Alkyl-substituted 1, 4, 7-triazacyclononane coordination metal peroxide catalyst, composite catalyst, preparation method and application

Abstract

The invention discloses an alkyl-substituted 1, 4, 7-triazacyclononane coordinated metal peroxide catalyst, a compound catalyst, a preparation method and application, the general formula of the alkyl-substituted 1, 4, 7-triazacyclononane coordinated metal peroxide catalyst is as shown in formula (I), the compound catalyst comprises alkyl-substituted 1, 4, 7-triazacyclononane coordinated metal peroxide catalyst, and the compound catalyst comprises alkyl-substituted 1, 4, 7-triazacyclononane coordinated metal peroxide catalyst and alkyl-substituted 1, 4, 7-triazacyclononane coordinated metal peroxide catalyst. The catalyst comprises a 1, 3, 5, 7-triazacyclononane coordination metal peroxide catalyst, an auxiliary catalyst, a regulator, a protective agent and a solvent. The alkyl-substituted 1, 4, 7-triazacyclononane coordination metal peroxide catalyst or the compound catalyst has the characteristics of high activity, high selectivity, low cost and recyclability in the application of air oxidation of fatty alcohol to preparation of fatty aldehyde, is particularly suitable for the oxidation reaction of C4-C18 fatty alcohol, and has excellent performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic catalysis, and in particular relates to an alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, a composite catalyst, a preparation method and applications. Background Art

[0002] Fatty aldehydes are aldehyde compounds in which an aldehyde group is connected to an aliphatic hydrocarbon group (or hydrogen atom). The general formula is R-CHO. Low-level fatty aldehydes have a pungent odor. 12 Saturated aliphatic aldehydes possess a pleasant aroma in dilute conditions and often serve as top notes in fragrance formulations. Aldehydes comprise up to 10% of all fragrance compounds, playing a crucial role in flavors and fragrances. Furthermore, aliphatic aldehydes are highly reactive and can undergo a variety of organic reactions, including carbonyl addition, alpha-hydrogen atom reactions, and oxidation reactions, making them important organic raw materials and intermediates.

[0003] Fatty aldehydes are generally produced through methods such as alcohol oxidation, olefin hydroformylation, aldol condensation, and acid or ester reduction. Simple, high-purity fatty aldehydes are currently primarily obtained by oxidation of the corresponding fatty alcohols. Hydroformylation often presents the problem of difficult isomer removal, while aldol condensation or acid / ester reduction methods typically require harsh conditions, expensive materials, and low selectivity, making them difficult to produce economically on a large scale. Fatty alcohol oxidation methods are further categorized as chemical oxidation and molecular oxygen oxidation. Oxygen, a cheap, readily available, clean, and atom-economic oxidant, offers significant advantages over other methods for producing fatty aldehydes by directly oxidizing fatty alcohols. The potassium chromate method for producing n-fatty aldehydes from n-fatty alcohols is a more commonly used method, but yields are relatively low, ranging from approximately 30% to 50%. This is because the resulting n-fatty aldehydes are susceptible to further oxidation, forming a large number of byproducts such as acid or vinegar.

[0004] Existing methods for preparing fatty aldehydes, such as those reported in Chemical Reagents, Vol. 16, No. 1, 1994, p. 62, report that adding a phase transfer catalyst, tetrabutylammonium bromide, to the potassium chromate oxidation of n-octanol to produce n-octanal increased the yield from 30-40% to 90%. While this method offers a high yield, it requires a relatively large amount of dichloromethane, intended to ensure that the generated n-octanal rapidly enters the organic phase and separates from the aqueous phase, preventing further oxidation.

[0005] U.S. Patent No. 2003 / 0105363A1 discloses a method for preparing n-octanal using a fluorosulfide via Corey-Kim oxidation. A fluorosulfide was added to a toluene solution of N-chlorosuccinimide at 0°C. The reaction mixture was cooled to -25°C, and a solution of octanol in toluene was added. After stirring at -25°C for 2 hours, the yield was 88%.

[0006] Adv. Synth. Catal. 2009, Vol. 351, pp. 2209-2216, reported an effective catalytic system consisting of a 2,2,6,6-tetramethylpiperidin-1-oxide (TEMPO)-functionalized imidazolium salt ([Imim-TEMPO]+X), a carboxylic acid-substituted imidazolium salt ([ImimCOOH]+X), and sodium nitrite. This system was used to oxidize n-heptanol to n-heptanal in a 12-hour reaction, achieving a 94% conversion and 76% yield. Similarly, sec-octanol was oxidized to sec-octanal in a 12-hour reaction, achieving an 81% conversion and 66% yield. However, the oxidation of hexadecanol to hexadecanal in a 12-hour reaction yielded only 45% conversion and 41% yield.

[0007] Chinese patent CN113582821B discloses a method for oxidizing 8-methyldecanol to 8-methyldecanal using sodium hypochlorite. This method uses 2,2,6,6-tetramethylpiperidinium oxide as a catalyst, tetrabutylammonium hydrogen sulfate as a pH adjuster, and 1.5 equivalents of sodium hypochlorite for oxidation, achieving a yield of 93%. Kao Corporation's patent EP0448740 reports a method for oxidizing 8-methyldecanol to 8-methyldecanal using pyridinium chlorochromate (PCC), achieving an 88% yield. Both methods offer good yields, but the equivalent amounts of sodium hypochlorite and pyridinium chlorochromate generate large amounts of waste, waste gas, and wastewater, posing significant environmental risks and high costs, making them unsuitable for long-term development.

[0008] Anhui Chemical Industry, 2015, 41(01):39-41, reports a method for selectively oxidizing undecanol using activated dimethyl sulfoxide. The method uses oxalyl chloride as an activator at a reaction temperature of -10°C for 30 minutes, achieving a conversion rate of 96.7% to undecanol. This method produces a high-quality, easily separable product with a high yield. However, the method requires the use of 40 times the amount of dichloromethane as a solvent, and the amounts of oxalyl chloride and DMSO are both 1.5-2 times that of the substrate, resulting in extremely high production costs and making it unsuitable for large-scale production.

[0009] The above-reported synthesis methods all have disadvantages in the preparation experiments of fatty aldehydes, such as lengthy reaction steps, complex operations, high raw material costs or post-processing costs, and are difficult to apply to industrial-scale production. Summary of the Invention

[0010] The present invention aims to provide an alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, a composite catalyst, a preparation method and an application thereof. The composite catalyst has the advantages of high activity, high selectivity and low cost in the reaction of oxidizing fatty alcohols to prepare fatty aldehydes.

[0011] In order to achieve the above object, a specific embodiment of the present invention provides the following technical solutions:

[0012] An alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, the general formula of which is shown in formula (I):

[0013]

[0014] (I)

[0015] Wherein, B is selected from any one of copper ion, sodium ion, iron ion, potassium ion, zinc ion, ammonium ion, dodecyldimethylbenzylammonium ion, tetrabutylphosphonium ion, tributylethylphosphonium ion, tributylhexylphosphonium ion, tetramethylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, and octyltributylphosphonium ion;

[0016] M is selected from any one of molybdenum, chromium, lanthanum, cerium, tungsten, scandium, titanium, zirconium, vanadium, nickel, chromium, cobalt, manganese, copper, potassium, sodium, iron, magnesium, and zinc;

[0017] R1 is selected from C1-C 15 alkyl;

[0018] R2 is selected from C1-C 15 alkyl;

[0019] x is selected from any integer between 1 and 18;

[0020] y is selected from any integer between 1-18.

[0021] Another specific embodiment of the present invention provides a technical solution as follows:

[0022] A method for preparing an alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst comprises the following steps:

[0023] Dissolving a metal compound in deionized water, adjusting the solution to be acidic, and then adding peroxide to obtain a metal peroxide solution;

[0024] The metal peroxide solution, alkyl-substituted 1,4,7-triazacyclononane and salt are mixed, filtered and dried to obtain the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst.

[0025] In one or more embodiments of the present invention, the pH value of the solution of the metal compound dissolved in deionized water is 4-6.

[0026] In one or more embodiments of the present invention, the metal compound is selected from any one of chromium chloride, lanthanum nitrate, lanthanum chloride, cerium sulfate, cerium nitrate, scandium chloride, scandium nitrate, titanium chloride, titanium sulfate, zirconium chloride, zirconium nitrate, manganese sulfate, potassium permanganate, copper sulfate, copper chloride, potassium chloride, potassium nitrate, ferric chloride, ferrous sulfate, magnesium chloride, magnesium sulfate, zinc chloride, zinc sulfate, sodium molybdate, sodium tungstate, molybdenum acetylacetonate, tungsten hexacarbonyl, cobalt sulfate, nickel nitrate, nickel acetate and sodium metavanadate; and / or,

[0027] The peroxide is selected from any one of hydrogen peroxide and sodium percarbonate; and / or,

[0028] The alkyl-substituted 1,4,7-triazacyclononane is selected from any one of 1,4,7-trimethyl-1,4,7-triazacyclononane, 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane, 1,4-diethyl-7-methyl-1,4,7-triazacyclononane, and 1,4-dimethyl-7-isopropyl-1,4,7-triazacyclononane; and / or

[0029] The salt is selected from any one of octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, manganese bromide, ferric bromide, copper bromide, tetrabutylphosphonium bromide, dodecyltrimethylammonium chloride, tributylethylphosphonium bromide, octyltributylphosphonium bromide, tributylhexylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, and benzyltriethylammonium chloride.

[0030] Another specific embodiment of the present invention provides a technical solution as follows:

[0031] A composite catalyst comprises the above-mentioned alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst.

[0032] In one or more embodiments of the present invention, a cocatalyst is further included, and the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the cocatalyst is 100:(1-200);

[0033] The cocatalyst is selected from one or more of potassium salts, sodium salts, iron salts, magnesium salts, zinc salts, nickel salts, chromium salts, cobalt salts, manganese salts, copper salts, calcium salts, molybdenum salts, lanthanum salts, cerium salts, tungsten salts, scandium salts, titanium salts, zirconium salts, vanadium salts, potassium oxides, sodium oxides, iron oxides, magnesium oxides, zinc oxides, nickel oxides, chromium oxides, cobalt oxides, manganese oxides, copper oxides, calcium oxides, molybdenum oxides, lanthanum oxides, cerium oxides, tungsten oxides, scandium oxides, titanium oxides, zirconium oxides, and vanadium oxides.

[0034] In one or more embodiments of the present invention, a regulator is further included, and the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the regulator is 100: (1-200);

[0035] The regulator is selected from one or more of phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdicvanadic acid.

[0036] In one or more embodiments of the present invention, a protective agent is further included, and the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the protective agent is 100: (10-200);

[0037] The protective agent is selected from one or more of sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide.

[0038] In one or more embodiments of the present invention, a solvent is further included, and the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the solvent is 100: (10-1000);

[0039] The solvent is selected from one or more of dichloromethane, 1,4-dioxane, dibutyl ether, methyl tert-butyl ether, acetonitrile, methanol, ethanol, formic acid, dichloroethane, propionic acid, ethyl acetate and dichloropropyl acetate.

[0040] Another specific embodiment of the present invention provides a technical solution as follows:

[0041] A method for preparing a composite catalyst comprises the following steps:

[0042] The solvent and the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 1 are mixed, heated to 35° C.-80° C., and stirred for 40 min-120 min.

[0043] In one or more embodiments of the present invention, the following steps are further included:

[0044] Mix the protective agent and the solvent to obtain a solution;

[0045] Add alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the solution, heat to 35°C-80°C, and stir for 40min-120min;

[0046] Then add the co-catalyst and ultrasonicate at 35-80°C for 40-60 minutes;

[0047] Then add the regulator and stir at 35°C-80°C for 40min-60min to obtain a composite catalyst.

[0048] Another specific embodiment of the present invention provides a technical solution as follows:

[0049] A use of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst or the composite catalyst in the oxidation preparation of fatty aldehydes using fatty alcohols as raw materials.

[0050] In one or more embodiments of the present invention, the general formula of the fatty alcohol is as shown in formula (II):

[0051]

[0052] (II)

[0053] Wherein, m is selected from any integer between 1 and 20;

[0054] R3 is selected from any one of hydrogen, alkyl, alkoxy, ester, hydroxy, amine, halogen or aromatic groups, wherein the alkyl group is a C n H 2n+1 The general structural formula is a straight-chain or branched aliphatic hydrocarbon group, wherein n is any integer between 1 and 8;

[0055] R4 is selected from any one of hydrogen, alkyl, alkoxy, ester, hydroxy, amine, halogen or aromatic groups, wherein the alkyl group is a C n H 2n+1 The general structural formula is a straight-chain or branched aliphatic hydrocarbon group, wherein n is any integer between 1 and 8.

[0056] Compared with the existing technology, the present invention activates the peroxy ligand to generate active oxygen through the change of the valence state of the metal center M, regulates the electron cloud, adapts to the steric hindrance, activates the substrate and promotes the reaction, and at the same time, the B ion and R group ensure the charge balance and system polarity, so that the prepared alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst can effectively catalyze the oxidation of fatty alcohols to generate fatty aldehydes.

[0057] In addition, the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst is used in combination with a cocatalyst, a protective agent, and a regulator. Through the synergistic effect between the components, the prepared composite catalyst has the characteristics of high activity, high selectivity and recyclability when used in the oxidation reaction of fatty alcohols. Moreover, the composite catalyst is particularly suitable for C4-C 18 Oxidation reaction of fatty alcohols, excellent performance. DETAILED DESCRIPTION

[0058] To help those skilled in the art better understand the technical solutions of the present disclosure, the following clearly and completely describes the technical solutions in the embodiments of the present disclosure. Obviously, the described embodiments are only a part of the embodiments of the present disclosure, not all of them. Based on the embodiments of the present disclosure, all other embodiments obtained by those skilled in the art without creative work should fall within the scope of protection of the present disclosure.

[0059] A specific embodiment of the present invention provides an alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, the general formula of which is shown in formula (I): ;

[0060] Wherein, B is selected from any one of copper ion, sodium ion, iron ion, potassium ion, zinc ion, ammonium ion, dodecyldimethylbenzylammonium ion, tetrabutylphosphonium ion, tributylethylphosphonium ion, tributylhexylphosphonium ion, tetramethylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, and octyltributylphosphonium ion; M is selected from any one of molybdenum, chromium, lanthanum, cerium, tungsten, scandium, titanium, zirconium, vanadium, nickel, chromium, cobalt, manganese, copper, potassium, sodium, iron, magnesium, and zinc; R1 is selected from any one of C1-C 15 Alkyl; R2 is selected from C1-C 15 alkyl; x is selected from any integer between 1-18; y is selected from any integer between 1-18.

[0061] Preferably, B is selected from any one of tetrabutylammonium ion, benzyltrimethylammonium ion, iron ion, potassium ion, zinc ion, ammonium ion, and tetrabutylphosphonium ion.

[0062] More preferably, B is selected from any one of butylethylphosphonium ion, sodium ion, magnesium ion, potassium ion, and zinc ion, R1 is selected from methyl, ethyl, and isopropyl, and R2 is selected from methyl, ethyl, and isopropyl, x is 1, and y is 1 or 2.

[0063] Another specific embodiment of the present invention provides a method for preparing an alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, comprising steps 1-2.

[0064] Step 1: dissolving a metal compound in deionized water, adjusting the solution to be acidic, and then adding peroxide to obtain a metal peroxide solution.

[0065] Specifically, the pH of a solution of a metal compound dissolved in deionized water is adjusted to 4-6. The metal compound is selected from any one of chromium chloride, lanthanum nitrate, lanthanum chloride, cerium sulfate, cerium nitrate, scandium chloride, scandium nitrate, titanium chloride, titanium sulfate, zirconium chloride, zirconium nitrate, manganese sulfate, potassium permanganate, copper sulfate, copper chloride, potassium chloride, potassium nitrate, ferric chloride, ferrous sulfate, magnesium chloride, magnesium sulfate, zinc chloride, zinc sulfate, sodium molybdate, sodium tungstate, molybdenum acetylacetonate, tungsten hexacarbonyl, cobalt sulfate, nickel nitrate, nickel acetate, and sodium metavanadate. The peroxide is selected from any one of hydrogen peroxide and sodium percarbonate. Hydrochloric acid or sulfuric acid is used to adjust the pH of the solution.

[0066] Step 2: Mix the metal peroxide solution, the alkyl-substituted 1,4,7-triazacyclononane and the salt, filter and dry to obtain the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst.

[0067] Specifically, the metal peroxide solution is first heated to 50° C.-90° C., and then mixed with the alkyl-substituted 1,4,7-triazacyclononane and the salt.

[0068] The present invention provides M with metal salt n+ , active M is generated by pH control and peroxide treatment n+ -peroxide species, and then the chelate coordination of the ligand alkyl-substituted 1,4,7-triazacyclononane is used to form a stable skeleton, and finally a metal peroxide complex catalyst with high yield is obtained.

[0069] Metal salts are dissolved in water to form M n+ The pH of the solution is adjusted to a weak acidic state in order to change the M n+ The stable mononuclear form under weak acidic conditions is easier to coordinate with subsequent ligands (such as hydrogen peroxide and triazacyclic ligands). In combination, the peroxide bond (-OO-) in the peroxide compound is broken to form a peroxide anion (O2 2- ), and M n+ Coordinate to form peroxy M n+ Intermediate [M n+ (O2)] + By adding water to control M n+ -Concentration of peroxygen species.

[0070] When heated to 50℃-90℃, the M in the solution n+ -peroxy species (such as [M (O2)] + ) coordinates with alkyl-substituted 1,4,7-triazacyclononane: M n+As the central ion, it accepts the lone pair electrons of the three nitrogen atoms in the ligand L while retaining the coordination of the peroxide ligand (-OO-), forming a stable five- or six-coordinate complex (i.e., the core skeleton of the target catalyst). The complex can be simplified as: [M(O2) L] + .

[0071] Further, the alkyl-substituted 1,4,7-triazacyclononane is selected from any one of 1,4,7-trimethyl-1,4,7-triazacyclononane, 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane, 1,4-diethyl-7-methyl-1,4,7-triazacyclononane, and 1,4-dimethyl-7-isopropyl-1,4,7-triazacyclononane; the salt is selected from octadecyl trimethyl any one of octadecyltrimethylammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, manganese bromide, iron bromide, copper bromide, tetrabutylphosphonium bromide, dodecyltrimethylammonium chloride, tributylethylphosphonium bromide, octyltributylphosphonium bromide, tributylhexylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, and benzyltriethylammonium chloride.

[0072] Another specific embodiment of the present invention provides a composite catalyst, comprising the above-mentioned alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, cocatalyst, regulator, protective agent and solvent, wherein the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, cocatalyst, regulator, protective agent and solvent is 100: (1-200): (1-200): (10-200): (10-1000).

[0073] Specifically, the cocatalyst is selected from one or more of potassium salts, sodium salts, iron salts, magnesium salts, zinc salts, nickel salts, chromium salts, cobalt salts, manganese salts, copper salts, calcium salts, molybdenum salts, lanthanum salts, cerium salts, tungsten salts, scandium salts, titanium salts, zirconium salts, vanadium salts, potassium oxides, sodium oxides, iron oxides, magnesium oxides, zinc oxides, nickel oxides, chromium oxides, cobalt oxides, manganese oxides, copper oxides, calcium oxides, molybdenum oxides, lanthanum oxides, cerium oxides, tungsten oxides, scandium oxides, titanium oxides, zirconium oxides, and vanadium oxides.

[0074] Exemplarily, the cocatalyst can be selected from one or more of phosphomolybdic acid, sodium bromide, chromium trioxide, chromium chloride, potassium dichromate, calcium chloride, calcium hypochlorite, cerium nitrate, cerium sulfate, cerium acetate, manganese acetate, manganese nitrate, manganese sulfate, vanadium oxide, cobalt oxide, silver nitrate, zirconium oxide, zirconium acetate, ferric nitrate, ferric sulfate, ferric chloride, copper sulfate, copper acetate, copper nitrate, magnesium sulfate, magnesium acetate, zinc acetate, zinc sulfate, sodium molybdate, potassium acetate and potassium sulfate.

[0075] The regulator is selected from one or more of phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdovanadic acid; the protective agent is selected from one or more of sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide; and the solvent is selected from one or more of dichloromethane, 1,4-dioxane, dibutyl ether, methyl tert-butyl ether, acetonitrile, methanol, ethanol, formic acid, dichloroethane, propionic acid, ethyl acetate and dichloropropyl acetate.

[0076] The above-mentioned auxiliary catalysts, regulators, protective agents and solvents are selected and matched with an alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to prepare a composite catalyst, which can improve the selectivity and reaction activity of the fatty alcohol oxidation reaction.

[0077] Preferably, the protective agent is selected from one or more of ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide and N-hydroxyphthalimide; the solvent is selected from one or more of formic acid, ethylene dichloride and propionic acid; the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst is one or more of alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxides with chromium, molybdenum, vanadium, cobalt or nickel as the central metal; the cocatalyst is selected from one or more of manganese sulfate, cerium sulfate, cerium nitrate, copper nitrate, manganese acetate, silver nitrate, ferric nitrate, zirconium acetate and magnesium sulfate; and the regulator is selected from one or more of phosphomolybdic acid, phosphotungstic acid and silicotungstic acid.

[0078] Preferably, the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, cocatalyst, regulator, protective agent and solvent is 100:(1-50):(1-50):(10-100):(100-500), more preferably, the mass ratio is 100:(1-50):(1-50):(10-100):(120-500). The alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst is one of the alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxides with chromium, molybdenum, vanadium, cobalt, or zirconium as the central metal. The cocatalyst is selected from one or more of manganese acetate, zirconium acetate, magnesium acetate, and cerium acetate. The regulator is selected from one or more of phosphomolybdic acid, phosphotungstic acid, and silicotungstic acid. The protective agent is selected from one or more of ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, and N-hydroxyphthalimide. The solvent is selected from one or more of methanol, ethanol, and acetonitrile. The catalytic effect of the composite catalyst is further enhanced by optimizing the component ratio and type.

[0079] Another specific embodiment of the present invention provides a preparation method of a composite catalyst, comprising the following steps: mixing a protective agent and a solvent to obtain a solution; adding the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 1 to the solution, heating to 35°C-80°C, and stirring for 40min-120min; then adding a cocatalyst, ultrasonicating at 35°C-80°C for 40min-60min; then adding a regulator, stirring at 35°C-80°C for 40min-60min to obtain a composite catalyst.

[0080] Another specific embodiment of the present invention provides an application of the above-mentioned alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst or composite catalyst in the oxidation preparation of fatty aldehydes using fatty alcohols as raw materials.

[0081] Furthermore, the general formula of fatty alcohol is shown in formula (II): ;

[0082] wherein m is selected from any integer between 1 and 20; R3 is selected from any one of hydrogen, alkyl, alkoxy, ester, hydroxyl, amine, halogen or aromatic groups; alkyl is a C n H 2n+1 The general structure is a straight-chain or branched aliphatic hydrocarbon group, n is any integer between 1 and 8; R4 is selected from any one of hydrogen, alkyl, alkoxy, ester, hydroxyl, amine, halogen or aromatic groups, and the alkyl group is a C n H 2n+1 The general structural formula is a straight-chain or branched aliphatic hydrocarbon group, wherein n is any integer between 1 and 8.

[0083] Specifically, the alkyl group is a straight-chain or branched hydrocarbon group of any one of methyl, ethyl, propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-butyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0084] Furthermore, taking a composite catalyst as an example, a fatty alcohol and a reaction solvent are mixed, 0.05%-0.5% of the composite catalyst by weight of the fatty alcohol is added, air is introduced at a rate of 30 mL / min-100 mL / min, and the reaction is stirred at 25°C-70°C for 4-12 hours. The reaction solvent is ethylene dichloride. Preferably, the amount of the composite catalyst added is 0.5%-2% by weight of the fatty alcohol.

[0085] The present invention is further described in detail below with reference to specific embodiments.

[0086] Example 1

[0087] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0088] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 60 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0089] Step 2: Heat solution d to 80°C. Add 1,4,7-trimethyl-1,4,7-triazacyclononane (17.12 g, 0.10 mol) and tetrabutylammonium bromide (70.92 g, 0.22 mol) to solution d. Stir while heating for approximately 1.5 hours, then centrifuge for 15 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 71.23 g of a pale yellow solid. This yellow solid is the 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-001, with a catalyst yield of 90.13%. The NMR characterization data for 1,4,7-trimethyl-1,4,7-triazacyclononane are as follows:

[0090] 1HNMR (500MHz, Chloroform-d) δ2.51 (s, 1H).

[0091] Example 2

[0092] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0093] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 60 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0094] Step 2: Heat solution d to 50°C. Add 1,4,7-trimethyl-1,4,7-triazacyclononane (17.12 g, 0.10 mol) and phenyltrimethylammonium bromide (47.54 g, 0.22 mol) to solution d. Stir while heating for approximately 1.5 hours, then centrifuge for 15 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 68.14 g of a pale yellow solid. This yellow solid is the 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-002, with a catalyst yield of 88.16%. The NMR characterization data for 1,4,7-trimethyl-1,4,7-triazacyclononane are as follows:

[0095] 1HNMR (500MHz, Chloroform-d) δ2.51 (s, 1H).

[0096] Example 3

[0097] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0098] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute hydrochloric acid dropwise to Solution a until the pH reaches 5, obtaining Solution b. Continue stirring for approximately 3 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0099] Step 2: Heat solution d to 50°C. Add 1,4,7-trimethyl-1,4,7-triazacyclononane (37.66 g, 0.22 mol) and magnesium acetate (15.66 g, 0.22 mol) to solution d. Stir while heating for approximately 2 hours, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 64.52 g of a yellow solid. This yellow solid is the 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-003, with a catalyst yield of 90.61%. The NMR characterization data for 1,4,7-trimethyl-1,4,7-triazacyclononane are as follows:

[0100] 1HNMR (500MHz, Chloroform-d) δ2.51 (s, 1H).

[0101] Example 4

[0102] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0103] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute phosphoric acid dropwise to Solution a until the pH reaches 6, obtaining Solution b. Continue stirring for approximately 1.5 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0104] Step 2: Heat solution d to 80°C. Add 1,4,7-trimethyl-1,4,7-triazacyclononane (17.12 g, 0.10 mol) and ammonium acetate (8.41 g, 0.12 mol) to solution d. Stir while heating for approximately 2 hours, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 63.61 g of a yellow solid. This yellow solid is the 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-004, with a catalyst yield of 87.62%. The NMR characterization data for 1,4,7-trimethyl-1,4,7-triazacyclononane are as follows:

[0105] 1HNMR (500MHz, Chloroform-d) δ2.51 (s, 1H).

[0106] Example 5

[0107] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0108] Step 1: Add 300 mL of deionized water to solid cobalt acetylacetonate (25.91 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute hydrochloric acid dropwise to Solution a until the pH reaches 6, obtaining Solution b. Continue stirring for approximately 50 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0109] Step 2: Heat solution d to 80°C. Add 1,4,7-trimethyl-1,4,7-triazacyclononane (20.54 g, 0.12 mol) and benzyltriphenylphosphonium bromide (53.50 g, 0.12 mol) to solution d. Stir while heating for approximately 2 hours, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 61.52 g of a yellow solid. This yellow solid is the 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-005, with a catalyst yield of 89.16%. The NMR characterization data for 1,4,7-trimethyl-1,4,7-triazacyclononane are as follows:

[0110] 1HNMR (500MHz, Chloroform-d) δ2.51 (s, 1H).

[0111] Example 6

[0112] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0113] Step 1: Add 300 mL of deionized water to solid cobalt acetylacetonate (25.91 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 30 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total volume reaches 450 mL, obtaining Solution d.

[0114] Step 2: Heat solution d to 60°C. Add 1,4,7-trimethyl-1,4,7-triazacyclononane (20.54 g, 0.12 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d. Stir while heating for approximately 2 hours, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 62.13 g of a yellow solid. This yellow solid is the 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-006, with a catalyst yield of 87.99%. The NMR characterization data for 1,4,7-trimethyl-1,4,7-triazacyclononane are as follows:

[0115] 1HNMR (500MHz, Chloroform-d) δ2.51 (s, 1H).

[0116] Example 7

[0117] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0118] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 30 minutes, then slowly add 100 mL of 30% sodium peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0119] Step 2: Heat solution d to 50°C. Add 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane (20.37 g, 0.11 mol) and tetrabutylammonium bromide (70.92 g, 0.22 mol) to solution d. Stir while heating for approximately 1 hour, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to yield 56.1 g of a yellow solid, which is the 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-007. The catalyst yield reaches 88.15%. The NMR characterization data of 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane are as follows:

[0120] 1HNMR(500MHz,Chloroform-d)δ2.52–2.44(m,2H),1.04(t,J=7.0Hz,0H).

[0121] Example 8

[0122] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0123] Step 1: Add 300 mL of deionized water to solid cobalt sulfate (15.50 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH is 4-6, obtaining Solution b. Continue stirring for approximately 30 minutes, then slowly add 100 mL of 30% tert-butyl hydroperoxide solution to Solution b to obtain Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0124] Step 2: Heat solution d to 90°C. Add 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane (20.37 g, 0.11 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d. Stir while heating for approximately 2 hours, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 57.12 g of a purple-red solid. This purple-red solid is the 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-008. The catalyst yield of 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane reaches 86.12%. NMR characterization data are as follows:

[0125] 1HNMR(500MHz,Chloroform-d)δ2.52–2.44(m,2H),1.04(t,J=7.0Hz,0H).

[0126] Example 9

[0127] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0128] Step 1: Add 300 mL of deionized water to solid chromium nitrate nonahydrate (40.01 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 60 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0129] Step 2: Heat solution d to 60°C. Add 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane (20.37 g, 0.11 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d. Stir while heating for approximately 1 hour, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to yield 61.12 g of a purple-red solid. This purple-red solid is the 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-009, with a catalyst yield of 85.12%. The NMR characterization data for 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane are as follows:

[0130] 1HNMR(500MHz,Chloroform-d)δ2.52–2.44(m,2H),1.04(t,J=7.0Hz,0H).

[0131] Example 10

[0132] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0133] Step 1: Add 300 mL of deionized water to solid nickel sulfate (15.48 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 60 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0134] Step 2: Heat solution d to 60°C. Add 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane (20.37 g, 0.11 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d. Stir while heating for approximately 1 hour, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 51.46 g of a purple-red solid. This purple-red solid is the 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-010, with a catalyst yield of 80.15%. The NMR characterization data for 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane are as follows:

[0135] 1HNMR(500MHz,Chloroform-d)δ2.52–2.44(m,2H),1.04(t,J=7.0Hz,0H).

[0136] Example 11

[0137] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0138] Step 1: Add 300 mL of deionized water to solid nickel sulfate (15.48 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 30 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0139] Step 2: Heat solution d to 60°C. Add 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane (20.37 g, 0.11 mol) and tetrabutylammonium bromide (70.92 g, 0.22 mol) to solution d. Stir while heating for approximately 2 hours, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 57.15 g of a blue solid. This blue solid is the 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-011, with a catalyst yield of 89.14%. The NMR characterization data for 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane are as follows:

[0140] 1HNMR(500MHz,Chloroform-d)δ2.52–2.44(m,2H),1.04(t,J=7.0Hz,0H).

[0141] Example 12

[0142] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0143] Step 1: Add 300 mL of deionized water to solid sodium metavanadate (12.19 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 50 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0144] Step 2: Heat solution d to 60°C. Add 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane (20.37 g, 0.11 mol) and octadecyltrimethylammonium chloride (76.57 g, 0.22 mol) to solution d. Stir while heating for approximately 1 hour, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to yield 52.13 g of a white solid, which is the 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-012. The catalyst yield reaches 93.55%. The NMR characterization data of 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane are as follows:

[0145] 1HNMR(500MHz,Chloroform-d)δ2.52–2.44(m,2H),1.04(t,J=7.0Hz,0H).

[0146] Example 13

[0147] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0148] Step 1: Add 300 mL of deionized water to solid sodium metavanadate (12.19 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 60 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0149] Step 2: Heat solution d to 50°C. Add 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane (20.37 g, 0.11 mol) and tetrabutylammonium bromide (70.92 g, 0.22 mol) to solution d. Stir while heating for approximately 2 hours, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 49.15 g of a yellow solid. This yellow solid is the 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-013, with a catalyst yield of 94.16%. The NMR characterization data for 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane are as follows:

[0150] 1HNMR(500MHz,Chloroform-d)δ2.52–2.44(m,2H),1.04(t,J=7.0Hz,0H).

[0151] Example 14

[0152] The preparation method of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst in this embodiment comprises the following steps:

[0153] Step 1: Add 300 mL of deionized water to solid nickel sulfate (15.48 g, 0.1 mol) at room temperature. Once the solid is completely dissolved, obtain Solution a. Add dilute sulfuric acid dropwise to Solution a until the pH reaches 4, obtaining Solution b. Continue stirring for approximately 30 minutes, then slowly add 100 mL of 30% hydrogen peroxide solution to Solution b, obtaining Solution c. Add deionized water to Solution c until the total liquid volume reaches 450 mL, obtaining Solution d.

[0154] Step 2: Heat solution d to 55°C. Add 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane (20.37 g, 0.11 mol) and ammonium acetate (8.41 g, 0.12 mol) to solution d. Stir while heating for approximately 2 hours, then centrifuge for 20 minutes. Filter and dry the resulting solid in a vacuum oven to obtain 34.15 g of a yellow solid. This yellow solid is the 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-014, with a catalyst yield of 91.58%. The NMR characterization data for 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane are as follows:

[0155] 1HNMR(500MHz,Chloroform-d)δ2.52–2.44(m,2H),1.04(t,J=7.0Hz,0H).

[0156] Example 15

[0157] The preparation method of the composite catalyst in this embodiment is as follows:

[0158] Step (1): add 20.0 g of ethanol to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0159] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane coordinated metal peroxide catalyst YG-73-7-001 to the mixed solution of step (1), and heat with stirring at 70° C. for 30 min to obtain a mixture B;

[0160] Step (3): adding 0.5 g of cerium cobalt acetate to the mixture B formed in step (2) to obtain a mixture C;

[0161] Step (4): Add 0.1 g of phosphotungstic acid to the mixture C formed in step (3), and stir at 80° C. for 60 min to obtain a total of 39.1 g of the composite catalyst.

[0162] Example 16

[0163] The preparation method of the composite catalyst in this embodiment is as follows:

[0164] Step (1): add 20.0 g of acetonitrile to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0165] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-002 to the mixed solution of step (1), and heat with stirring at 50° C. for 45 min to obtain a mixture B;

[0166] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0167] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 70° C. for 60 min to obtain a total of 39.3 g of the composite catalyst.

[0168] Example 17

[0169] The preparation method of the composite catalyst in this embodiment is as follows:

[0170] Step (1): add 20.0 g of methanol to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0171] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-003 to the mixed solution of step (1), and heat with stirring at 60° C. for 30 min to obtain a mixture B;

[0172] Step (3): adding 0.5 g of zinc acetate to the mixture B formed in step (2) to obtain a mixture C;

[0173] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 39.8 g of the composite catalyst.

[0174] Example 18

[0175] The preparation method of the composite catalyst in this embodiment is as follows:

[0176] Step (1): add 20.0 g of ethanol to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0177] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-004 to the mixed solution of step (1), and heat with stirring at 45° C. for 30 min to obtain a mixture B;

[0178] Step (3): adding 0.5 g of zinc acetate to the mixture B formed in step (2) to obtain a mixture C;

[0179] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 40.1 g of the composite catalyst.

[0180] Example 19

[0181] The preparation method of the composite catalyst in this embodiment is as follows:

[0182] Step (1): add 20.0 g of methanol to 10.0 g of phenyltrimethylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0183] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-005 to the mixed solution of step (1), and heat with stirring at 70° C. for 30 min to obtain a mixture B;

[0184] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0185] Step (4): Add 0.1 g of phosphotungstic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 38.6 g of the composite catalyst.

[0186] Example 20

[0187] The preparation method of the composite catalyst in this embodiment is as follows:

[0188] Step (1): add 20.0 g of methanol to 10.0 g of phenyltrimethylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0189] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-006 to the mixed solution of step (1), and heat with stirring at 70° C. for 30 min to obtain a mixture B;

[0190] Step (3): adding 0.5 g of manganese acetate to the mixture B formed in step (2) to obtain a mixture C;

[0191] Step (4): Add 0.1 g of phosphotungstic acid to the mixture C formed in step (3), and stir at 60° C. for 60 min to obtain a total of 39.1 g of the composite catalyst.

[0192] Example 21

[0193] The preparation method of the composite catalyst in this embodiment is as follows:

[0194] Step (1): add 20.0 g of dibutyl ether to 10.0 g of phenyltrimethylammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0195] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-007 to the mixed solution of step (1), and heat at 100° C. with stirring for 20 min to obtain a mixture B;

[0196] Step (3): adding 0.5 g of magnesium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0197] Step (4): Add 0.1 g of phosphotungstic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 39.1 g of the composite catalyst.

[0198] Example 22

[0199] The preparation method of the composite catalyst in this embodiment is as follows:

[0200] Step (1): add 20.0 g of dibutyl ether to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0201] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-008 to the mixed solution of step (1), and heat with stirring at 80° C. for 20 min to obtain a mixture B;

[0202] Step (3): adding 0.5 g of manganese acetate to the mixture B formed in step (2) to obtain a mixture C;

[0203] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 40.1 g of the composite catalyst.

[0204] Example 23

[0205] The preparation method of the composite catalyst in this embodiment is as follows:

[0206] Step (1): add 20.0 g of dibutyl ether to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0207] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-009 to the mixed solution of step (1), and heat with stirring at 70° C. for 30 min to obtain a mixture B;

[0208] Step (3): adding 0.5 g of sodium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0209] Step (4): Add 0.1 g of silicotungstic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 38.9 g of the composite catalyst.

[0210] Example 24

[0211] The preparation method of the composite catalyst in this embodiment is as follows:

[0212] Step (1): add 20.0 g of dibutyl ether to 10.0 g of N-hydroxyphthalimide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0213] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-010 to the mixed solution of step (1), and heat with stirring at 80° C. for 30 min to obtain a mixture B;

[0214] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0215] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 38.7 g of the composite catalyst.

[0216] Example 25

[0217] The preparation method of the composite catalyst in this embodiment is as follows:

[0218] Step (1): add 20.0 g of methanol to 10.0 g of N-hydroxyphthalimide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0219] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-011 to the mixed solution of step (1), and heat with stirring at 60° C. for 30 min to obtain a mixture B;

[0220] Step (3): adding 0.5 g of sodium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0221] Step (4): Add 0.1 g of phosphomolybdic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 39.8 g of the composite catalyst.

[0222] Example 26

[0223] The preparation method of the composite catalyst in this embodiment is as follows:

[0224] Step (1): add 20.0 g of ethanol to 10.0 g of N-hydroxyphthalimide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0225] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-012 to the mixed solution of step (1), and heat with stirring at 60° C. for 30 min to obtain a mixture B;

[0226] Step (3): adding 0.5 g of zirconium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0227] Step (4): Add 0.1 g of phosphotungstic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 39.6 g of the composite catalyst.

[0228] Example 27

[0229] The preparation method of the composite catalyst in this embodiment is as follows:

[0230] Step (1): add 20.0 g of methanol to 10.0 g of N-hydroxyphthalimide, and stir at room temperature until the solid is completely dissolved to obtain a mixture A;

[0231] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-013 to the mixed solution of step (1), and heat with stirring at 60° C. for 30 min to obtain a mixture B;

[0232] Step (3): adding 0.5 g of cerium acetate to the mixture B formed in step (2) to obtain a mixture C;

[0233] Step (4): Add 0.1 g of silicotungstic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 39.2 g of the composite catalyst.

[0234] Example 28

[0235] The preparation method of the composite catalyst in this embodiment is as follows:

[0236] Step (1): add 20.0 g of dibutyl ether to 10.0 g of ammonium bromide, and stir at room temperature until the solid is completely dissolved to obtain mixture A;

[0237] Step (2): add 10.0 g of alkyl-substituted 1,4,7-trimethyl-1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-014 to the mixed solution of step (1), and heat at 100° C. with stirring for 30 min to obtain a mixture B;

[0238] Step (3): adding 0.5 g of manganese acetate to the mixture B formed in step (2) to obtain a mixture C;

[0239] Step (4): Add 0.1 g of silicotungstic acid to the mixture C formed in step (3), and stir at 90° C. for 60 min to obtain a total of 38.9 g of the composite catalyst.

[0240] Example 29

[0241] In this embodiment, a mixed alcohol of n-hexanol, n-octanol, and n-nonanol (mass ratio of 8:1:1) was used as a raw material to oxidize and prepare a mixed aldehyde of n-hexanal, n-octanal, and n-nonanal, as follows:

[0242] To a 250 mL titanium autoclave, sodium bromide (0.1 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-001 (0.25 g), sodium acetate (0.1 g), phosphotungstic acid (0.05 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% was considered sufficient to indicate a good airtightness. After venting the nitrogen, the temperature was raised to 50°C, and air was introduced continuously to a pressure of 1.0 MPa. The air flow was controlled at 50 mL / min, and the reaction was terminated after six hours. The reaction solution was light orange, and the total weight of the solution was 103.1 g.

[0243] 0.2g of the reaction solution was taken, and toluene was used as the internal standard. 0.05g of toluene was diluted with 10g of ethyl acetate and then injected into the sample for testing. Substituting the test data into the internal standard curve, the remaining amount of mixed alcohol was 0.92g, mixed aldehydes 42.08g, and mixed acids 2.7g. The calculated fatty alcohol conversion was 98.22%, and the fatty aldehyde selectivity reached 83.92%.

[0244] Example 30

[0245] In this embodiment, a mixed alcohol of n-hexanol, 2-methylpentanol, n-octanol, 2-methylheptanol, n-nonanol, and 2-methylhexanol (mass ratio of 2:1:2:2:2:1) was used as a raw material to oxidize and prepare a mixed aldehyde of n-hexanal, 2-methylpentanal, n-octanol, 2-methylheptanal, n-nonanal, and 2-methylhexanal, as follows:

[0246] To a 250 mL titanium autoclave, sodium bromide (0.25 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-002 (0.25 g), zinc acetate (0.25 g), phosphomolybdic acid (0.05 g), acetonitrile (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. The pressure drop was considered airtight if it did not exceed 5%. After venting the nitrogen, the temperature was raised to 45°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 70 mL / min. The reaction was terminated after five hours. The reaction solution was light orange, and the total weight of the solution was 102.9 g.

[0247] 0.2 g of the reaction solution was taken, with toluene as the internal standard. 0.1 g of toluene was diluted with 10 g of acetonitrile and then injected into the sample for testing. Substituting the test data into the internal standard curve, the remaining amount of mixed alcohol was 0.13 g, mixed aldehydes 37.97 g, and mixed acids 9.58 g. The calculated conversion of mixed alcohol was 99.75%, and the selectivity for mixed aldehydes reached 74.57%.

[0248] Example 31

[0249] In this embodiment, a mixed alcohol of n-hexanol, n-octanol, and n-nonanol (mass ratio of 3:3:4) was used as a raw material to oxidize and prepare a mixed aldehyde of n-hexanal, n-octanal, and n-nonanal, as follows:

[0250] To a 250 mL titanium autoclave, hexadecyltrimethylammonium bromide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-003 (0.5 g), zirconium acetate (0.25 g), phosphotungstic acid (0.05 g), methanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% indicated good airtightness. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 80 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 102.8 g.

[0251] 0.1 g of the reaction solution was diluted with 10 g of acetonitrile using toluene as the internal standard. Substituting the test data into the internal standard curve, the remaining amount was 0.31 g of mixed alcohol, 36.32 g of mixed aldehydes, and 11.25 g of octanoic acid. The calculated conversion of the mixed alcohol was 99.40%, and the selectivity for the mixed aldehydes was 71.46%.

[0252] Example 32

[0253] In this embodiment, a mixed alcohol of n-hexanol, n-octanol, and n-nonanol (mass ratio of 2:4:4) was used as a raw material to oxidize and prepare a mixed aldehyde of n-hexanal, n-octanal, and n-nonanal, as follows:

[0254] To a 250 mL titanium autoclave, sodium bromide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-004 (0.5 g), manganese acetate (0.25 g), phosphomolybdic acid (0.05 g), acetonitrile (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. The autoclave was considered airtight if the pressure dropped by no more than 5%. After venting the nitrogen, the temperature was raised to 65°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 100 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 102.6 g.

[0255] 0.1 g of the reaction solution was diluted with 10 g of acetonitrile using toluene as the internal standard. Substituting the test data into the internal standard curve, the remaining amount was 1.49 g of mixed alcohol, 34.36 g of mixed aldehydes, and 11.25 g of octanoic acid. The calculated conversion of the mixed alcohol was 97.13%, and the selectivity for the mixed aldehydes was 69.19%.

[0256] Example 33

[0257] In this embodiment, a mixed alcohol of n-hexanol, n-octanol, and n-nonanol (mass ratio of 2:4:4) was used as a raw material to oxidize and prepare a mixed aldehyde of n-hexanal, n-octanal, and n-nonanal, as follows:

[0258] To a 250 mL titanium autoclave, phenyltrimethylammonium bromide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-005 (0.5 g), cerium acetate (0.25 g), phosphomolybdic acid (0.05 g), methanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. The pressure drop was considered airtight if it did not exceed 5%. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 75 mL / min. The reaction was terminated after six hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 103.6 g.

[0259] 0.1 g of the reaction solution was diluted with 10 g of acetonitrile using toluene as the internal standard. Substituting the test data into the internal standard curve, the remaining amount was 2.12 g of mixed alcohol, 40.40 g of mixed aldehyde, and 2.22 g of mixed acid. The calculated conversion of the mixed alcohol was 95.92%, and the selectivity for the mixed aldehyde reached 82.41%.

[0260] Example 34

[0261] In this embodiment, a mixed alcohol of n-hexanol, n-octanol, and n-nonanol (mass ratio of 3:3:4) was used as a raw material to oxidize and prepare a mixed aldehyde of n-hexanal, n-octanal, and n-nonanal, as follows:

[0262] To a 250 mL titanium autoclave, phenyltrimethylammonium bromide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-006 (0.5 g), manganese acetate (0.25 g), phosphomolybdic acid (0.05 g), methanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% indicated good airtightness. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 90 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 103.1 g.

[0263] 0.1 g of the reaction solution was diluted with 10 g of acetonitrile using toluene as the internal standard. Substituting the test data into the internal standard curve, the remaining amount was 0.61 g of mixed alcohol, 38.52 g of mixed aldehyde, and 10.32 g of mixed acid. The calculated conversion of the mixed alcohol was 98.83%, and the selectivity for the mixed aldehyde reached 76.25%.

[0264] Example 35

[0265] In this embodiment, n-octanol is used as a raw material to prepare n-octanal, specifically as follows:

[0266] To a 250 mL titanium autoclave, phenyltrimethylammonium bromide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-007 (0.5 g), magnesium acetate (0.25 g), phosphotungstic acid (0.05 g), methanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% indicated good airtightness. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 50 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 102.3 g.

[0267] 0.1 g of the reaction solution was diluted with toluene as the internal standard, and 0.1 g of toluene was diluted with 10 g of acetonitrile and injected into the sample for testing. Substituting the test data into the internal standard curve, the remaining amount of mixed alcohol was 0.6 g, mixed aldehyde was 50.1 g, and mixed acid was 0.3 g. The calculated conversion of mixed alcohol was 96.19%, and the selectivity of mixed aldehyde was 99.32%.

[0268] Example 36

[0269] In this embodiment, a mixed alcohol of n-hexanol and n-heptanol (mass ratio of 6:4) was used as a raw material to oxidize and prepare a mixed aldehyde of n-hexanal and n-heptanal, specifically as follows:

[0270] To a 250 mL titanium autoclave, ammonium bromide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-008 (0.5 g), manganese acetate (0.25 g), phosphotungstic acid (0.05 g), ethanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% indicated good airtightness. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 50 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 103.5 g.

[0271] 0.1 g of the reaction solution was diluted with toluene as the internal standard, and 0.1 g of toluene was diluted with 10 g of acetonitrile and injected into the sample for testing. Substituting the test data into the internal standard curve, the remaining amount was 4.16 g of mixed alcohol, 45.25 g of mixed aldehyde, and 1.59 g of mixed acid. The calculated conversion of the mixed alcohol was 97.75%, and the selectivity for the mixed aldehyde reached 96.67%.

[0272] Example 37

[0273] In this embodiment, a mixed alcohol of 2-ethylpentanol and 2-ethylhexanol (mass ratio of 5:5) was used as a raw material to oxidize and prepare a mixed aldehyde of 2-ethylpentanal and 2-ethylhexanal, as follows:

[0274] To a 250 mL titanium autoclave, ammonium bromide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-009 (0.5 g), magnesium acetate (0.25 g), silicotungstic acid (0.05 g), ethanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. A pressure drop of no more than 5% indicated good airtightness. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 50 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 103.6 g.

[0275] 0.1 g of the reaction solution was diluted with 10 g of acetonitrile using toluene as the internal standard. Substituting the test data into the internal standard curve, the remaining amount of mixed alcohol was 0.64 g, mixed aldehydes 35.11 g, and mixed acids 10.50 g. The calculated conversion of mixed alcohol was 98.76%, and the selectivity for mixed aldehydes reached 69.55%.

[0276] Example 38

[0277] In this embodiment, a mixed alcohol of 3-methylhexanol and 3-methylheptanol (mass ratio of 5:6) was used as a raw material to oxidize and prepare a mixed aldehyde of 3-methylhexanal and 3-methylheptanal, as follows:

[0278] To a 250 mL titanium autoclave, N-hydroxyphthalimide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-010 (0.5 g), cerium acetate (0.25 g), phosphomolybdic acid (0.05 g), acetonitrile (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. The pressure drop was considered airtight if it did not exceed 5%. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 50 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 102.6 g.

[0279] 0.1 g of the reaction solution was diluted with toluene as the internal standard, and 0.1 g of toluene was diluted with 10 g of acetonitrile and injected into the sample for testing. Substituting the test data into the internal standard curve, the remaining amount of mixed alcohol was 3.32 g, mixed aldehyde was 45.03 g, and mixed acid was 1.00 g. The calculated conversion of mixed alcohol was 87.82%, and the selectivity of mixed aldehyde was 95.2%.

[0280] Example 39

[0281] In this embodiment, a mixed alcohol of 4-methylhexanol and 4-methylheptanol (mass ratio of 5:5) was used as a raw material to oxidize and prepare a mixed aldehyde of 4-methylhexanal and 4-methylheptanal, as follows:

[0282] To a 250 mL titanium autoclave, N-hydroxyphthalimide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-011 (0.5 g), manganese acetate (0.25 g), phosphomolybdic acid (0.05 g), methanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. The pressure drop was considered airtight if it did not exceed 5%. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 50 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 103.7 g.

[0283] 0.1 g of the reaction solution was diluted with toluene as the internal standard, and 0.1 g of toluene was diluted with 10 g of acetonitrile and injected into the sample for testing. Substituting the test data into the internal standard curve, the remaining amount of mixed alcohol was 2.80 g, mixed aldehyde was 43.01 g, and mixed acid was 2.98 g. The calculated conversion of mixed alcohol was 94.59%, and the selectivity of mixed aldehyde was 92.13%.

[0284] Example 40

[0285] In this embodiment, a mixed alcohol of n-pentanol, n-hexanol, and n-heptanol (mass ratio of 4:4:2) was used as a raw material to oxidize and prepare a mixed aldehyde of n-valeraldehyde, n-hexanal, and n-heptanal, as follows:

[0286] To a 250 mL titanium autoclave, N-hydroxyphthalimide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-012 (0.5 g), zirconium acetate (0.25 g), silicotungstic acid (0.05 g), ethanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. The airtightness of the autoclave was considered good if the pressure drop did not exceed 5%. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 100 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the reaction solution was 102.6 g.

[0287] 0.1 g of the reaction solution was diluted with toluene as the internal standard, and 0.1 g of toluene was diluted with 10 g of acetonitrile and injected into the sample. Substituting the test data into the internal standard curve, the remaining amount of mixed alcohol was 1.01 g, mixed aldehyde was 43.96 g, and mixed acid was 2.07 g. The calculated conversion of mixed alcohol was 98.03%, and the selectivity of mixed aldehyde was 90.68%.

[0288] Example 41

[0289] In this embodiment, a mixed alcohol of n-pentanol, n-hexanol, and n-heptanol (mass ratio of 2:2:6) was used as a raw material to oxidize and prepare a mixed aldehyde of n-valeraldehyde, n-hexanal, and n-heptanal, as follows:

[0290] To a 250 mL titanium autoclave, N-hydroxyphthalimide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-013 (0.5 g), cerium acetate (0.25 g), silicotungstic acid (0.05 g), methanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. The reactor was considered airtight if the pressure dropped by no more than 5%. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 100 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the reaction solution was 101.9 g.

[0291] 0.1 g of the reaction solution was diluted with 10 g of acetonitrile using toluene as the internal standard. Substituting the test data into the internal standard curve, the remaining amount was 2.83 g of mixed alcohol, 41.26 g of mixed aldehyde, and 3.39 g of mixed acid. The calculated conversion of the mixed alcohol was 94.20%, and the selectivity for the mixed aldehyde reached 89.6%.

[0292] Example 42

[0293] In this embodiment, a mixed alcohol of n-pentanol, n-hexanol, and n-heptanol (mass ratio of 2:2:6) was used as a raw material to oxidize and prepare a mixed aldehyde of n-valeraldehyde, n-hexanal, and n-heptanal, as follows:

[0294] To a 250 mL titanium autoclave, ammonium bromide (0.5 g), alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst YG-73-7-014 (0.5 g), manganese acetate (0.25 g), silicotungstic acid (0.05 g), methanol (1.0 g), ethylene dichloride (52 g), and a mixed alcohol (52 g) were added in sequence. After the autoclave was assembled, nitrogen was introduced to a pressure of 1.5 MPa and maintained for 15 minutes. The autoclave was considered airtight if the pressure dropped by no more than 5%. After venting the nitrogen, the temperature was raised to 60°C, and air was introduced continuously to a pressure of 1.0 MPa. Air was then introduced at a controlled flow rate of 100 mL / min. The reaction was terminated after five hours. The reaction solution was orange-yellow in color, and the total weight of the solution was 104.2 g.

[0295] 0.1 g of the reaction solution was diluted with toluene as the internal standard, and 0.1 g of toluene was diluted with 10 g of acetonitrile and injected into the sample. Substituting the test data into the internal standard curve, the remaining amount of mixed alcohol was 1.75 g, mixed aldehyde was 43.21 g, and mixed acid was 336 g. The calculated conversion of mixed alcohol was 96.50%, and the selectivity of mixed aldehyde was 91.36%.

[0296] Comparative Example

[0297] The experimental operation method of the comparative example is consistent with that of Example 35, except for the amount of material added. The material addition amount and experimental results are specifically shown in Table 1.

[0298] Table 1 Comparative Example Material Addition Amount and Experimental Results

[0299]

[0300] As can be seen from Table 1, compared with Comparative Example 8 which does not use an alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst, the conversion rate of fatty alcohol and the selectivity of fatty aldehyde in Example 35 are both optimal, indicating that the alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst in the present invention can significantly improve the activity and selectivity of the oxidation reaction of fatty alcohol to prepare fatty aldehyde.

[0301] Comparative Examples 1-7 demonstrate that using an alkyl-substituted 1,4,7-triazacyclononane-coordinated metal peroxide catalyst as the primary catalyst, in conjunction with a cocatalyst, a regulator, and a protective agent, while controlling the component ratios, can achieve a synergistic effect among the components, resulting in excellent reaction activity and selectivity. Adjusting any component or ratio can significantly impact the reaction performance, so an appropriate ratio should be used for the reaction.

[0302] It will be apparent to those skilled in the art that the present disclosure is not limited to the details of the exemplary embodiments described above, and that the present disclosure can be implemented in other specific forms without departing from the spirit or essential characteristics of the present disclosure. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the present disclosure is defined by the appended claims rather than the foregoing description, and all variations that come within the meaning and range of equivalents of the claims are intended to be included in the present disclosure.

[0303] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. An alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst, characterized in that: Its general formula is shown in formula (I): （Ⅰ） Wherein, B is selected from any one of copper ion, sodium ion, iron ion, potassium ion, zinc ion, ammonium ion, dodecyldimethylbenzylammonium ion, tetrabutylphosphonium ion, tributylethylphosphonium ion, tributylhexylphosphonium ion, tetramethylammonium ion, dodecyltrimethylammonium ion, octadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, and octyltributylphosphonium ion; M is selected from any one of molybdenum, chromium, lanthanum, cerium, tungsten, scandium, titanium, zirconium, vanadium, nickel, chromium, cobalt, manganese, copper, potassium, sodium, iron, magnesium, and zinc; R1 is selected from C1-C 15 alkyl; R2 is selected from C1-C 15 alkyl; x is selected from any integer between 1 and 18; y is selected from any integer between 1-18.

2. A method for preparing the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 1, characterized in that: The steps include: Dissolving a metal compound in deionized water, adjusting the solution to be acidic, and then adding peroxide to obtain a metal peroxide solution; The metal peroxide solution, alkyl-substituted 1,4,7-triazacyclononane and salt are mixed, filtered and dried to obtain the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst.

3. The method for preparing the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 2, characterized in that: The pH value of the solution of the metal compound dissolved in deionized water is 4-6.

4. The method for preparing the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 2, characterized in that: The metal compound is selected from any one of chromium chloride, lanthanum nitrate, lanthanum chloride, cerium sulfate, cerium nitrate, scandium chloride, scandium nitrate, titanium chloride, titanium sulfate, zirconium chloride, zirconium nitrate, manganese sulfate, potassium permanganate, copper sulfate, copper chloride, potassium chloride, potassium nitrate, ferric chloride, ferrous sulfate, magnesium chloride, magnesium sulfate, zinc chloride, zinc sulfate, sodium molybdate, sodium tungstate, molybdenum acetylacetonate, tungsten hexacarbonyl, cobalt sulfate, nickel nitrate, nickel acetate and sodium metavanadate; and / or, The peroxide is selected from any one of hydrogen peroxide and sodium percarbonate; and / or, The alkyl-substituted 1,4,7-triazacyclononane is selected from any one of 1,4,7-trimethyl-1,4,7-triazacyclononane, 1-ethyl-4,7-dimethyl-1,4,7-triazacyclononane, 1,4-diethyl-7-methyl-1,4,7-triazacyclononane, and 1,4-dimethyl-7-isopropyl-1,4,7-triazacyclononane; and / or The salt is selected from any one of octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium bromide, manganese bromide, ferric bromide, copper bromide, tetrabutylphosphonium bromide, dodecyltrimethylammonium chloride, tributylethylphosphonium bromide, octyltributylphosphonium bromide, tributylhexylphosphonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, and benzyltriethylammonium chloride.

5. A composite catalyst, characterized in that: The invention comprises the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 1.

6. The composite catalyst according to claim 5, characterized in that Also included is a cocatalyst, wherein the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the cocatalyst is 100:(1-200); The cocatalyst is selected from one or more of potassium salts, sodium salts, iron salts, magnesium salts, zinc salts, nickel salts, chromium salts, cobalt salts, manganese salts, copper salts, calcium salts, molybdenum salts, lanthanum salts, cerium salts, tungsten salts, scandium salts, titanium salts, zirconium salts, vanadium salts, potassium oxides, sodium oxides, iron oxides, magnesium oxides, zinc oxides, nickel oxides, chromium oxides, cobalt oxides, manganese oxides, copper oxides, calcium oxides, molybdenum oxides, lanthanum oxides, cerium oxides, tungsten oxides, scandium oxides, titanium oxides, zirconium oxides, and vanadium oxides.

7. The composite catalyst according to claim 5, characterized in that Also included is a regulator, wherein the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the regulator is 100:(1-200); The regulator is selected from one or more of phosphomolybdic acid, phosphotungstic acid, tetrabutylammonium bromide, boric acid, silicotungstic acid and phosphomolybdicvanadic acid.

8. The composite catalyst according to claim 5, characterized in that It also includes a protective agent, and the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the protective agent is 100: (10-200); The protective agent is selected from one or more of sodium acetate, ammonium bromide, hexadecyltrimethylammonium bromide, phenyltrimethylammonium bromide, sodium molybdate and N-hydroxyphthalimide.

9. The composite catalyst according to claim 5, characterized in that Also included is a solvent, wherein the mass ratio of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst to the solvent is 100:(10-1000); The solvent is selected from one or more of dichloromethane, 1,4-dioxane, dibutyl ether, methyl tert-butyl ether, acetonitrile, methanol, ethanol, formic acid, dichloroethane, propionic acid, ethyl acetate and dichloropropyl acetate.

10. A method for preparing a composite catalyst, characterized in that: The steps include: The solvent and the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 1 are mixed, heated to 35° C.-80° C., and stirred for 40 min-120 min.

11. The method for preparing the composite catalyst according to claim 10, characterized in that: The following steps are also included: Mix the protective agent and the solvent to obtain a solution; Add the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 1 to the solution, heat to 35° C.-80° C., and stir for 40 min-120 min; Then add the co-catalyst and ultrasonicate at 35-80°C for 40-60 minutes; Then add the regulator and stir at 35°C-80°C for 40min-60min to obtain a composite catalyst.

12. Use of the alkyl-substituted 1,4,7-triazacyclononane coordinated metal peroxide catalyst according to claim 1 or the composite catalyst according to any one of claims 5 to 9 in the oxidation preparation of fatty aldehydes using fatty alcohols as raw materials.

13. The use according to claim 12, characterized in that The general formula of the fatty alcohol is shown in formula (II): （Ⅱ） Wherein, m is selected from any integer between 1 and 20; R3 is selected from any one of hydrogen, alkyl, alkoxy, ester, hydroxy, amine, halogen or aromatic groups, wherein the alkyl group is a C n H 2n+1 The general structural formula is a straight-chain or branched aliphatic hydrocarbon group, wherein n is any integer between 1 and 8; R4 is selected from any one of hydrogen, alkyl, alkoxy, ester, hydroxy, amine, halogen or aromatic groups, wherein the alkyl group is a C n H 2n+1 The general structural formula is a straight-chain or branched aliphatic hydrocarbon group, wherein n is any integer between 1 and 8.

Images