CN116854626A - 一种2-乙烯基吡啶的制备方法 - Google Patents
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- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- QRBVCAWHUSTDOT-UHFFFAOYSA-N Methyridine Chemical compound COCCC1=CC=CC=N1 QRBVCAWHUSTDOT-UHFFFAOYSA-N 0.000 claims abstract description 29
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 238000005336 cracking Methods 0.000 claims abstract description 9
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- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 11
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 11
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- -1 bis (cyclopentadienyl) cobalt Chemical compound 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
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- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 0.000 claims description 7
- HAFGILPEWSXQTJ-UHFFFAOYSA-N 1h-indene;sodium Chemical compound [Na].C1=CC=C2CC=CC2=C1 HAFGILPEWSXQTJ-UHFFFAOYSA-N 0.000 claims description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
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- FNAYLSDQHZLYQB-UHFFFAOYSA-N 2-methyloxolane;toluene Chemical compound CC1CCCO1.CC1=CC=CC=C1 FNAYLSDQHZLYQB-UHFFFAOYSA-N 0.000 claims description 3
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 3
- GNWXVOQHLPBSSR-UHFFFAOYSA-N oxolane;toluene Chemical group C1CCOC1.CC1=CC=CC=C1 GNWXVOQHLPBSSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
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- 208000012839 conversion disease Diseases 0.000 abstract description 2
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- 239000012295 chemical reaction liquid Substances 0.000 description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010606 normalization Methods 0.000 description 4
- BXGYBSJAZFGIPX-UHFFFAOYSA-N 2-pyridin-2-ylethanol Chemical compound OCCC1=CC=CC=N1 BXGYBSJAZFGIPX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- SFPQDYSOPQHZAQ-SCSAIBSYSA-N (2r)-2-methoxypropanenitrile Chemical compound CO[C@H](C)C#N SFPQDYSOPQHZAQ-SCSAIBSYSA-N 0.000 description 1
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- UDBORWKCIDLNIG-UHFFFAOYSA-N sodium;1h-inden-1-ide Chemical compound [Na+].C1=CC=C2[CH-]C=CC2=C1 UDBORWKCIDLNIG-UHFFFAOYSA-N 0.000 description 1
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
- C07D213/12—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明专利涉及一种2‑乙烯基吡啶的制备方法，其以3‑甲氧基丙腈和乙炔为原料，在环合催化剂及溶剂存在下，于温度140‑180℃、压力0.6‑2.0 MPa下进行反应，反应结束，蒸出溶剂，减压蒸馏得到2‑甲氧基乙基吡啶；将2‑甲氧基乙基吡啶在裂解催化剂、阻聚剂存在下于80‑180℃催化裂解，经减压精馏后得到2‑乙烯基吡啶。本发明方法具有原料易得、反应转化率高等优点。
Description
技术领域
本发明属于烯基吡啶化合物的合成技术领域，具体涉及一种2-乙烯基吡啶（2-VP）的制备方法。
背景技术
2-乙烯基吡啶是丁苯吡胶乳合成的关键原料。2-乙烯基吡啶的合成，国内外主要以2-甲基吡啶为原料，经与甲醛或多聚甲醛缩合得到中间体2-羟乙基吡啶，然后脱水得到。专利CN105237468B采用2-甲基吡啶和聚甲醛在有机酸催化下，并在二甲基甲酰胺存在下制备中间体2-羟乙基吡啶，反应时间长达30-40 h，该方法存在反应时间长、生产效率低等缺陷。中国专利CN1250527C采用2-羟乙基吡啶为原料，在硫酸、磷酸、氢氧化钠或氢氧化钾存在下，脱水得到2-乙烯吡啶, 但收率只有70-86%。美国专利US45588815采用丙烯腈为原料，与乙炔直接催化制备2-乙烯基吡啶，该方法虽然路线简洁，但催化剂的制备困难，并且丙烯腈与乙炔直接合成2-乙烯基吡啶时，气液反应条件下需要把产物2-乙烯基吡啶及时取出，以避免2-乙烯基吡啶长时间受热条件下的自聚，这样极大的增加了工艺难度。
基于此，亟待研究和开发新的2-乙烯基吡啶的合成工艺，以克服和解决现有技术存在的问题。
发明内容
本发明目的在于克服现有技术缺陷，提供一种2-乙烯基吡啶的制备方法，该方法具有原料易得、成本低，所使用的催化剂制备方便，原料转化率高，中间体性质稳定，易于实现工业生产等优点。本发明以3-甲氧基丙腈和乙炔为原料，在环合催化剂及溶剂存在下，以高转化率合成得到2-甲氧基乙基吡啶，再经催化裂解、分离，高收率得到2-乙烯基吡啶。
为实现上述目的，本发明采用如下技术方案：
一种2-乙烯基吡啶的制备方法，其包括如下步骤：
1）以3-甲氧基丙腈和乙炔为原料，在环合催化剂及溶剂存在下，于温度140-180℃下持续通入乙炔气体，保持压力在0.6-2.0 MPa进行反应，反应 5-12 h ，结束反应后蒸出溶剂，然后再减压蒸馏，得到2-甲氧基乙基吡啶；反应温度优选150-170℃，压力优选 1.0-1.5 MPa；
2）将2-甲氧基乙基吡啶在裂解催化剂、阻聚剂存在下于80-180℃（优选90-130℃）催化裂解，经减压精馏蒸得裂解产物2-VP和甲醇混合物，再蒸馏后得到2-VP，或采用闪蒸分出甲醇后得到2-VP。
上述技术方案的步骤1）和2）， 采用间歇反应方式完成，也可以采用连续反应，将有机溶剂、3-甲氧基丙腈和环合催化剂溶液混合后逐步加入管道反应器，控制温度150-170℃，连续通入乙炔，系统压力控制在0.7-1.6 MPa，反应液由管道反应器另一端的出口经闪蒸、减压放出，再将反应液中的溶剂、产物蒸馏分离后、进一步精馏分离得到2-甲氧基乙基吡啶，蒸馏剩余物降温后分离沉降除去不溶物，催化剂返回使用。2-甲氧基乙基吡啶的裂解采用连续反应精馏方式，减少产物在较高温度条件下的停留时间。
上述的技术方案中，具体地，步骤1）中，3-甲氧基丙腈和乙炔反应生成2-甲氧基乙基吡啶所使用的环合催化剂为二茚基钴或双(环戊二烯基)钴的四氢呋喃-甲苯溶液、或2-甲基四氢呋喃-甲苯溶液。
具体的，步骤1）中，所述3-甲氧基丙腈与二茚基钴或双(环戊二烯基)钴（以氯化钴计）的摩尔比为50-300:1，优选100-300:1。
进一步的，步骤1）中，所述溶剂选用苯、甲苯、二甲苯或其混合物等芳烃，溶剂与原料3-甲氧基丙腈的重量比为 0.5-5:1。
上述的技术方案中，具体的，步骤2）中，所述裂解催化剂为氢氧化锂、氢氧化钠、氢氧化钾中的一种或多种，所述裂解催化剂与2-甲氧基乙基吡啶的重量比为0.01-10: 1。
进一步的，步骤2）中，所述阻聚剂为对苯二酚、叔丁基对苯二酚中的一种或两种，阻聚剂用量为2-甲氧基乙基吡啶的重量的0.1-1%。
上述的技术方案中，进一步优选的，步骤2）中，催化裂解时需要加入极性溶剂，所选极性溶剂为水、二甲基亚砜、环丁砜、聚氧乙烯醚、烷氧基聚氧乙烯醚（烷氧基包含甲氧基、乙氧基、丁氧基，聚合度范围3-200）等中的一种或多种，极性溶剂与2-甲氧基乙基吡啶的重量比为0.1- 5:1。
进一步的，所述环合催化剂溶液经下述方法制备获得：
a）在反应器中加入THF或2-甲基四氢呋喃和氨基钠，然后在氮气保护下加入茚或环戊二烯，温度保持在5-30℃反应1-4 h，得到茚钠或环戊二烯钠的THF或2-甲基四氢呋喃溶液；
b）另一反应器中，加入溶剂甲苯和无水氯化钴，然后加入步骤a）所得的茚钠或环戊二烯钠的THF或2-甲基四氢呋喃溶液，加热回流2-4 h，冷却后，过滤除去不溶物，即得环合催化剂溶液。
具体的，步骤a）中，四氢呋喃或2-甲基四氢呋喃和氨基钠的重量比为4-15:1，氨基钠和茚或环戊二烯的摩尔比为0.9-1.1:1。步骤b）中，溶剂甲苯和无水氯化钴的重量比为5-20:1，无水氯化钴与氨基钠的摩尔比为0.45-0.55:1。
和现有技术相比，本发明方法的有益效果如下：
本发明方法以3-甲氧基丙腈和乙炔为原料，经两步反应，第一步在环合催化剂存在下，经环加成反应得到2-甲氧基乙基吡啶，3-甲氧基丙腈的单程转化率可达到96%以上。第二步2-甲氧基乙基吡啶在裂解催化剂作用下，催化裂解生成2-VP，转化率在97%以上。并且，第一步的起始原料3-甲氧基丙腈可由丙烯腈与甲醇以定量收率制得，丙烯腈为大宗化工产品，市场价格波动小。本发明方法第一步反应的环合催化剂为钴配合物的THF-甲苯溶液或2-甲基四氢呋喃-甲苯溶液，由氯化钴与茚基钠或环戊二烯基钠反应制得，不需要进一步纯化精制直接使用，催化剂制备方便。第二步反应以氢氧化钾或氢氧化钠等为2-甲氧基乙基吡啶的裂解催化剂，催化裂解转化率高，实时真空精馏后得到产物2-VP。本发明作为由丙烯腈制备2-VP的间接方法，避免了直接方法对催化剂及反应条件的苛刻限制，具有原料易得、反应转化率高（产品收率达90%以上，产品纯度在98%以上）等优点，适于工业化生产。
具体实施方式
以下结合实施例对本发明的技术方案作进一步地详细介绍，但本发明的保护范围并不局限于此。
下述实施例中，如无特殊说明，所用原料均为可以直接购买的普通市售产品或者采用本领域常规方法可以制备获得。
实施例1
一种2-乙烯基吡啶的制备方法，其具体包括如下步骤：
1）3-甲氧基丙腈与乙炔反应催化剂的制备：
在反应瓶中加入16.0g THF和 1.6g氨基钠（0.04mol），然后在氮气保护下滴加茚4.9 g（0.04mol），在温度10-15℃反应2h，得到茚钠的THF溶液。在另一反应瓶中，加入25.0g甲苯和2.6g无水氯化钴（0.02 mol），然后加入上述制备所得茚钠的THF溶液，加热回流保持2h，冷却后过滤，得到催化剂溶液。
2）2-甲氧基乙基吡啶的合成：
将甲苯200.0 g、3-甲氧基丙腈200.0g（2.35mol）和催化剂溶液加入到压力反应器中，逐渐加热到140-160℃，不断通入乙炔气体，压力保持在1.3-1.5 MPa，反应时间9-10 h结束通气。降温后取出反应液，气相色谱测定原料转化率98.0%。将反应液中的溶剂THF、甲苯蒸出，最后在130-135℃减压蒸馏（真空度0.090-0.095kpa），得到2-甲氧基乙基吡啶310.1 g，含量99.1%（GC测定，面积归一），以3-甲氧基丙腈计收率95.4%.。
。
3）2-甲氧基乙基吡啶的裂解：
取150.0 g 2-甲氧基乙基吡啶，加入5.0 g氢氧化钠、25.0g二甲基亚砜、0.50 g对苯二酚，加热至120-125℃并保持2.5 h，减压精馏得到产物2-VP和甲醇，气相色谱测定原料转化率97.2%，然后进一步精馏，真空度0.080-0.090kpa，收集60-100℃馏分，得到2-乙烯基吡啶 109.1g，含量99.4%（GC，面积归一），收率94.3%。
。
实施例2
一种2-乙烯基吡啶的制备方法，其具体包括如下步骤：
1）3-甲氧基丙腈与乙炔反应催化剂的制备：
在反应瓶中加入16.0g 2-甲基四氢呋喃和 1.6g氨基钠（0.04mol），然后在氮气保护下加入环戊二烯2.7g（0.04mol），在温度15-20℃反应2 h，得到环戊二烯钠的2-甲基四氢呋喃溶液。在另一反应瓶中，加入25.0 g甲苯和2.6g无水氯化钴（0.02mol），然后加入上述制备所得环戊二烯钠的2-甲基四氢呋喃溶液，加热保持回流2 h后冷却，过滤得到催化剂溶液。
2）2-甲氧基乙基吡啶的合成：
将二甲苯230.0 g、3-甲氧基丙腈230.0 g（2.71mol）和步骤1）所得催化剂溶液混合，加入到压力反应容器中，加热到150-165℃，然后不断通入乙炔气体，压力保持在0.8-1.0MPa进行反应，反应 7-9 h后反应结束。反应液气相色谱测定原料转化率98.5%。将反应液中的 2-甲基四氢呋喃、甲苯、二甲苯蒸出，最后减压蒸馏得到2-甲氧基乙基吡啶359.3 g（温度120-128℃，真空度0.095-0.098kpa)，含量98.6%，以3-甲氧基丙腈计收率95.2%。
3）2-甲氧基乙基吡啶的裂解：
反应瓶中，加入30%氢氧化钾水溶液50g和阻聚剂对苯二酚0.2g，在140℃下，将2-甲氧基乙基吡啶150.1g逐渐滴入，减压蒸馏蒸出2-VP和甲醇的混合物，气相色谱测定原料转化率96.4%，再真空精馏，真空度0.080-0.090kpa，收集60-100℃馏分，得到2-乙烯基吡啶105.4 g，含量99.1 %（GC，面积归一），收率90.9%。
实施例3
一种2-乙烯基吡啶的制备方法，其具体包括如下步骤：
1）2-甲氧基丙腈与乙炔反应催化剂的制备：
在反应瓶中加入15g 2-甲基四氢呋喃和 1.6g氨基钠（0.04mol），然后在氮气保护下滴加环戊二烯2.7g（0.04mol），在温度25℃反应2h，得到环戊二烯钠的2-甲基四氢呋喃溶液。在另一反应瓶中，加入25g甲苯和2.6g无水氯化钴（0.02mol），然后加入上述制备所得环戊二烯钠的2-甲基四氢呋喃溶液，加热保持回流3h，冷却、过滤得到催化剂溶液。
2）2-甲氧基乙基吡啶的合成：
将二甲苯230.0g、3-甲氧基丙腈230.0g（2.71mol）和步骤1）所得催化剂溶液混合，然后加入到压力反应容器中，加热到160℃，然后不断通入乙炔气体，使压力维持在1.0-1.5MPa，保持8.5 h，反应结束。降温后取出反应液，气相色谱测定原料转化率97.9%。将反应液中 2-甲基四氢呋喃、甲苯、二甲苯依次蒸出，最后在129-132℃减压蒸馏（0.090-0.096kpa），得到2-甲氧基吡啶366.5g，含量97.9%，以3-甲氧基丙腈计收率96.7%.
3）2-甲氧基乙基吡啶的合成裂解：
反应瓶中加入4.0 g氢氧化钾、50.0g二甲基亚砜，叔丁基对苯二酚0.5g，在120℃下，将2-甲氧基乙基吡啶150.0g逐步滴入，减压精馏出2-VP和甲醇，气相色谱测定原料转化率97.0%，再真空精馏，真空度0.080-0.090kpa，收集60-100℃馏分，得到2-乙烯基吡啶105.6 g，含量98.1%（GC，面积归一），收率90.1 %。
Claims (10)
1.一种2-乙烯基吡啶的制备方法，其特征在于，包括如下步骤：
1）以3-甲氧基丙腈和乙炔为原料，在环合催化剂及溶剂存在下，温度140-180℃、维持压力0.6-2.0MPa下进行反应，反应时间5-12h，结束反应后蒸出溶剂，然后减压蒸馏，得到2-甲氧基乙基吡啶；
2）将2-甲氧基乙基吡啶在裂解催化剂、阻聚剂存在下于80-180℃催化裂解，经减压精馏、再蒸馏后得到2-乙烯基吡啶。
2.如权利要求1所述2-乙烯基吡啶的制备方法，其特征在于，步骤1）中，所述环合催化剂为二茚基钴或双(环戊二烯基)钴的四氢呋喃-甲苯溶液、或2-甲基四氢呋喃-甲苯溶液。
3.如权利要求1所述2-乙烯基吡啶的制备方法，其特征在于，步骤1）中，所述3-甲氧基丙腈与二茚基钴或双(环戊二烯基)钴的摩尔比为50-300:1。
4.如权利要求1所述2-乙烯基吡啶的制备方法，其特征在于，步骤1）中，所述溶剂选用苯、甲苯、二甲苯或其混合物，溶剂与原料3-甲氧基丙腈的重量比为 0.5-5:1。
5.如权利要求1所述2-乙烯基吡啶的制备方法，其特征在于，步骤2）中，所述裂解催化剂为氢氧化锂、氢氧化钠、氢氧化钾中的一种或多种，所述裂解催化剂与2-甲氧基乙基吡啶的重量比为0.01-10: 1。
6.如权利要求1所述2-乙烯基吡啶的制备方法，其特征在于，步骤2）中，催化裂解时加入所选极性溶剂中的一种或多种，所选极性溶剂为水、二甲基亚砜、环丁砜、聚氧乙烯醚或烷氧基聚氧乙烯醚，其中烷氧基包含甲氧基、乙氧基、丁氧基，聚氧乙烯醚的聚合度范围3-200，极性溶剂与2-甲氧基乙基吡啶的重量比为0.1-5:1。
7.如权利要求1所述2-乙烯基吡啶的制备方法，其特征在于，步骤2）中，所述阻聚剂为对苯二酚、叔丁基对苯二酚中的一种或两种。
8.如权利要求2所述2-乙烯基吡啶的制备方法，其特征在于，所述环合催化剂溶液经下述方法制备得到：
a）在反应器中加入四氢呋喃（THF）或2-甲基四氢呋喃和氨基钠，然后在氮气保护下加入茚或环戊二烯，温度保持在5-30℃反应1-4 h，得到茚钠或环戊二烯钠的THF或2-甲基四氢呋喃溶液；
b）另一反应器中，加入甲苯和无水氯化钴，然后加入步骤a）所得的茚钠或环戊二烯钠的THF或2-甲基四氢呋喃溶液，加热回流2-4 h，冷却后，滤除不溶物，即得。
9.如权利要求8所述2-乙烯基吡啶的制备方法，其特征在于，步骤a）中，四氢呋喃或2-甲基四氢呋喃和氨基钠的重量比为4-15:1，氨基钠和茚或环戊二烯的摩尔比为1.0-1.1:1。
10.如权利要求8所述2-乙烯基吡啶的制备方法，其特征在于，步骤b）中，甲苯和无水氯化钴的重量比为5-20:1，无水氯化钴与氨基钠的摩尔比为0.45-0.55:1。
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