CN115041227A - 一种金属羧酸基离子液体催化剂及其制备方法与应用 - Google Patents
一种金属羧酸基离子液体催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000001450 anions Chemical class 0.000 claims abstract description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- -1 imidazole cations Chemical class 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000002390 rotary evaporation Methods 0.000 claims description 30
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- ANZUDYZHSVGBRF-UHFFFAOYSA-N 3-ethylnonane-1,2,3-triol Chemical compound CCCCCCC(O)(CC)C(O)CO ANZUDYZHSVGBRF-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000012263 liquid product Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
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- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
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- 230000003197 catalytic effect Effects 0.000 abstract description 20
- NCZPCONIKBICGS-UHFFFAOYSA-N 3-(2-ethylhexoxy)propane-1,2-diol Chemical compound CCCCC(CC)COCC(O)CO NCZPCONIKBICGS-UHFFFAOYSA-N 0.000 abstract description 12
- 229940100524 ethylhexylglycerin Drugs 0.000 abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
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- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 208000012839 conversion disease Diseases 0.000 abstract description 3
- 239000011968 lewis acid catalyst Substances 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 11
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 10
- 230000009967 tasteless effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- 229910015900 BF3 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
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- 230000003020 moisturizing effect Effects 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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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- B01J31/0278—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
- B01J31/0285—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 also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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Abstract
本发明涉及一种金属羧酸基离子液体催化剂的制备方法及应用,本发明提供一种由金属咪唑阳离子和弱酸阴离子构成的一种具有协同催化作用的离子液体催化体系。与传统路易斯酸催化剂相比,反应过程温和易控,并进一步提高了反应转化率和选择性,且解决了传统催化剂残余氯等在化妆品的危害问题。本发明催化剂在催化过程中不仅起到了催化作用,同时残留在合成的乙基己基甘油中还具有一定的抗菌作用。
Description
技术领域
本发明涉及催化剂技术领域,具体涉及一种金属羧酸基离子液体催化剂及其制备方法,以及催化丙酮与2-乙基己基缩水甘油醚合成乙基己基甘油的应用。
背景技术
乙基己基甘油兼具保湿作用和除臭抑菌作用,其与苯乙醇的复配物是一种重要的“无添加”防腐增效剂,将其用于化妆品中,既能显著改善化妆品的皮肤感觉,又能增加香味的扩散能力,是一种全球公认的多功能的化妆品添加剂。2015年,中国新实施了《化妆品安全技术规范》,高度重视防腐剂的安全性问题,这使得“无添加”防腐剂及天然防腐剂成为持久发展的重要途径。因此,乙基己基甘油具有巨大的市场应用潜力。
目前,乙基己基甘油合成工艺主要分为三种,一种是醇与缩水甘油醚制备乙基己基甘油,另一种是酸酐或者羧酸与缩水甘油醚加成反应后水解,第三种是通过对2-乙基己基缩水甘油醚的环氧基与酮进行羰基加成反应后水解制得。其中,第三种工艺反应条件温和,反应过程易控制。该工艺一般采用传统路易斯酸作为催化剂,进攻羰基碳进行加成反应,然后在碱性条件下水解合成乙基己基甘油,但容易发生聚合等副反应,产生的杂质会导致乙基己基甘油颜色加深并有异味,且残留的传统路易斯酸催化剂和杂质会影响毒理反应,无法作为添加剂使用在化妆品中。
发明内容
发明目的:
本发明提出一种金属羧酸基离子液体催化剂的制备方法及应用,其目的在于提供一种由金属咪唑阳离子和弱酸阴离子构成的一种具有协同催化作用的离子液体催化体系。与传统路易斯酸催化剂相比,反应过程温和易控,并进一步提高了反应转化率和选择性,且解决了传统催化剂残余氯等在化妆品的危害问题。该催化剂在催化过程中不仅起到了催化作用,同时残留在合成的乙基己基甘油中还具有一定的抗菌作用。
技术方案:
一种金属羧酸基离子液体催化剂,该催化剂的结构如通式I所示,
式中,R=CnH2n+1;
M=Na,K,Li;
CnH2n n=0、1、2、3、....;
A-代表弱酸阴离子。
优选的,M的原料源于氢氧化钠、氢氧化钾或者氢氧化锂。
优选的,阴离子A-的原料源于甲酸、醋酸、磷酸或者钼酸。
一种金属羧酸基离子液体催化剂的制备方法,步骤为:
(1)首先向反应器中加入烷基咪唑原料,然后加入等摩尔的含羧酸基团的卤代烷烃原料,再加入乙醇溶剂,其用量与上述两种反应原料总体积的比例为3-5:1,60-80℃氮气保护下冷凝回流磁力搅拌反应10-16h,反应结束后得到液体产物,将液体产物50-70℃真空旋蒸除去溶剂,然后加入与反应原料总体积比为1-3:1的乙酸乙酯洗涤去除未反应原料,并于50-70℃条件下再次旋蒸,最后将产物于60-70℃条件下真空干燥16-24h,得中间体Ⅰ淡黄色液体;
(2)将摩尔比1:0.5-2的中间体Ⅰ与含钾、钠或者锂的氢氧化物加入反应器,再加入蒸馏水,其用量与上述反应原料总体积比为2-4:1,并在30-45℃回流搅拌4-6h,70-90℃真空旋蒸除去水溶剂,然后再加入与反应原料总体积比为1-2:1的甲醇洗涤并真空旋蒸,70-90℃真空干燥16-24h得中间体Ⅱ;
(3)将等摩尔量的中间体Ⅱ与醋酸钠加入反应器,再加入乙醇溶剂,其用量与上述反应原料总体积比为2-4:1,并在30-45℃回流搅拌4-8h,反应结束后将体系中的固体颗粒过滤掉,滤液于50-70℃条件下真空旋蒸除去乙醇溶剂,然后再加入与反应原料总体积比为1-2:1的乙醇洗涤并在同样条件下真空旋蒸,得粗产物于60-70℃条件下真空干燥16-24h,制得白色膏状的金属羧酸基离子液体催化剂。
优选的,步骤(2)中,含钠的氢氧化物为氢氧化钠,中间体Ⅰ与氢氧化钠的摩尔配比为1:1.5。
一种金属羧酸基离子液体催化剂在合成乙基己基甘油中的应用。
有益效果:
(1)该催化体系与单纯的含氮类催化剂相比,具有更强的配位和亲核能力,游离的弱酸阴离子可与金属离子及羧酸功能基团产生协同效应,进一步提高反应物的转化率和产物选择性。此外,还可以根据不同的催化反应需求改变金属种类和咪唑烷基侧链长度及官能团类型,以实现高效催化过程。
(2)金属羧酸基离子液体催化剂基于离子液体物性,常温下为膏状,易溶于水,乙醇等多种溶剂,不易燃烧、不易被氧化,具有较好的热稳定性和化学稳定性。
(3)金属羧酸基离子液体催化剂具有优异的反应选择性,且在水解反应阶段与加入的甲酸产生协同催化效应,促进水解反应的进行,使乙基己基甘油收率和纯度显著提高。
(4)该催化剂在合成乙基己基甘油过程中,除了起到催化作用,还具有一定的抗菌作用。
附图说明
图1为催化剂制备过程示意图;
图2为所制备的催化剂的FT-IR分析图,(A[MIM-K]+[CH3COO]-;B[MIM-Na]+[CH3COO]-;C[MIM-Li]+[CH3COO]-);
图3为所制备的催化剂的XRD分析图,(A[MIM-K]+[CH3COO]-;B[MIM-Na]+[CH3COO]-;C[MIM-Li]+[CH3COO]-)。
具体实施方式
下面通过实施例对本发明进一步详细说明。
本文以烷基咪唑(Imidazole)为基础原料,设计并制备金属羧酸基离子液体催化剂,并将其用于催化丙酮与2-乙基己基缩水甘油醚合成乙基己基甘油,该催化剂不仅催化活性高、过程温和无污染,且安全性好,并具有一定的抗菌效果。
如图1所示,本发明涉及一种金属羧酸基离子液体催化剂的制备方法及催化丙酮与2-乙基己基缩水甘油醚合成乙基己基甘油的应用。该催化剂是金属羧酸基烷基咪唑作为阳离子,弱酸作为阴离子构成离子液体催化体系。
该催化剂的结构如通式I所示,
式中,R=CnH2n+1;M=Na,K,Li;CnH2n n=0、1、2、3、....;A-代表弱酸阴离子。
M的原料源于氢氧化钠、氢氧化钾、氢氧化锂。
阴离子A-的原料源于甲酸、醋酸、磷酸、钼酸。
该催化剂基于离子液体性质稳定,易存放,绿色无污染,并且弱酸阴离子可与金属离子及羧酸功能基团产生协同催化效应,进一步增强催化活性,提高反应转化率和选择性。利用红外光谱仪(FT-IR)、X射线衍射分析(XRD)等表征了催化剂的结构。
图2的红外谱图表明,离子液体有机杂环上的C-H伸缩振动吸收峰在3063cm-1附近,侧链的CH3、CH2的振动吸收峰在2962cm-1、2926cm-1、2856cm-1附近;咪唑环上的C=C、C=N的双键振动吸收峰在1629cm-1、1445cm-1附近,N-H的振动吸收峰在2363cm-1附近,C-H的伸缩振动峰在1161cm-1和1057cm-1附近,咪唑环的弯曲振动峰在746cm-1附近,羧基官能团对应的特征峰在1712cm-1附近。由此可初步判断目标催化剂制备成功。
图3的XRD谱图可以得知,三种催化剂中金属钾、钠和锂的结晶峰明显,并且衍射峰相差不大,对应的衍射角分别为30.48°、48.26°、50.22°、55.34°等,这正是金属钾、钠和锂的典型衍射峰,因此,XRD谱图分析进一步证明了三种金属羧酸基离子液体催化剂制备成功。
将制备的金属羧酸基离子液体作为催化剂,用以催化丙酮与2-乙基己基缩水甘油醚为反应,合成乙基己基甘油。以乙基己基甘油收率、纯度、色泽和气味作为评价指标,考察制备的金属羧酸基离子液体催化剂的催化性能,并对产物乙基己基甘油进行抗菌效果测试。
一种金属羧酸基离子液体催化剂的制备方法及催化丙酮与2-乙基己基缩水甘油醚合成乙基己基甘油的反应具体实施方法如下:
分别称取1:2.5的2-乙基己基缩水甘油醚和丙酮倒入装有转子的三口烧瓶中,再加入制备的催化剂,其用量占2-乙基己基缩水甘油醚质量的0.3%。通入氮气检测密闭性,并吹扫排出烧瓶内的空气,开启磁力搅拌,室温条件下反应2h。反应结束后加入终止剂甲胺水溶剂,保持10min,减压蒸馏去除过量丙酮,再加入甲酸水溶液进行水解反应,升温75-95℃反应4h。水解产物静置分液后,油相用碱(碳酸氢钠)中和至中性后,蒸馏水洗涤3次,加入稳定剂,于70-90℃条件下旋蒸除水,即得目标产物为乙基己基甘油。
实施例1:
(1)中间体Ⅰ的制备
首先向反应器中加入0.1mol的N-甲基咪唑,加入0.1mol的氯乙酸。加入60mL的乙醇,75℃氮气(纯度99.99%)保护下冷凝回流磁力搅拌反应12h,反应结束后液体产物70℃真空旋蒸除去溶剂,然后加入30mL乙酸乙酯洗涤并再次70℃旋蒸,65℃真空干燥24h,得中间体Ⅰ淡黄色液体。
(2)中间体Ⅱ的制备
将0.1mol的中间体Ⅰ与0.1mol氢氧化钾加入三口烧瓶,加入60mL蒸馏水,45℃回流搅拌4h,80℃真空旋蒸除去溶剂,然后加入20mL甲醇洗涤并真空旋蒸,80℃真空干燥24h得中间体Ⅱ。
(3)催化剂A的制备
将0.1mol中间体Ⅱ与0.1mol的乙酸钾加入三口烧瓶,加入60mL的乙醇,45℃回流搅拌8h,反应结束后过滤,滤液70℃真空旋蒸除去溶剂,然后加入20mL的乙醇洗涤并真空旋蒸,65℃真空干燥24h得白色膏状的目标产物催化剂A,即催化剂[MIM-K]+[CH3COO]-。
实施例2:
(1)中间体Ⅰ的制备
首先向反应器中加入0.1mol的N-甲基咪唑,加入0.1mol的氯乙酸。加入60mL的乙醇,75℃氮气(纯度99.99%)保护下冷凝回流磁力搅拌反应12h,反应结束后液体产物70℃真空旋蒸除去溶剂,然后加入30mL乙酸乙酯洗涤并再次70℃旋蒸,65℃真空干燥24h,得中间体Ⅰ淡黄色液体。
(2)中间体Ⅱ的制备
将0.1mol的中间体Ⅰ与0.1mol氢氧化钠加入三口烧瓶,加入60mL蒸馏水,45℃回流搅拌4h,80℃真空旋蒸除去溶剂,然后加入20mL甲醇洗涤并真空旋蒸,80℃真空干燥24h得中间体Ⅱ。
(3)催化剂B的制备
将0.1mol中间体Ⅱ与0.1mol的乙酸钠加入三口烧瓶,加入60mL的乙醇,45℃回流搅拌8h,反应结束后过滤,滤液70℃真空旋蒸除去溶剂,然后加入20mL的乙醇洗涤并真空旋蒸,65℃真空干燥24h得白色膏状的目标产物催化剂B,即催化剂[MIM-Na]+[CH3COO]-。
实施例3:
(1)中间体Ⅰ的制备
首先向反应器中加入0.1mol的N-甲基咪唑,加入0.1mol的氯乙酸。加入60mL的乙醇,75℃氮气(纯度99.99%)保护下冷凝回流磁力搅拌反应12h,反应结束后液体产物70℃真空旋蒸除去溶剂,然后加入30mL乙酸乙酯洗涤并再次70℃旋蒸,65℃真空干燥24h,得中间体Ⅰ淡黄色液体。
(2)中间体Ⅱ的制备
将0.1mol的中间体Ⅰ与0.1mol氢氧化锂加入三口烧瓶,加入60mL蒸馏水,45℃回流搅拌4h,80℃真空旋蒸除去溶剂,然后加入20mL甲醇洗涤并真空旋蒸,80℃真空干燥24h得中间体Ⅱ。
(3)催化剂C的制备
将0.1mol中间体Ⅱ与0.1mol的乙酸锂加入三口烧瓶,加入60mL的乙醇,45℃回流搅拌8h,反应结束后过滤,滤液70℃真空旋蒸除去溶剂,然后加入20mL的乙醇洗涤并真空旋蒸,65℃真空干燥24h得白色膏状的目标产物催化剂C,即催化剂[MIM-Li]+[CH3COO]-。
将实施例1-3制备的催化剂及传统催化剂三氟化硼分别用于催化丙酮与2-乙基己基缩水甘油醚合成乙基己基甘油。得催化评价结果如表1所示。
表1 实施例1-3及传统催化剂的催化效果评价
实施例 | 催化剂名称 | 收率(%) | 纯度(%) | 颜色 | 气味 |
传统催化剂 | 三氟化硼 | 81.5 | 98.7 | 浅黄色 | 无味 |
实施例1 | [MIM-K]<sup>+</sup>[CH<sub>3</sub>COO]<sup>-</sup> | 90.2 | 98.9 | 浅黄色 | 无味 |
实施例2 | [MIM-Na]<sup>+</sup>[CH<sub>3</sub>COO]<sup>-</sup> | 92.7 | 99.4 | 无色 | 无味 |
实施例3 | [MIM-Li]<sup>+</sup>[CH<sub>3</sub>COO]<sup>-</sup> | 91.6 | 99.1 | 无色 | 无味 |
从表1中数据可知,本发明催化效果显著,与传统催化剂三氟化硼相比,乙基己基甘油产品收率由传统催化剂的81.58%提高到90%以上,其中催化剂[MIM-Na]+[CH3COO]-的催化效果最佳,乙基己基甘油产品收率高达92.7%,纯度高达99.4%。这是由于基于离子液体有意的反应选择性,且在水解反应阶段与加入的甲酸产生协同催化效应,促进水解反应的进行,进而促使乙基己基甘油收率和纯度显著提高。
实施例4
催化剂D制备方法的步骤与实施例2相同,将第三步的乙酸钠替代为钼酸钠,置换金属羧酸基离子液体催化剂的阴离子为钼酸阴离子,得目标催化剂[MIM-Na]+[HMoO4]-。
实施例5
催化剂E制备方法的步骤与实施例2相同,将第三步的乙酸钠替代为磷酸钠,置换金属羧酸基离子液体催化剂的阴离子为磷酸阴离子,得目标催化剂[MIM-Na]+[H2PO4]-。
将实施例4-5制备的催化剂分别用于催化丙酮与2-乙基己基缩水甘油醚合成乙基己基甘油,得催化评价结果如表2所示。
表2 实施例4-5的催化效果评价
实施例 | 催化剂名称 | 收率(%) | 纯度(%) | 颜色 | 气味 |
实施例2 | [MIM-Na]<sup>+</sup>[CH<sub>3</sub>COO]<sup>-</sup> | 92.7 | 99.4 | 无色 | 无味 |
实施例4 | [MIM-Na]<sup>+</sup>[HMoO<sub>4</sub>]<sup>-</sup> | 90.4 | 98.3 | 无色 | 无味 |
实施例5 | [MIM-Na]<sup>+</sup>[H<sub>2</sub>PO<sub>4</sub>]<sup>-</sup> | 89.6 | 99.2 | 浅黄色 | 无味 |
由表2可知,该离子液体催化体系引入不同的阴离子会对产品收率和纯度产生不同的影响,当阴离子为乙酸根时,其反应活性最佳,即实施例2的效果最佳。
实施例6
催化剂F制备方法的步骤与实施例2相同,只是将中间体Ⅰ与氢氧化钠的摩尔比更改为1:0.5。
实施例7
催化剂G制备方法的步骤与实施例2相同,只是将中间体Ⅰ与氢氧化钠的摩尔比更改为1:1.5。
实施例8
催化剂H制备方法的步骤与实施例2相同,只是将中间体Ⅰ与氢氧化钠的摩尔比更改为1:2。
将实施例6-8(改变中间体Ⅰ与氢氧化钠的摩尔比)制得的催化剂[MIM-Li]+[CH3COO]-分别在同样条件下催化丙酮与2-乙基己基缩水甘油醚合成乙基己基甘油,结果见表3。
表3 实施例6-8的催化效果评价
实施例 | 摩尔配比 | 收率(%) | 纯度(%) | 颜色 | 气味 |
实施例2 | 1:1 | 92.7 | 99.4 | 无色 | 无味 |
实施例6 | 1:0.5 | 91.8 | 99.2 | 无色 | 无味 |
实施例7 | 1:1.5 | 92.9 | 99.5 | 无色 | 无味 |
实施例8 | 1:2 | 92.8 | 99.4 | 无色 | 无味 |
由表3可知,随着含钠化合物加入量的逐渐增加,其反应活性逐渐增加,当中间体Ⅰ和氢氧化钠的摩尔比为1:1.5时,其收率、纯度均趋于稳定,因此中间体Ⅰ与氢氧化钠最佳的摩尔配比为1:1.5。
通过传统催化剂三氟化硼和实施例2[MIM-Na]+[CH3COO]-作为催化剂催化合成的乙基己基甘油产品对大肠埃希氏菌和金黄色葡萄球菌等人体常见致病微生物进行抑菌效果测定,实验结果见表4。
表4 实施例2与传统催化剂合成产品的抑菌效果评价
由表4可知,同样条件下,与传统的三氟化硼催化合成的乙基己基甘油产品相比,[MIM-Na]+[CH3COO]-作为催化剂催化合成的乙基己基甘油产品对人体常见病菌的最小抑菌浓度更低,这说明催化剂[MIM-Na]+[CH3COO]-对产品的抑菌性能有优异。
综上所述,金属羧酸基离子液体在催化合成乙基己基甘油产品的过程中表现出更优的催化效果和抑菌作用,当[MIM-Na]+[CH3COO]-的中间体Ⅰ与氢氧化钠为最佳摩尔配比1:1.5时,催化效果最佳,乙基己基甘油产品收率高达92.9%,纯度高达99.5%,且抗菌实验测试结果证明该催化剂合成的乙基己基甘油产品具有更好的抗菌性能。
Claims (6)
2.根据权利要求1所述的一种金属羧酸基离子液体催化剂,其特征在于:M的原料源于氢氧化钠、氢氧化钾或者氢氧化锂。
3.根据权利要求1所述的一种金属羧酸基离子液体催化剂,其特征在于:阴离子A-的原料源于甲酸、醋酸、磷酸或者钼酸。
4.一种如权利要求1所述的一种金属羧酸基离子液体催化剂的制备方法,其特征在于:步骤为:
(1)首先向反应器中加入烷基咪唑原料,然后加入等摩尔的含羧酸基团的卤代烷烃原料,再加入乙醇溶剂,其用量与上述两种反应原料总体积的比例为3-5:1,60-80℃氮气保护下冷凝回流磁力搅拌反应10-16h,反应结束后得到液体产物,将液体产物50-70℃真空旋蒸除去溶剂,然后加入与反应原料总体积比为1-3:1的乙酸乙酯洗涤去除未反应原料,并于50-70℃条件下再次旋蒸,最后将产物于60-70℃条件下真空干燥16-24h,得中间体Ⅰ淡黄色液体;
(2)将摩尔比1:0.5-2的中间体Ⅰ与含钾、钠或者锂的氢氧化物加入反应器,再加入蒸馏水,其用量与上述反应原料总体积比为2-4:1,并在30-45℃回流搅拌4-6h,70-90℃真空旋蒸除去水溶剂,然后再加入与反应原料总体积比为1-2:1的甲醇洗涤并真空旋蒸,70-90℃真空干燥16-24h得中间体Ⅱ;
(3)将等摩尔量的中间体Ⅱ与醋酸钠加入反应器,再加入乙醇溶剂,其用量与上述反应原料总体积比为2-4:1,并在30-45℃回流搅拌4-8h,反应结束后将体系中的固体颗粒过滤掉,滤液于50-70℃条件下真空旋蒸除去乙醇溶剂,然后再加入与反应原料总体积比为1-2:1的乙醇洗涤并在同样条件下真空旋蒸,得粗产物于60-70℃条件下真空干燥16-24h,制得白色膏状的金属羧酸基离子液体催化剂。
5.根据权利要求4所述的一种金属羧酸基离子液体催化剂的制备方法,其特征在于:步骤(2)中,含钠的氢氧化物为氢氧化钠,中间体Ⅰ与氢氧化钠的摩尔配比为1:1.5。
6.一种如权利要求1所述的金属羧酸基离子液体催化剂在合成乙基己基甘油中的应用。
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