEPIL-12的XRD图。
具体实施方式
以下结合具体实施例对本发明做进一步说明,但本发明不仅仅限于这些实施例。
实施例1:端羟基聚醚(PE-1)的合成
步骤S101:在配有磁力搅拌的反应瓶中,依次加入15mL 1.2-二氯乙烷,0.35mL乙二醇,1.5mL三氟化硼-乙醚,冷至0-5℃,滴加25ml环氧氯丙烷,控制温度不超过5℃,加毕保温反应6h。加15-30mL蒸馏水终止反应,搅拌10min,加入氨水调节有机相呈中性。分液,旋蒸得到无色粘稠产物,产率为87.6%。
FT-IR(KBr),ν/cm-1:3425,2875,1431,1351,1116,747。
实施例2:端羟基聚醚(PE-2与PE-3)的合成
实施例1中乙二醇换成1,2-丙二醇,加入量为0.62mL,其它同实施例1。目标产物PE-2产率为91.7%。
FT-IR(KBr),ν/cm-1:3435,2955,2862,1630,1431,1115,750。
实施例1中乙二醇换成1,3丙二醇),加入量为0.62mL,其它同实施例1。目标产物PE-3产率为91.7%。
FT-IR(KBr),ν/cm-1:3446,2969,2878,1633,1429,1112,748。
实施例3:端羟基聚醚(PE-4)的合成
实施例1中乙二醇换成1,4-丁二醇,加入量为0.86mL,其它同实施例1。目标产物产率为93%。
FT-IR(KBr),ν/cm-1:3477,2958,2875,1433,1346,1124,747。
实施例4:聚醚官能化季铵盐的合成
步骤S401:在氮气保护下,反应瓶中依次加入羟基聚醚(PE-1或PE-2或PE-3或PE-4)、无水乙醇。搅拌溶解,升温至45℃,滴加三甲胺或三乙胺或三乙醇胺的醇溶液,加毕保温反应12h。抽滤,乙醇淋洗、真空干燥至恒重。聚醚与三甲胺或三乙胺或三乙醇胺的摩尔比为1:m*1.05:(m为聚醚的聚合度)。产率91-95%。
实施例5
步骤S501:将0.5g聚醚官能化季铵盐POS-1(分子式:n[C8H20O3N+][Cl-],n取值20~120)充分溶于10ml去离子水,缓慢滴加2.36g H4PMo11VO40或2.05g H5PMo10V2O40或1.79gH6PMo9V3O40或1.45g H7[P2Mo17V1O62]或1.18g H8[P2Mo16V2O62]或0.87g H9[P2Mo15V3O62]溶于10ml无离子水的水溶液,加毕室温条件下搅拌反应12h。混合物依次抽滤、无离子水淋洗、70℃下真空干燥至恒重,得到目标产物,依次为[C8H20O3N+]4n[PMo11VO40 -4]n(PEPIL-1)、[C8H20O3N+]5n[PMo10V2O40 -5]n(PEPIL-2)、[C8H20O3N+]6n[PMo9V3O40 -6]n(PEPIL-3)、[C8H20O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-4)[C8H20O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-5)、[C8H20O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-6),产率为86-91%。
FT-IR(KBr)(PEPIL-1),ν/cm-1:3459,1617,1410,1109,962,782。
FT-IR(KBr)(PEPIL-2),ν/cm-1:3488,1627,1405,1061,962,782,614。
FT-IR(KBr)(PEPIL-3),ν/cm-1:3488,1627,1402,1139,952,819,743。
FT-IR(KBr)(PEPIL-4),ν/cm-1:3452,1638,1137,1405,961,870,786。
FT-IR(KBr)(PEPIL-5),ν/cm-1:3422,1633,1409,1131,960,866,786。
FT-IR(KBr)(PEPIL-6),ν/cm-1:3488,1627,1405,1133,966,871,780。
聚离子液体XRD没出现杂多酸特征峰,表明聚离子液体以非晶态形式存在。
其中由聚醚季铵盐POS-1出发与六种杂多酸经分子自组装得到聚离子液体、PEPIL-1-6;
由POS-2出发得到PEPIL-7-12,以此类推。
实施例6
步骤S601:将0.4g聚醚官能化季铵盐POS-5(分子式:n[C8H20O3N+][Cl-],n取值20~120)充分溶于10ml去离子水,缓慢滴加2.17g H4PMo11VO40或1.85gH5PMo10V2O40或1.53gH6PMo9V3O40或1.21g H7[P2Mo17V1O62]或1.08g H8[P2Mo16V2O62]或0.82g H9[P2Mo15V3O62]溶于10ml无离子水的水溶液,加毕室温条件下搅拌反应12h。混合物依次抽滤、无离子水淋洗、70℃下真空干燥至恒重,得到目标产物,依次为[C8H20O3N+]4n[PMo11VO40 -4]n(PEPIL-25)、[C8H20O3N+]5n[PMo10V2O40 -5]n(PEPIL-26)、[C8H20O3N+]6n[PMo9V3O40 -6]n(PEPIL-27)、[C8H20O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-28)[C8H20O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-29)、[C8H20O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-30),产率为87-90%。
FT-IR(KBr)(PEPIL-25),ν/cm-1:3443,1630,1402,1100,962,781,609。
FT-IR(KBr)(PEPIL-26),ν/cm-1:3456,1625,1409,1066,962,787,612。
FT-IR(KBr)(PEPIL-27),ν/cm-1:3493,1627,1400,1128,957,790,615。
FT-IR(KBr)(PEPIL-28),ν/cm-1:3477,1630,1405,1104,961,804,786。
FT-IR(KBr)(PEPIL-29),ν/cm-1:3431,1638,1409,1109,965,811,789。
FT-IR(KBr)(PEPIL-30),ν/cm-1:3467,1626,1401,1113,963,818,782。
聚离子液体XRD没出现杂多酸特征峰,表明聚离子液体以非晶态形式存在。
实施例7
步骤S701:将0.3g聚醚官能化季铵盐POS-9(n[C11H26O6N+][Cl-])充分溶于10ml去离子水,缓慢滴加2.13g H4PMo11VO40或1.76g H5PMo10V2O40或1.35gH6PMo9V3O40或1.05g H7[P2Mo17V1O62]或0.96g H8[P2Mo16V2O62]或0.55g H9[P2Mo15V3O62]溶于10ml无离子水的水溶液,加毕室温条件下搅拌反应12h。混合物依次抽滤、无离子水淋洗、70℃下真空干燥至恒重,得到目标产物,依次为[C8H20O3N+]4n[PMo11VO40 -4]n(PEPIL-49)、[C8H20O3N+]5n[PMo10V2O40 -5]n(PEPIL-50)、[C8H20O3N+]6n[PMo9V3O40 -6]n(PEPIL-51)、[C8H20O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-52)[C8H20O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-53)、[C8H20O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-54),产率为88-90%。
FT-IR(KBr)(PEPIL-49),ν/cm-1:3451,1623,1401,1072,960,783,611。
FT-IR(KBr)(PEPIL-50),ν/cm-1:3472,1625,1405,1065,964,789,610。
FT-IR(KBr)(PEPIL-51),ν/cm-1:3468,1627,1410,1117,959,783,612。
FT-IR(KBr)(PEPIL-52),ν/cm-1:3459,1630,1407,1102,963,799,780。
FT-IR(KBr)(PEPIL-53),ν/cm-1:3447,1638,1409,1115,965,811,789。
FT-IR(KBr)(PEPIL-54),ν/cm-1:3486,1626,1398,1109,963,815,780。
由聚醚季铵盐POS-9出发,与六种杂多酸分子自组装,得到了PEPIL-49到PEPIL-54六种聚醚官能化杂多酸聚离子液体。
聚离子液体XRD没出现杂多酸特征峰,表明聚离子液体以非晶态形式存在。
实施应用例1:聚醚官能化钒掺杂杂多酸聚离子液体催化的环己烯、环戊烯的接力氧化
在配有磁力搅拌的反应釜中,依次加入0.3g聚离子液体(催化剂)、15ml的1,2-二氯乙烷、1.0g环己烯、室温下搅拌均匀,升温至60℃,滴加35%(质量比)过氧化氢水溶液5ml,加毕保温反应4h。混合物冷却至室温,静置分相,分去水相,升温到60℃,滴加35%(质量比)过氧化氢水溶液5ml,加毕保温反应4h。加入乙醚萃取,抽滤或离心分出聚离子液体,有机相依次无水硫酸镁干燥、过滤、减压蒸馏得到产物环己内酯、环戊内酯。产率23~49%。
表1聚醚官能化钒掺杂杂多酸聚离子液体催化的环烯接力氧化结果
注:反应条件:按物质的量比,环烯:过氧化氢:聚离子液体=1:8:0.0006,温度60℃,70℃,反应时间4h,4h
聚合度m=40[1-24为三甲胺;25-48为三乙胺;49-72为乙三醇胺]
表2聚醚官能化钒掺杂杂多酸聚离子液体催化的环烯接力氧化结果
实施应用例2:聚醚官能化钒掺杂杂多酸聚离子液体的再生与循环使用
将实施应用例1中抽滤或离心得到的聚离子液体,依次用乙醚、去离子水充分洗涤后,将杂多酸聚离子液体于真空干燥至恒重,完成杂多酸聚离子液体的再生。
将所得的再生杂多酸离子杂化体、环烯(环己烯或环戊烯)、加入反应釜中,室温下搅拌均匀后,升温至60℃滴加总量一半的35%(质量比)过氧化氢水溶液,加毕保温反应4h。静置分相,分去水相,体系升温至70℃滴加总量一半的35%(质量比)过氧化氢水溶液,加毕保温反应4h。加入乙醚萃取,抽滤或离心分出聚离子液体,有机相依次无水硫酸镁干燥、过滤、减压蒸馏得到目标产物。投料,按物质的量比,环烯烃:过氧化氢:聚离子液体=1:8:0.0006。
第一循环使用环己内酯产率47%(PEPIL-86),第二次循环使用环己内酯产率48%,第三次循环使用环己内酯产率47%、第四次循环使用环己内酯产率47%,第五次循环使用环己内酯产率46%。
Claims (5)
1.聚醚官能化钒掺杂杂多酸聚离子液体,其特征在于:聚离子液体的构建单元为长链线性聚季铵盐有机阳离子和三种Keggin构型钒掺杂杂多酸阴离子、三种Dawson构型钒掺杂杂多酸阴离子;长链线性聚季铵盐有机阳离子为N,N,N -三甲基-N-羟乙基或N-羟异丙基或N-羟丙基或N-羟正丁基聚醚季铵阳离子或N,N,N -三乙基-N-羟乙基或N-羟异丙基或N-羟丙基或N-羟正丁基聚醚季铵阳离子或N,N,N -三羟乙基-N-羟乙基或N-羟异丙基或N-羟丙基或N-羟正丁基聚醚季铵阳离子;Keggin构型钒掺杂杂多酸阴离子为[PMo11VO40]-4或[PMo10V2O40]-5或[P2Mo9V3O40]-6;Dawson构型钒掺杂杂多酸阴离子为[P2Mo1VO62]-7或[P2Mo16V2O62]-8或[P2Mo15V3O62]-9。
2.根据权利要求1所述的聚醚官能化钒掺杂杂多酸聚离子液体,其特征在于:所述聚离子液体包括[N,N,N -三甲基-N-羟乙基聚醚季铵] 或[N,N,N –三甲基-N-羟异丙基聚醚季铵]或[N,N,,N N –三甲基-N-羟正丙基聚醚季铵]或[N,N,N–三甲基-N-羟正丁基聚醚季铵][1钒11钼磷酸根]盐或[2钒10钼磷酸根]盐或[3钒9钼磷酸根]盐或 [1钒17钼磷酸根]盐或[2钒16钼磷酸根]盐或[3钒15钼磷酸根]盐;[N,N,N –三乙基-N-羟乙基聚醚季铵]或[N,N,N –三乙基-N-羟异丙基聚醚季铵]或[N,N,N –三乙基-N-羟丙基聚醚季铵]或[N,N,N –三乙基-N-羟正丁基聚醚季铵] [1钒11钼磷酸根]盐或[2钒10钼磷酸根]盐或[3钒9钼磷酸根]盐或 [1钒17钼磷酸根]盐或[2钒16钼磷酸根]盐或[3钒15钼磷酸根]盐;[N,N,N –三羟乙基-N-羟乙基聚醚季铵]或[N,N,N –三羟乙基-N-羟异丙基聚醚季铵]或[N,N,N –三羟乙基-N-羟丙基聚醚季铵]或[N,N,N –三羟乙基-N-羟丁基聚醚季铵] [1钒11钼磷酸根]盐或[2钒10钼磷酸根]盐或[3钒9钼磷酸根]盐或 [1钒17钼磷酸根]盐或[2钒16钼磷酸根]盐或[3钒15钼磷酸根]盐;相对应化学式依次为:[C8H20O3N+]4n[PMo11VO40 -4]n(PEPIL-1)、[C8H20O3N+]5n[PMo10V2O40 -5]n(PEPIL -2)、[C8H20O3N+]6n[PMo9V3O40 -6]n(PEPIL -3)、[C8H20O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-4)[C8H20O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-5)、[C8H20O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-6)或[C9H22O3N+]4n[PMo11VO40 -4]n(PEPIL-7)、[C9H22O3N+]5n[PMo10V2O40 -5]n(PEPIL-8)、
[C9H22O3N+]6n[PMo9V3O40 -6]n(PEPIL-9)、[C9H22O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-10)、
[C9H22O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-11)、[C9H22O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-12)
或[C9H22O3N+]4n[PMo11VO40 -4]n(PEPIL-13)、[C9H22O3N+]5n[PMo10V2O40 -5]n(PEPIL -14)、
[C9H22O3N+]6n[PMo9V3O40 -6]n(PEPIL -15)、[C9H22O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-16)、
[C9H22O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-17)、[C9H22O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-18)
或[C10H24O3N+]4n[PMo11VO40 -4]n(PEPIL-19)、[C10H24O3N+]5n[PMo10V2O40 -5]n(PEPIL -20)、
[C10H24O3N+]6n[PMo9V3O40 -6]n(PEPIL-21)、[C10H24O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-22)、
[C10H24O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-23)、[C10H24O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-24)
或[C11H26O3N+]4n[PMo11VO40 -4]n(PEPIL-25)、[C11H26O3N+]5n[PMo10V2O40 -5]n(PEPIL -26)、[C11H26O3N+]6n[PMo9V3O40 -6]n(PEPIL-27)、[C11H26O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-28)[C11H26O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-29)、[C11H26O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-30)
或[C12H28O3N+]4n[PMo11VO40 -4]n(PEPIL-31)、[C12H26O3N+]5n[PMo10V2O40 -5]n(PEPIL-32)、
[C12H28O3N+]6n[PMo9V3O40 -6]n(PEPIL-33)、[C12H26O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-34)、
[C12H26O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-35)、[C12H26O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-36)
或[C12H28O3N+]4n[PMo11VO40 -4]n(PEPIL-37)、[C12H28O3N+]5n[PMo10V2O40 -5]n(PEPIL-38)、
[C12H28O3N+]6n[PMo9V3O40 -6]n(PEPIL-39)、[C12H28O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-40)、
[C12H28O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-41)、[C12H28O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-42)
或[C13H30O3N+]4n[PMo11VO40 -4]n(PEPIL-43)、[C13H30O3N+]5n[PMo10V2O40 -5]n(PEPIL -44)、[C13H30O3N+]6n[PMo9V3O40 -6]n(PEPIL-45)、[C13H30O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-46)[C13H30O3N+]8n[P2Mo16V2O62 -8]n(PEPIL-47)、[C13H30O3N+]9n[P2Mo15V3O62 -9]n(PEPIL-48)
或[C11H26O6N+]4n[PMo11VO40 -4]n(PEPIL-49)、[C11H26O6N+]5n[PMo10V2O40 -5]n(PEPIL -50)、[C11H26O6N+]6n[PMo9V3O40 -6]n(PEPIL-51)、[C11H26O3N+]7n[P2Mo17V1O62 -7]n(PEPIL-52)[C11H26O6N+]8n[P2Mo16V2O62 -8]n(PEPIL-53)、[C11H26O6N+]9n[P2Mo15V3O62 -9]n(PEPIL-54)或[C12H28O6N+]4n[PMo11VO40 -4]n(PEPIL-55)、[C12H28O6N+]5n[PMo10V2O40 -5]n(PEPIL-56)、
[C12H28O6N+]6n[PMo9V3O40 -6]n(PEPIL-57)、[C12H28O6N+]7n[P2Mo17V1O62 -7]n(PEPIL-58)、
[C12H28O6N+]8n[P2Mo16V2O62 -8]n(PEPIL-59)、[C12H28O6N+]9n[P2Mo15V3O62 -9]n(PEPIL-60)
或[C12H28O6N+]4n[PMo11VO40 -4]n(PEPIL-61)、[C12H28O6N+]5n[PMo10V2O40 -5]n(PEPIL-62)、
[C12H28O6N+]6n[PMo9V3O40 -6]n(PEPIL-63)、[C12H28O6N+]7n[P2Mo17V1O62 -7]n(PEPIL-64)、
[C12H28O6N+]8n[P2Mo16V2O62 -8]n(PEPIL-65)、[C12H28O6N+]9n[P2Mo15V3O62 -9]n(PEPIL-66)
或[C13H30O6N+]4n[PMo11VO40 -4]n(PEPIL-67)、[C13H30O6N+]5n[PMo10V2O40 -5]n(PEPIL -68)、
[C13H30O6N+]6n[PMo9V3O40 -6]n(PEPIL-69)、[C13H30O6N+]7n[P2Mo17V1O62 -7]n(PEPIL-70)、
[C13H30O6N+]8n[P2Mo16V2O62 -8]n(PEPIL-71)、[C13H30O6N+]9n[P2Mo15V3O62 -9]n(PEPIL-72);
n取值范围为10~120。
3.根据权利要求2所述的聚醚官能化钒掺杂杂多酸聚离子液体,其特征在于:所述的聚离子液体结构的合成包括以下步骤:
步骤S101:在配有磁力搅拌的反应瓶中,依次加入15 mL二氯乙烷、4 mL乙二醇或1,2-丙二醇或1,3-丙二醇或丁二醇,2 mL三氟化硼乙醚络合物,冷至0-5℃,滴加25mL环氧氯丙烷,加毕保温反应6h;加15-30mL适量的水终止反应;水洗、静置分相、旋蒸,得到无色粘稠状的端羟基聚醚,产率89-93%;
步骤S102:氮气保护下,在配有磁力搅拌的反应瓶中,将上述步骤S101所得的任一种聚醚溶于无水乙醇,升温至45℃滴加三甲胺或三乙胺或三乙醇胺的醇溶液,加毕保温反应12h。抽滤,乙醇淋洗、真空干燥至恒重;聚醚与三甲胺或三乙胺或三乙醇胺的摩尔比为1:m*1.05:m为聚醚聚合度;
步骤S103:氮气保护下,在配有磁力搅拌的反应瓶中,将上述步骤S102所得的任一种聚醚季铵盐溶于去离子水,室温下滴加H4PMo11VO40或H5PMo10V2O40或H6PMo9V3O40或H7 P2Mo17V1O62或H8 P2Mo16V2O62或H9 P2Mo15V3O62水溶液,加毕室温下反应12h;抽滤,无离子水淋洗、真空干燥至恒重;聚醚季铵盐与杂多酸的摩尔比为1:n/4或1:n/5或1:n/6或1:n/7或1:/或1:n/9;n为聚醚聚合度。
4.一种如权利要求1所述的聚醚官能化钒掺杂杂多酸聚离子液体的应用,其特征在于:所述的聚醚基官能化钒掺杂杂多酸聚离子液体为催化体系,工业级35wt%过氧化氢为氧化剂,环己烯、环戊烯接力氧化合成环己内酯、环戊内酯。
5.根据权利要求4所述的所述的聚醚官能化钒掺杂杂多酸聚离子液体的应用,其特征在于:具体包括以下步骤:
在配有磁力的反应瓶中,按摩尔比计,环烯:过氧化氢:聚离子液体=1:8:0.0006,依次加入聚离子液体、环烯,升温至50℃,先滴加为总质量一半的35wt%过氧化氢水溶液,加毕保温反应4h;静置分相,分去下层水相,减压蒸馏除去未反应的环烯烃,混合升温至70℃,滴加剩下总质量一半的35wt%过氧化氢水溶液,加毕保温反应4h;无水乙醚3×10mL萃取,静置分相、过滤,有机相经无水硫酸镁干燥、抽滤、离心、旋蒸得到目标产物,产率为23~49%;所述环烯为环己烯或环戊烯。
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