CN112174876A - 一种吡啶类离子液体酸性催化剂的制备方法及其应用 - Google Patents
一种吡啶类离子液体酸性催化剂的制备方法及其应用 Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
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- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims description 27
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 24
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 17
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 17
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 17
- 239000005642 Oleic acid Substances 0.000 claims description 17
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 17
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 11
- 239000010689 synthetic lubricating oil Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229940049964 oleate Drugs 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
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- 239000012467 final product Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- QTIMEBJTEBWHOB-PMDAXIHYSA-N [3-[(z)-octadec-9-enoyl]oxy-2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]propyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COC(=O)CCCCCCC\C=C/CCCCCCCC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC QTIMEBJTEBWHOB-PMDAXIHYSA-N 0.000 abstract description 11
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- -1 butylene disulfate hydrogen salt Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- VHGCUBAXVOMNBB-UHFFFAOYSA-N 2-ethenylpyridine;trifluoromethanesulfonic acid Chemical compound C=CC1=CC=CC=[NH+]1.[O-]S(=O)(=O)C(F)(F)F VHGCUBAXVOMNBB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- LDRUAENASKHEDL-UHFFFAOYSA-N 4-ethenylpyridine;trifluoromethanesulfonic acid Chemical compound C=CC1=CC=NC=C1.OS(=O)(=O)C(F)(F)F LDRUAENASKHEDL-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- RPAXCVOJZANFHG-UHFFFAOYSA-N OS(C(F)(F)F)(=O)=O.C1=CC=NC=C1.Cl Chemical compound OS(C(F)(F)F)(=O)=O.C1=CC=NC=C1.Cl RPAXCVOJZANFHG-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- YWVYZMVYXAVAKS-UHFFFAOYSA-N pyridin-1-ium;trifluoromethanesulfonate Chemical compound C1=CC=[NH+]C=C1.[O-]S(=O)(=O)C(F)(F)F YWVYZMVYXAVAKS-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- C07D213/20—Quaternary compounds thereof
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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
- B01J31/02—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
- B01J31/0281—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 nitrogen being a ring member
- B01J31/0284—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 nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
本发明公开了一种吡啶类离子液体酸性催化剂的制备方法及其应用,包括:加入DMF溶解1,3‑丙磺酸内酯,在搅拌条件下缓慢加入吡啶类物质,在加热、搅拌条件下反应,反应结束后,对反应液减压蒸馏除去甲醇,经干燥,制得吡啶类离子液体中间体;将吡啶类离子液体中间体用蒸馏水溶解,加入三氟甲烷磺酸,在加热、搅拌条件下反应,反应结束后,对反应液减压蒸馏除去水,制得吡啶类离子液体单体。本发明通过二步法合成一系列吡啶类离子液体酸性催化剂,用于催化合成季戊四醇四油酸酯,所需反应条件温和易于控制,吡啶类离子液体催化剂催化活性高,产物与吡啶类离子液体酸性催化剂可以离心或者沉降分离,后处理方便。
Description
技术领域
本发明属于润滑油合成技术领域,具体涉及一种吡啶类离子液体酸性催化剂的制备 方法以及将其作为催化剂催化季戊四醇与油酸酯化反应制备季戊四醇油酸酯的应用方法。
背景技术
润滑油在使用过程中大约有50%通过挥发、泄漏等方式进入环境,其中液压油在使 用过程中的损失高达70%~80%,这些润滑油95%以上来源于石油,而石油基润滑油的生 物降解性很差,降解率只有10%~30%(Wagner H,Luther R,Mang T.Lubricant basefluids based on renewable raw materials:Their catalytic manufacture andmodification[J].Applied Catalysis A General,2001,221(s 1–2):429-442.)。另一方面,全球石油资源的日益匮乏, 导致了石油基润滑油资源性短缺的紧张局面。因而,以来源广泛的可再生资源为原料合 成环境可接受型润滑油基础油受到广泛关注,具有很大的市场潜力。
季戊四醇油酸酯不仅满足可再生和生物可降解这两方面的要求,还具有石油基润滑 油的优越性能:具有较宽的液体范围,较高的黏度指数,优良的黏度性能和低温性能;热安定性好,热分解温度在340℃以上;分子结构中含有较高活性的酯基基团,易于吸 附在金属表面形成牢固的润滑油膜,具有较好的摩擦润滑特性。
季戊四醇和油酸通过酯化反应合成季戊四醇四油酸酯中,催化剂有着很重要的作用,对季戊四醇四油酸酯的转化率、收率都有较大影响。目前,工业上的传统合成方法 中采用以对甲苯磺酸为催化剂(廖德仲等,季戊四醇油酸酯的合成[J].湖南理工学院学 报(自然科学版),2007(01):77-79.),由于对甲苯磺酸的强氧化性会导致该过程会产生磺化 和碳化聚合等副反应发生,致使产品收率低、颜色深、反应工艺的后处理复杂以及反应 温度较高(160~180℃)等缺点。李凯(李凯等,季戊四醇油酸酯的合成工艺[J].中国 油脂,2007,032(012):53-56.)等研究了在以对甲苯磺酸为催化剂的条件下,不需要脱色 剂直接酯化反应得到了收率大于95%的高透明度的季戊四醇四油酸酯,但是作为催化剂 的对甲苯磺酸在反应结束后难以与产品分离,后处理工艺复杂,同时对甲苯磺酸对设备 具有一定的腐蚀性且反应温度较高(160℃)。
梁金花(梁金花等,酸性功能化双核离子液体制备及催化合成醋酸丁酯研 究[J].高校化学工程学报(3):160-164.)等采用两步法制备了四种阳离子相同,阴离子不 同的酸性双核咪唑离子液体:双-(3-甲基-1-咪唑)亚丁基二磷酸二氢盐、双-(3-甲基-1-咪唑)亚丁基二乙酸盐、双-(3-甲基-1-咪唑)亚丁基二草酸盐、双-(3-甲基-1-咪唑) 亚丁基二硫酸氢盐,以乙酸与正丁醇为原料,离子液体作为催化剂催化合成乙酸正丁酯, 其中双-(3-甲基-1-咪唑)亚丁基二硫酸氢盐离子液体作为催化剂,催化剂用量为1.6 wt.%,90℃条件下反应4h,选择性接近99.9%,乙酸转化率可达82%。但该酸性双核咪 唑离子液体制备较为复杂,酯化反应活性较低。
综上所述,急需一个新型催化剂和技术来解决这些问题。
发明内容
发明目的:为了克服现有技术中存在的不足,提供一种吡啶类离子液体酸性催化剂 的制备方法以及将其作为催化剂催化季戊四醇与油酸酯化反应制备季戊四醇油酸酯的应用方法。
技术方案:为实现上述目的,本发明提供一种吡啶类离子液体酸性催化剂的制备方 法,包括如下步骤:
S1:加入DMF溶解1,3-丙磺酸内酯,在搅拌条件下缓慢加入吡啶类物质,在加热、搅拌条件下反应,反应结束后,对反应液减压蒸馏除去甲醇,经干燥,制得吡啶类离子 液体中间体;
S2:将步骤S1制得的吡啶类离子液体中间体用蒸馏水溶解,加入三氟甲烷磺酸,在加热、搅拌条件下反应,反应结束后,对反应液减压蒸馏除去水,制得吡啶类离子液 体单体。
进一步的,所述步骤S1中吡啶类离子液体中间体的反应式如下:
进一步的,所述步骤S2中吡啶类离子液体单体的结构式如下:
进一步的,所述步骤S1中1,3-丙磺酸内酯和吡啶类物质以摩尔比1:1~1.10进料,加热温度为35~70℃,搅拌反应时间为6~8h。
进一步的,所述步骤S2中加热温度为110~130℃,搅拌反应时间为10~12h。
进一步的,所述步骤S2中三氟甲烷磺酸和吡啶类离子液体中间体的摩尔质量相同。
一种吡啶类离子液体酸性催化剂的应用方法,将吡啶类离子液体酸性催化剂应用于 季戊四醇与油酸酯化反应,用于催化季戊四醇与油酸酯化反应制备季戊四醇油酸酯合成 润滑油。
进一步的,所述酯化反应的方法步骤为:
加入季戊四醇与油酸,在温度条件下使物料溶解,将吡啶类离子液体酸性催化剂加 入,在N2保护条件下加热,并持续搅拌反应,反应结束后冷却沉降或者离心分离出吡 啶类离子液体酸性催化剂,产品精制得最终产品。
进一步的,所述酯化反应中:季戊四醇与油酸以摩尔比1:4.0~4.2进料,吡啶类离子液体酸性催化剂用量为所加入原料质量的0.5wt.%~2.5wt.%,加热温度为90~120℃,搅拌反应时间为5~8h,将反应液冷却至70℃左右,离心分离出离子液体,再精制得产 品。
本发明的创新性在于吡啶类离子液体酸性催化剂的合成制备方法,以及将其用于催 化酯化反应制备合成润滑油。该类型离子液体由咪唑类物质、1,3-丙磺酸内酯、三氟甲烷磺酸通过二步法制得,是一种酸催化剂,具有催化活性高、易于制备等优点,可在反 应器中高效实现均相催化反应;因此,可利用其酸性促进酯化反应连续进行。本发明的 催化剂能作为制备合成润滑油的催化剂,进行酯化反应过程,离子液体在合成润滑油生 产领域具有极大的应用潜力,为促进绿色高性能合成润滑油在国内推广奠定基础。
有益效果:本发明与现有技术相比,具备如下优点:
1、所选吡啶类离子液体酸性催化剂易于合成,合成条件温和,制备时间短,可大规模生产;
2、所选吡啶类离子液体酸性催化剂催化活性高,选择性高;
3、所选吡啶类离子液体酸性催化剂对生产设备无腐蚀,对环境污染小,提升了环境友好性;
4、所选吡啶类离子液体酸性催化剂催化合成季戊四醇四油酸酯,酯化率高,反应条件温和,反应时间短,该离子液体与反应产物分离简单,降低了后期分离工艺的难度, 通过沉降或者离心分离,再精制得产品,产品色泽好。
具体实施方式
下面结合具体实施例,进一步阐明本发明,应理解这些实施例仅用于说明本发明而 不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
实施例1:
本实施例制备的吡啶类离子液体酸性催化剂为吡啶三氟甲烷磺酸盐酸催化剂,其具 体的合成制备步骤为:
将1,3-丙磺酸内酯和吡啶以摩尔比为1:1,冰浴、搅拌条件下加料,DMF做溶剂,在35℃条件下,匀速搅拌反应6小时。反应结束后,通过旋转蒸发仪减压蒸馏除去DMF, 得离子液体中间体。
将所得的离子液体中间体用蒸馏水溶解,在冰浴、搅拌的条件下缓慢滴加已经加水 溶解后的与吡啶等摩尔质量的三氟甲烷磺酸,滴加完毕后,自然升温至室温并持续搅拌15min,之后在110℃,搅拌条件下反应10h。反应结束后,通过减压蒸馏除去溶剂水, 得吡啶三氟甲烷磺酸盐,记为催化剂A,催化剂A的反应式如下。
实施例2:
本实施例制备的吡啶类离子液体酸性催化剂为2-乙烯基吡啶三氟甲烷磺酸盐酸催 化剂,其具体的合成制备步骤为:
将1,3-丙磺酸内酯和2-乙烯基吡啶以摩尔比为1:1.05,冰浴、搅拌条件下加料,DMF 做溶剂,在60℃条件下,匀速搅拌反应7小时。反应结束后,通过旋转蒸发仪减压蒸馏除去DMF,得离子液体中间体。
将所得的离子液体中间体用蒸馏水溶解,在冰浴、搅拌的条件下缓慢滴加加水溶解 后的与吡啶等摩尔质量的三氟甲烷磺酸,滴加完毕后,自然升温至室温并持续搅拌15min,之后在120℃,搅拌条件下反应11h。反应结束后,通过减压蒸馏除去溶剂水, 得2-乙烯基吡啶三氟甲烷磺酸盐,记为催化剂B,,催化剂B的反应式如下。
实施例3:
本实施例制备的吡啶类离子液体酸性催化剂为4-乙烯基吡啶三氟甲烷磺酸盐酸催 化剂,其具体的合成制备步骤为:
将1,3-丙磺酸内酯和4-乙烯基吡啶以摩尔比为1:1.1,冰浴、搅拌条件下加料,DMF做溶剂,在70℃条件下,匀速搅拌反应8小时。反应结束后,通过旋转蒸发仪减压蒸 馏除去DMF,得离子液体中间体。
将所得的离子液体中间体用蒸馏水溶解,在冰浴、搅拌的条件下缓慢滴加加水溶解 后的与吡啶等摩尔质量的三氟甲烷磺酸,滴加完毕后,自然升温至室温并持续搅拌15min,之后在130℃,搅拌条件下反应12h。反应结束后,通过减压蒸馏除去溶剂水, 得4-乙烯基吡啶三氟甲烷磺酸盐,记为催化剂C,催化剂C的反应式如下。
实施例4:
本实施例中将实施例1制得的催化剂A用于季戊四醇与油酸酯化反应当中,用于催化合成季戊四醇四油酸酯合成润滑油基础油,具体过程为:
在配有磁力搅拌器的、回流冷凝管和温度计的四口烧瓶中加入13.62g的三羟甲基丙烷和112.98g的油酸(醇酸比1:4),在匀速搅拌、持续通入N2的条件下,升温至60℃, 待原料溶解后,加入催化剂A 0.63g(0.5wt.%),升温至90℃,反应5小时。将反应 液冷却至70℃左右,离心分离出离子液体,产品经5%氢氧化钠溶液漂洗除去少量未反 应的原料,再水洗三次漂洗,再脱水,得到季戊四醇四油酸酯合成润滑油基础油。
本实施例的酯化反应的酯化率为97.91%,明显高于现有工艺方法,产品指标合格, 产品色泽好,为浅黄色。
实施例5:
本实施例中将实施例2制得的催化剂B用于季戊四醇与油酸酯化反应当中,用于催化合成季戊四醇四油酸酯合成润滑油基础油,具体过程为:
在配有磁力搅拌器的、回流冷凝管和温度计的四口烧瓶中加入13.62g的三羟甲基丙烷和115.81g的油酸(醇酸比1:4.1),在匀速搅拌、持续通入N2的条件下,升温至 60℃,待原料溶解后,加入催化剂B 1.94g(1.5wt.%),升温至110℃,反应7小时。 将反应液冷却至70℃左右,离心分离出离子液体,产品经5%氢氧化钠溶液漂洗除去少 量未反应原料,再水洗三次漂洗,再脱水,得到季戊四醇四油酸酯合成润滑油基础油。
本实施例的酯化反应的酯化率为98.24%,,明显高于现有工艺方法,产品指标合格, 产品色泽好,为浅黄色。
实施例6:
本实施例中将实施例3制得的催化剂C用于季戊四醇与油酸酯化反应当中,用于催化合成季戊四醇四油酸酯合成润滑油基础油,具体过程为:
在配有磁力搅拌器的、回流冷凝管和温度计的四口烧瓶中加入13.62g的三羟甲基丙烷和118.63g的油酸(醇酸比1:4.2),在匀速搅拌、持续通入N2的条件下,升温至 60℃,待原料溶解后,加入催化剂C 3.31g(2.5wt.%),升温至120℃,反应8小时。 将反应液冷却至70℃左右,沉降分离出离子液体,产品经5%氢氧化钠溶液漂洗除去少 量未反应原料,再水洗三次漂洗,再脱水,得到季戊四醇四油酸酯合成润滑油基础油。
本实施例的酯化反应的酯化率为99.43%,,明显高于现有工艺方法,产品指标合格, 产品色泽好,为浅黄色。
根据实施例4~6可见,酯化反应后可通过离心或者沉降方式对产品和剩余的催化剂 直接分离,从而极大的降低了分离难度和复杂度,不但大幅提高了分离效率,而且能够保证很好的分离效果。
Claims (9)
1.一种吡啶类离子液体酸性催化剂的制备方法,其特征在于,包括如下步骤:
S1:加入DMF溶解1,3-丙磺酸内酯,在搅拌条件下缓慢加入吡啶类物质,在加热、搅拌条件下反应,反应结束后,对反应液减压蒸馏除去甲醇,经干燥,制得吡啶类离子液体中间体;
S2:将步骤S1制得的吡啶类离子液体中间体用蒸馏水溶解,加入三氟甲烷磺酸,在加热、搅拌条件下反应,反应结束后,对反应液减压蒸馏除去水,制得吡啶类离子液体单体。
4.根据权利要求1所述的一种吡啶类离子液体酸性催化剂的制备方法,其特征在于,所述步骤S1中1,3-丙磺酸内酯和吡啶类物质以摩尔比1:1~1.10进料,加热温度为35~70℃,搅拌反应时间为6~8h。
5.根据权利要求1所述的一种吡啶类离子液体酸性催化剂的制备方法,其特征在于,所述步骤S2中加热温度为110~130℃,搅拌反应时间为10~12h。
6.根据权利要求1所述的一种吡啶类离子液体酸性催化剂的制备方法,其特征在于,所述步骤S2中三氟甲烷磺酸和吡啶类离子液体中间体的摩尔质量相同。
7.一种吡啶类离子液体酸性催化剂的应用方法,其特征在于,将吡啶类离子液体酸性催化剂应用于季戊四醇与油酸酯化反应,用于催化季戊四醇与油酸酯化反应制备季戊四醇油酸酯合成润滑油。
8.根据权利要求7所述的一种吡啶类离子液体酸性催化剂的应用方法,其特征在于,所述酯化反应的方法步骤为:
加入季戊四醇与油酸,在温度条件下使物料溶解,将吡啶类离子液体酸性催化剂加入,在N2保护条件下加热,并持续搅拌反应,反应结束后冷却沉降或者离心分离出吡啶类离子液体酸性催化剂,产品精制得最终产品。
9.根据权利要求8所述的一种吡啶类离子液体酸性催化剂的应用方法,其特征在于,所述酯化反应中:季戊四醇与油酸以摩尔比1:4.0~4.2进料,吡啶类离子液体酸性催化剂用量为所加入原料质量的0.5wt.%~2.5wt.%,加热温度为90~120℃,搅拌反应时间为5~8h,将反应液冷却至70℃左右,离心分离出离子液体,再精制得产品。
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