CN113600234A - Oleophylic and hydrophobic solid base catalyst for organic condensation reaction - Google Patents
Oleophylic and hydrophobic solid base catalyst for organic condensation reaction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 35
- 238000006482 condensation reaction Methods 0.000 title claims abstract description 32
- 239000007787 solid Substances 0.000 title claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 16
- -1 ketone aldehyde Chemical class 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 150000002576 ketones Chemical class 0.000 claims abstract description 12
- 125000000962 organic group Chemical group 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 239000003463 adsorbent Substances 0.000 claims abstract description 3
- 239000004005 microsphere Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 150000001343 alkyl silanes Chemical class 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 239000007859 condensation product Substances 0.000 claims description 8
- 239000004064 cosurfactant Substances 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004530 micro-emulsion Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical group CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- ULRCHFVDUCOKTE-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCN ULRCHFVDUCOKTE-UHFFFAOYSA-N 0.000 claims description 2
- TVTRDGVFIXILMY-UHFFFAOYSA-N 4-triethoxysilylaniline Chemical compound CCO[Si](OCC)(OCC)C1=CC=C(N)C=C1 TVTRDGVFIXILMY-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000000593 microemulsion method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001282 organosilanes Chemical group 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001241 acetals Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HEVMDQBCAHEHDY-UHFFFAOYSA-N (Dimethoxymethyl)benzene Chemical compound COC(OC)C1=CC=CC=C1 HEVMDQBCAHEHDY-UHFFFAOYSA-N 0.000 description 1
- XPIJMQVLTXAGME-UHFFFAOYSA-N 1,1-dimethoxycyclohexane Chemical compound COC1(OC)CCCCC1 XPIJMQVLTXAGME-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an oleophylic and hydrophobic solid base catalyst for organic condensation reaction, wherein the adsorbent is a catalyst applied to the condensation reaction of ketol, ketoaldehyde or aldol, the catalyst is an oleophylic and hydrophobic silica nano composite material modified by double organic groups, and the composite material is prepared by SiO2The microsphere is used as a substrate, and an alkylamino active group and a hydrophobic organic alkyl group are connected on the surface of the substrate. The invention designs and synthesizes an oleophylic and hydrophobic solid base catalyst which takes an alkylamino active group as a catalytic active center and takes a hydrophobic organic alkyl group as an oleophylic modification group aiming at the characteristics of ketone alcohol, ketone aldehyde or aldol condensation reaction.
Description
Technical Field
The invention belongs to the technical field of catalytic application of solid alkaline nano materials, and particularly relates to an oleophylic and hydrophobic solid base catalyst for organic condensation reaction, which is an oleophylic and hydrophobic silica nano composite material modified by double organic groups, is applied to ketone alcohol, ketone aldehyde or aldol condensation reaction, obtains the oleophylic and hydrophobic base catalyst by taking an introduced alkylamino active group as a catalytic active center and taking a hydrophobic organic alkyl group as an oleophylic modification group, further promotes the adsorption of substrate molecules and the desorption of the product molecules in the condensation reaction, and obtains high substrate conversion rate and condensation product selectivity.
Background
Acetals are a generic name for a class of organic compounds, and are products of condensation of one molecule of aldehyde with two molecules of alcohol, such as acetaldehyde diethyl acetal or benzaldehyde dimethyl acetal. Acetals generally have a pleasant fragrance. Similar to acetals, ketals are the products of condensation of one molecule of ketone with two molecules of alcohol, such as acetonitril or cyclohexanone-dimethyl acetal. In addition, aldehydes or ketones having an alpha hydrogen atom can form enolic anions under certain conditions, which then undergo addition reactions with another molecule of carbonyl compound and form beta-hydroxycarbonyl compounds, a type of reaction known as aldol condensation. The three types of reactions have common characteristics: (1) all belong to condensation reaction; (2) the reactant is organic matter; (3) the product is generated with water; (4) an acid or base is generally used as a catalyst. The three reactions are widely applied in the fields of organic synthesis, medicine and fine chemical industry. In the traditional catalytic process, inorganic acid or alkali is used as a catalyst, and the use of homogeneous inorganic acid or alkali causes the increase of separation cost and the increase of environmental protection pressure. The development of heterogeneous catalysts is considered to be an important way for solving the environmental protection pressure and realizing green production in the process. Especially, the continuous emergence of solid acid and alkali in recent years provides possibility for realizing a heterogeneous catalytic process. However, the existing catalyst has the problems of competitive adsorption caused by low acid-base amount and strong surface polarity, and the like, so that the catalytic activity needs to be improved.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an oleophylic and hydrophobic solid base catalyst for organic condensation reaction aiming at the defects of the prior art, wherein the catalyst has an alkaline center and simultaneously shows oleophylic and hydrophobic characteristics, and is beneficial to adsorption conversion of organic molecules of a substrate and desorption of the product in the condensation reaction when being applied to the condensation reaction of ketol, ketoaldehyde or aldol, and high substrate conversion rate and condensation product selectivity are obtained at the same time.
The technical scheme adopted by the invention for solving the technical problems is as follows: an oleophylic and hydrophobic solid base catalyst for organic condensation reaction features that its adsorbent is the catalyst for ketone alcohol, ketone aldehyde or aldol condensation reaction, and said catalyst is the oleophylic and hydrophobic nano-class silica composite modified by dual organic radicals and prepared from SiO2The microsphere is used as a substrate, and an alkylamino active group and a hydrophobic organic alkyl group are connected on the surface of the substrate.
Preferably, the alkylamino active group is an alkylamino group NH2L, the hydrophobic organic alkyl group is R, and the composite material adopts a general formula m (NH)2L)-SiO2- (R) n represents, wherein:
alkylamino radical NH2L is selected from NH2(C3H6)-(NH2Pr)、NH2-(CH2)2-NH-(CH2)3-(NH2Et) and 4-NH2One of Ph;
the organic alkyl group R is selected from one of methyl, ethyl, propyl, amyl, phenyl, trifluoropropyl, pentafluorophenyl and perfluorodecyl;
m and n are independent numbers, m ranges from 1 to 60, n ranges from 10 to 59, and m + n is less than or equal to 70.
Preferably, the alkylamino group NH in the composite material2L accounts for 5-80% of the total organic groups in mol percent, organic alkyl groups R accounts for 0.1-99% of the total organic groups in mol percent, and the total organic groups are alkylamino groups NH2The sum of L and an organic alkyl group R, wherein the total organic group accounts for 1-60% of the composite material by mass percent.
Preferably, the alkylamino group NH in the composite material2L accounts for 10-50% of the total organic groups in mole percent.
Preferably, the composite material is prepared by a reverse microemulsion method, and the preparation method comprises the following steps:
(1) mixing a surfactant, an organic phase and a cosurfactant to prepare an inverse microemulsion A; mixing ammonia water with the mass concentration of 25-28% and deionized water to prepare a solution B;
(2) mixing low-carbon alcohol orthosilicate, alkylaminosilane and alkylsilane serving as a mixed silicon source to prepare a solution C;
(3) mixing the inverse microemulsion A and the solution B to obtain a solution D; dropwise adding the solution C into the solution D under the stirring condition, and aging for 2-48h to obtain a solution E, wherein the solution E comprises the following components in parts by mass: 4-8 parts of surfactant, 1-4 parts of deionized water, 1-2 parts of ammonia water, 5-9 parts of organic phase, 2-6 parts of cosurfactant, (1-m/100-n/100) parts of low-carbon alcohol orthosilicate ester, m/100 parts of alkylaminosilane and n/100 parts of alkylsilane;
wherein m and n are independent numbers, m ranges from 1 to 60, n ranges from 10 to 59, and m + n is less than or equal to 70; m is the mole percentage of the alkylamino silane in the total silane, n is the mole percentage of the alkyl silane in the total silane, and the total silane is the mixture of the lower alcohol orthosilicate, the alkylamino silane and the alkyl silane in the step (2);
(4) adding acetone or ethanol with the volume 1-3 times that of the cosurfactant in the step (1) into the solution E for demulsification, and centrifuging to collect solids; washing the solid with hot ethanol for 2-6 times, and drying at 80-150 deg.C to obtain uniform granular nanometer material, i.e. oleophylic and hydrophobic solid base catalyst for organic condensation reaction.
Preferably, the lower alcohol ester of ortho-silicic acid is methyl orthosilicate or ethyl orthosilicate; the alkylaminosilane is one of gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane and 4-aminophenyltriethoxysilane; the alkyl silane is organosilane containing one of the following groups: one of methyl (Me), ethyl (Et), propyl (Pr), pentyl (Pe), phenyl (Ph), trifluoropropyl (Pf), pentafluorophenyl (Fp), and perfluorodecyl (FF).
Preferably, the surfactant is an anionic surfactant, a long-chain nonionic surfactant or a cationic surfactant, the anionic surfactant is linear alkyl benzene sodium sulfonate or alpha-alkenyl sodium sulfonate, the long-chain nonionic surfactant is an organic primary amine, an Np series surfactant or a Tween series surfactant, and the cationic surfactant is hexadecyl trimethyl ammonium bromide; the organic phase is cyclohexane, normal hexane or toluene; the cosurfactant is n-hexanol, n-butanol or n-octanol.
Preferably, the substrate molecules of the condensation reaction are ketone and alcohol, ketone and aldehyde or aldehyde and alcohol, and the condensation products are corresponding ketal, acetal and aldol condensation products.
Preferably, the reaction temperature of the condensation reaction is 0-150 ℃, the reaction time is 30-480 minutes, the substrate conversion rate is 50-99%, and the selectivity of the condensation product is more than 90%. Excellent catalytic performance can be obtained under the milder conditions.
Preferably, the condensation reaction is carried out at a temperature of 20 to 120 ℃ for 60 to 360 minutes.
Compared with the prior art, the invention has the following advantages: the invention designs and synthesizes an oleophylic and hydrophobic solid base catalyst which takes an alkylamino active group as a catalytic active center and takes a hydrophobic organic alkyl group as an oleophylic modification group aiming at the characteristics of ketone alcohol, ketone aldehyde or aldol condensation reaction.
Detailed Description
The present invention will be described in further detail with reference to examples.
The oleophilic and hydrophobic solid base catalyst for organic condensation reaction of example 1,
example 1: material A (2 NH)2-SiO2Preparation of-Pr 10)
Mixing 20g of Np-10, 30g of cyclohexane and 5g of n-octanol to prepare a reverse microemulsion A; adding 0.5g of ammonia water into 3g of deionized water to obtain a solution B; mixing 7.32g of methyl orthosilicate, 0.18g of gamma-aminopropyltriethoxysilane and 0.85g of propyltrimethoxysilane to obtain a solution C; pouring the solution B into the inverse microemulsion A to obtain a solution D, adding the solution C into the solution D under vigorous stirring, and aging for 8 hours to obtain a solution E; then, adding 10mL of acetone into the solution E, stirring for 30min, and centrifuging to obtain a light blue solid; adding 30mL of ethanol into the solid, heating and stirring for 10min, and centrifuging; repeating the steps for multiple times until the surfactant is completely removed; drying at 80 ℃ to obtain a silicon dioxide nano composite material A: 2NH2-SiO2-Pr10。
Example 2-example 8: preparation of Material B to Material H
Materials B to H were prepared according to the method of preparation of material A in example 1, with the difference that the type or ratio of alkylaminosilane and alkylsilane used was different, as shown in Table 1, and the general formula of the materials prepared is also shown in Table 1.
TABLE 1
2NH prepared as in example 12-SiO2the-Pr 10 silicon dioxide nano composite material is taken as an example, and is used as a solid base catalyst for catalyzing ketone alcohol condensation reaction.
Take 0.1g 2NH2-SiO2The catalyst-Pr 10 was added to the reactor, and 5.8g of acetone and 6.4g of methanol were added thereto. Starting a stirring device, reacting at the temperature of 25 ℃, and stopping the reaction after 120 minutes; and (3) taking out part of reactants after cooling, carrying out quantitative analysis on the acetone and the methanol and the product acetone formal by adopting a gas chromatograph internal standard method, and calculating the conversion rate and the selectivity according to the change of the reactants and the product before and after the reaction. The reaction results are shown in Table 2.
Materials B to H are respectively used as catalysts and applied to organic condensation reaction, the activity evaluation method of the catalysts is the same as that of the embodiment, internal standard gas chromatography is adopted for analysis, and specific substrate types, reaction conditions and reaction results are shown in Table 2.
TABLE 2
Claims (10)
1. The oleophylic and hydrophobic solid base catalyst for organic condensation reaction features that the adsorbent is catalyst for ketone alcohol, ketone aldehyde or aldol condensation reaction, the catalyst is oleophylic and hydrophobic silica nanometer composite material modified with double organic radicals and the composite material is SiO2The microsphere is used as a substrate, and an alkylamino active group and a hydrophobic organic alkyl group are connected on the surface of the substrate.
2. The lipophilic and hydrophobic solid base catalyst for organic condensation reaction as claimed in claim 1, wherein the alkylamino active group is alkylamino NH2L, the hydrophobic organic alkyl group is R, and the composite material adopts a general formula m (NH)2L)-SiO2- (R) n represents, wherein:
alkylamino radical NH2L is selected from NH2(C3H6)-(NH2Pr)、NH2-(CH2)2-NH-(CH2)3-(NH2Et) and 4-NH2One of Ph;
the organic alkyl group R is selected from one of methyl, ethyl, propyl, amyl, phenyl, trifluoropropyl, pentafluorophenyl and perfluorodecyl;
m and n are independent numbers, m ranges from 1 to 60, n ranges from 10 to 59, and m + n is less than or equal to 70.
3. According to the rightThe lipophilic and hydrophobic solid base catalyst for organic condensation reaction of claim 2, wherein the alkylamino group NH in the composite material2L accounts for 5-80% of the total organic groups in mol percent, organic alkyl groups R accounts for 0.1-99% of the total organic groups in mol percent, and the total organic groups are alkylamino groups NH2The sum of L and an organic alkyl group R, wherein the total organic group accounts for 1-60% of the composite material by mass percent.
4. The lipophilic and hydrophobic solid base catalyst for organic condensation reaction as claimed in claim 3, wherein the alkylamino group NH in the composite material2L accounts for 10-50% of the total organic groups in mole percent.
5. The oleophilic and hydrophobic solid base catalyst for organic condensation reaction as claimed in claim 2, wherein the composite material is prepared by reverse microemulsion method, which comprises the following steps:
(1) mixing a surfactant, an organic phase and a cosurfactant to prepare an inverse microemulsion A; mixing ammonia water with the mass concentration of 25-28% and deionized water to prepare a solution B;
(2) mixing low-carbon alcohol orthosilicate, alkylaminosilane and alkylsilane serving as a mixed silicon source to prepare a solution C;
(3) mixing the inverse microemulsion A and the solution B to obtain a solution D; dropwise adding the solution C into the solution D under the stirring condition, and aging for 2-48h to obtain a solution E, wherein the solution E comprises the following components in parts by mass: 4-8 parts of surfactant, 1-4 parts of deionized water, 1-2 parts of ammonia water, 5-9 parts of organic phase, 2-6 parts of cosurfactant, (1-m/100-n/100) parts of low-carbon alcohol orthosilicate ester, m/100 parts of alkylaminosilane and n/100 parts of alkylsilane;
wherein m and n are independent numbers, m ranges from 1 to 60, n ranges from 10 to 59, and m + n is less than or equal to 70; m is the mole percentage of the alkylamino silane in the total silane, n is the mole percentage of the alkyl silane in the total silane, and the total silane is the mixture of the lower alcohol orthosilicate, the alkylamino silane and the alkyl silane in the step (2);
(4) adding acetone or ethanol with the volume 1-3 times that of the cosurfactant in the step (1) into the solution E for demulsification, and centrifuging to collect solids; washing the solid with hot ethanol for 2-6 times, and drying at 80-150 deg.C to obtain uniform granular nanometer material, i.e. oleophylic and hydrophobic solid base catalyst for organic condensation reaction.
6. A lipophilic hydrophobic type solid base catalyst for organic condensation reaction according to claim 5, characterized in that the lower alcohol ester of ortho-silicic acid is methyl orthosilicate or ethyl orthosilicate; the alkylaminosilane is one of gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane and 4-aminophenyltriethoxysilane; the alkyl silane is organosilane containing one of the following groups: one of methyl, ethyl, propyl, pentyl, phenyl, trifluoropropyl, pentafluorophenyl and perfluorodecyl.
7. The lipophilic and hydrophobic solid base catalyst for organic condensation reaction of claim 5, wherein the surfactant is anionic surfactant, long-chain nonionic surfactant or cationic surfactant, the anionic surfactant is sodium linear alkylbenzene sulfonate or sodium alpha-olefin sulfonate, the long-chain nonionic surfactant is organic primary amine, Np series surfactant or Tween series surfactant, and the cationic surfactant is hexadecyl trimethyl ammonium bromide; the organic phase is cyclohexane, normal hexane or toluene; the cosurfactant is n-hexanol, n-butanol or n-octanol.
8. The lipophilic and hydrophobic solid base catalyst for organic condensation reaction of claim 1, wherein the substrate molecules of the condensation reaction are ketone and alcohol, ketone and aldehyde or aldehyde and alcohol, and the condensation products are corresponding ketal, acetal and aldol condensation products.
9. The lipophilic hydrophobic solid base catalyst for organic condensation reaction as claimed in claim 8, wherein the reaction temperature of condensation reaction is 0-150 ℃, the reaction time is 30-480 minutes, the substrate conversion rate is 50-99%, and the selectivity of condensation product is more than 90%.
10. The lipophilic and hydrophobic solid base catalyst for organic condensation reaction as claimed in claim 9, wherein the condensation reaction is carried out at 20-120 deg.C for 60-360 min.
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