CN100398196C - Al-Mg catalyst and catalytic synthesis process of alkoxyl carboxylate ether - Google Patents
Al-Mg catalyst and catalytic synthesis process of alkoxyl carboxylate ether Download PDFInfo
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Abstract
The present invention relates to an aluminium-magnesium catalyst and a method for synthesizing alkoxy carboxylic acid ester ether by means of the catalytic action of the aluminium-magnesium catalyst, which belongs to the technical field of catalyst preparation and organic compound synthesis. The present invention provides the aluminium-magnesium inorganic compound catalyst which can be used for catalyzing the embedded type alkoxylating reaction of carboxylic acid alkane ester and epoxy alkane which are used as raw material; besides, the present invention also provides the method for catalyzing one-step method synthesis of double sealing end alkoxylating carboxylic acid alkane ester ether by the catalyst. The catalyst is a metal inorganic compound and has the advantages of simple preparing process and low cost; a catalytic mechanism of the catalyst is double activity point catalysis, that is, a double-point embedded mode is used so that all the ester group C-O bonds of the carboxylic acid alkane ester are embedded into poly alkoxy through an epoxyalkane one-step method to obtain poly alkoxy ether ester which is simultaneously sealed by an acyl group and an alkyl group; end products having a high sealing end rate can be obtained, the end products have few impurities and high purity.
Description
Technical Field
An aluminum-magnesium catalyst and a method for synthesizing alkoxy carboxylic ester ether by using the same, belonging to the technical field of catalyst preparation and organic compound synthesis. In particular to an aluminum-magnesium inorganic composite catalyst and a method for synthesizing double-end-capping alkoxylated carboxylic alkyl esterether by using the catalyst in a one-step embedded way.
Background
At present, two-step process is mostly adopted for synthesizing double-end-capping alkoxylated carboxylic alkyl ester ether, namely carboxylic acid is subjected to alkylene oxide addition and then end capping through etherification reaction. This is because the alkoxylation reaction using alkylene oxide as a reagent has conventionally been carried out only on raw materials containing active hydrogen (such as alcohol, phenol, acid, amine, etc.), but the alkoxylation reaction cannot be directly carried out because the alkyl carboxylate structure does not contain active hydrogen. The two-step method for synthesizing the double-end-capping alkoxylated carboxylic acid alkyl ester ether comprises the following steps: alkyl carboxylates (e.g., fatty acid methyl esters) are hydrogenated to fatty alcohols under high pressure and then reacted with alkylene oxides. On the one hand, the process flow is prolonged, and the product cost is increased; on the other hand, hydrogenation to produce alcohol destroys the original double bond in some alkyl carboxylates, thereby deteriorating the product performance.
Another method for preparing double-end-capped alkoxylated carboxylic acid alkyl ester ether is disclosed in CN1071413A, wherein the polyoxyalkylation of fatty acid ester is catalyzed by a calcium-based catalyst prepared in two steps, the method requires introducing an alkoxylated alcohol to pre-exchange with a calcium-containing compound and a metal alkoxide during the preparation of the catalyst, and the essence of the catalytic reaction is that a one-step intermediate preparation reaction is added before the alkoxylation of fatty acid ester. This, on the one hand, complicates the catalyst preparation and increases the costs, and, on the other hand, introduces organic impurities in the double-ended alkoxylated carboxylic acid alkyl ester ether end product which are difficult to separate.
Disclosure of Invention
The invention aims to provide an aluminum-magnesium inorganic composite catalyst which is used for directly taking carboxylic alkyl ester and alkylene oxide as raw materials and synthesizing double-end-capping alkoxylated carboxylic alkyl ester ether in one step by an embedded alkoxylation reaction in the presence of the catalyst.
The double-end-capped alkoxylated carboxylic alkyl ester ether is a fine chemical with wide application and high additional value, and can be used in various industrial fields, such as washing products, personal hygiene products, spinning oil, metal processing preparations, defoaming agents, polyurethane foaming agents, polymerizable emulsifiers and the like. Particularly, the double-end-capped polyethoxy carboxylic acid methyl ester nonionic surfactant is used as a bulk product, the double-end-capped polyethoxy carboxylic acid methyl ester synthesized by an embedded alkoxylation one-step process can directly use cheap and easily available fatty acid methyl ester as a raw material, and the synthesized product has similar performance with fatty alcohol polyethoxy ether, and is better in the aspects of irritation, skin synergy, biodegradability, low-temperature phase behavior and the like. The polyethoxy nonionic surfactant is one of the surfactant varieties with the highest yield worldwide, the total yield of the polyethoxy nonionic surfactant reaches more than 300 million tons per year, and the demand is increased year by year. One new trend in the current production of polyethoxy nonionic surfactants is to double cap them, which can optimize product performance, such as reducing foaming, reducing irritation, increasing chemical and thermal stability, and the like. The embedded ethoxylation one-step process for synthesizing the double-end-capped polyethoxy carboxylic acid methyl ester meets the trend and can reduce the cost.
The technical scheme of the invention is as follows: the aluminum-magnesium inorganic composite catalyst provided by the invention is prepared by taking aluminum oxide and/or aluminum salt, magnesium oxide and/or magnesium salt as raw materials, wherein the molar ratio of aluminum to magnesium is 1: 0.1-12, and the aluminum-magnesium inorganic composite catalyst is prepared by the following steps: mixing and grinding the aluminum-magnesium raw materials according to a certain molar ratio, adding a certain amount of deionized water, fully dispersing to ensure that the total molar concentration of the aluminum-magnesium raw materials is 0.1-0.3mol/L, then adding 0.08-0.1mol of sodium hydroxide and 0.01mol of sodium carbonate under stirring, heating to 50-70 ℃, continuing stirring for 24-48 hours, filtering, and drying in an oven until weight loss does not occur, wherein the aluminum salt is one or more of nitrate, hydrochloride, phosphate, carbonate and sulfate of aluminum, and the magnesium salt is one or more of nitrate, hydrochloride, phosphate, carbonate and sulfate of magnesium.
The catalyst is applied to one-step embedded catalysis to synthesize the double-end-capping alkoxylated carboxylic alkyl ester ether, and the reaction formula is shown as follows,
wherein RCOO-is C1-C22 saturated or unsaturated, straight chain or branched chain, single-carbon or mixed-carbon mono-or multi-carboxylic acid group, and if RCOO-is multi-acid group, the synthesized alkoxylated carboxylic acid alkyl ester ether is fully substituted carboxylic acid alkyl ester ether; r 'O-is C1-C22 saturated or unsaturated, straight chain or branched chain, single carbon or mixed carbon monohydric or polyhydric alcohol group, if R' O-is polyhydric alcohol group, the synthesized alkoxylated carboxylic acid alkyl ester ether is fully substituted carboxylic acid alkyl ester ether; AO is alkylene oxide, including ethylene oxide or/and propylene oxide; (AO) n is a polyalkoxy group.
The specific process comprises the following steps: taking alkyl carboxylate and alkylene oxide as raw materials, wherein the proportion of the alkyl carboxylate and the alkylene oxide is determined according to the requirements of product application, the dosage of the aluminum-magnesium inorganic compound catalyst is 0.1-5% of the total weight of the raw materials, adding the alkyl carboxylate and the aluminum-magnesium inorganic compound catalyst into a autoclave, adding a kettle cover, uniformly screwing bolts, connecting an alkylene oxide metering tank with the autoclave, stirring at 20-80 ℃, vacuumizing for 5-60min to remove water and other low boiling point substances in a reaction system, replacing residual air in the autoclave for 3 times by N2, introducing the alkylene oxide after the temperature of the autoclave is raised to 100-150 ℃, keeping the system pressure at 0.3-0.4MPa until the required amount of the alkylene oxide is added, continuing to react for 30-60min, cooling, releasing pressure, and removing the product.
The invention has the beneficial effects that: the catalyst used in the present invention is an aluminum-magnesium inorganic composite catalyst, while the one used in the published patent CN1071413A is an organic calcium-based catalyst. The catalyst of the invention is characterized in that:
the aluminum-magnesium inorganic composite catalyst used in the invention is different from the calcium-based catalyst used in CN1071413A in chemical structure, the calcium-based catalyst is an organic metal catalyst prepared by a two-step method, and the aluminum-magnesium inorganic composite catalyst is an inorganic metal catalyst prepared by a one-step method, so that the preparation process of the aluminum-magnesium inorganic composite catalyst used in the invention is simple, and only lower manufacturing cost is needed.
The invention uses the aluminum-magnesium inorganic composite catalyst with a different catalysis mechanism from the calcium-based catalyst used in CN1071413A, and the organic calcium-based catalyst is a single-active-point catalyst and catalyzes the reaction in a bond breaking mode; the essence of this catalytic reaction is the addition of a one-step intermediate preparation reaction prior to the alkoxylation of the fatty acid ester. The aluminum-magnesium inorganic compound catalyst is double-active-point catalyst, all ester group C-O bonds of carboxylic alkyl ester are embedded into polyalkoxy by one-step method by using alkylene oxide in a double-point embedding mode, and polyalkoxy ester ether capped by acyl and alkyl at the same time is obtained by one-step reaction, so that the invention can obtain double-capped alkoxylated carboxylic alkyl ester ether end products with high capping rate.
The composition and preparation temperature of the catalyst have great operational flexibility, and in addition, other organic impurities are not introduced in the preparation process of the aluminum-magnesium inorganic composite catalyst, and the catalyst can be removed by simple filtration after the catalytic reaction is finished, so that the final product has less impurities and high purity.
Another feature of the catalyst of the invention is that it can catalyze the production of polyalkoxy groups of narrow distribution, for example, the soft ionization mass spectrum of the product of example 4 shows that the proportion of the central five components in the product is 70% or more.
Drawings
FIG. 1 shows the soft ionization mass spectrum of polyoxyethylene (9) dodecanoic acid methyl ester C11H23CO (OCH2CH2)9OCH3
Detailed Description
Example 1 preparation of aluminum-magnesium inorganic composite catalyst 1
0.01mol of aluminum nitrate, 0.005mol of magnesium phosphate and 0.1mol of magnesium oxide are mixed and milled, then the mixture is added into 1000ml of deionized water for full dispersion, 0.1mol of sodium hydroxide and 0.01mol of sodium carbonate are added under stirring, and the mixture is heated to 65 ℃ and stirred for 24 hours. Drying in an oven at a temperature higher than 120 ℃ after filtering until weight loss does not occur, and keeping for later use. The catalytic activity of the obtained aluminum-magnesium inorganic composite catalyst is 1.72 gEO/gCat/min.
Example 2 preparation of aluminum-magnesium inorganic composite catalyst 2
0.01mol of aluminum carbonate, 0.1mol of magnesium oxide and 0.18mol of aluminum oxide are mixed and ground, then added into 1000ml of deionized water for full dispersion, 0.09mol of sodium hydroxide and 0.01mol of sodium carbonate are added under stirring, and the mixture is heated to 50 ℃ and stirred for 48 hours. Drying in an oven at a temperature higher than 120 ℃ after filtering until weight loss does not occur, and keeping for later use.
Example 3 preparation of aluminum-magnesium inorganic composite catalyst 3
0.01mol of aluminum carbonate, 0.01mol of magnesium chloride, 0.2mol of magnesium oxide and 0.05mol of aluminum oxide are mixed and ground, thenthe mixture is added into 1000ml of deionized water for full dispersion, 0.08mol of sodium hydroxide and 0.015mol of sodium carbonate are added under stirring, and the mixture is heated to 55 ℃ and stirred for 48 hours. Drying in an oven at a temperature higher than 120 ℃ after filtering until weight loss does not occur, and keeping for later use.
Example 4 Synthesis of polyoxyethylene (9) methyl laurate C11H23CO (OCH2CH2)9OCH3 catalyzed by aluminum-magnesium inorganic composite catalyst
150g of methyl dodecanoate and 2.0g of an aluminum-magnesium inorganic complex catalyst were charged into a 0.5L autoclave. And adding a kettle cover, and uniformly screwing bolts. The ethylene oxide metering tank was connected to an autoclave. Stirring at 80 deg.C, vacuumizing to 2666Pa, maintaining for 5min to remove water and other low boiling point substances, and replacing residual air in the kettle with N2 for 3 times. After the temperature of the kettle rises to 140 ℃, introducing ethylene oxide according to the molar ratio of the methyl dodecanoate to the ethylene oxide of 1: 9, and keeping the system pressure at 0.3-0.4Mpa for about 2.5 h. And continuing to react for 30min, cooling, releasing pressure and removing the product. The polyalkoxy distribution index in the product was tested by electrospray mass spectrometry (ESI-MS) and tested for the presence of unreacted alkyl carboxylate and by-product polyethylene glycol (FIG. 1). The distribution index of the polyalkoxy group is about 75 percent (mol/mol), no residual methyl ester and byproduct polyethylene glycol are detected, and the result proves that the double-end-capped alkoxylated carboxylic acid alkyl ester ether is the narrow-distribution polyalkoxy ester ether which is simultaneously end-capped by acyl and alkyl through one-step reaction. The product was an off-white transparent liquid with a cloud point of 50 ℃. The product can be used for preparing spinning oil, and has the characteristics of high smoke point and good smoothness.
Example 5 Synthesis of Polyoxyethylene (21) palm oil catalyzed by aluminum-magnesium inorganic composite catalyst
395g of palm oil (with the average molecular weight of 791) and 5.0g of aluminum-magnesium inorganic composite catalyst are added into a 2L autoclave, and 462g of ethylene oxide is introduced for reaction after the temperature of the autoclave is raised to 140-145 ℃. The evacuation time was 20min and the rest of the reaction procedure was the same as in example 1. The product is yellow solid at room temperature, the freezing point is 40 ℃, and NMR and soft ionization mass spectrum analysis show that all ester group C-O bonds in the palm oil are embedded with narrow-distribution polyalkoxy groups by an alkylene oxide one-step method. The product can be used for preparing metal processing preparation.
Example 6 Synthesis of polyoxyethylene (1) ethyl acetate CH3COOCH2CH2OCH2CH3 catalyzed by aluminum-magnesium inorganic composite catalyst
220g of ethyl acetate and 2.5g of aluminum-magnesium inorganic composite catalyst are added into a 0.5L autoclave, and 44g of ethylene oxide is introduced for reaction after the temperature of the autoclave is raised to 105-115 ℃. After the crude product has been distilled off to remove unreacted ethyl acetate, the content of the main product CH3COOCH2CH20CH2CH3 in the residue is greater than 80%. The product can be used as polyurethane foaming agent.
Example 7 synthesis of polyoxyethylene (5) methyl acrylate CH2 ═ CHCO (OCH2CH2)5OCH3 catalyzed by aluminum-magnesium inorganic complex catalyst
86g of methyl acrylate and 3.og of aluminum-magnesium inorganic composite catalyst are added into a 0.5L autoclave, and after the temperature of the autoclave is raised to 115 ℃ and 125 ℃, 220g of ethylene oxide is introduced for reaction. 301g of pale yellow liquid product are obtained. The product can be used as a polymerizable emulsifier or a novel functional polymeric monomer.
EXAMPLE 8 catalysis of polyoxypropylene methyl (3) dodecanoate by aluminum-magnesium inorganic composite catalyst
Synthesis of C11H23CO (OCH2CHCH3)3OCH3
107g of methyl dodecanoate and 3.0g of aluminum-magnesium inorganic composite catalyst are added into a 0.5L autoclave, and 174g of propylene oxide is introduced for reaction after the temperature of the autoclave is raised to 115 ℃ and 125 ℃. The remaining reaction procedure was the same as in example 4 to obtain a water-insoluble oily liquid product.
Example 9 Synthesis of polyoxyethylene (9) polyoxypropylene (1) methyl dodecanoate C11H23CO (OCH2CH2)9(OCH2CHCH3) OCH3
150g of methyl dodecanoate and 2.0g of an aluminum-magnesium inorganic complex catalyst were charged into a 0.5L autoclave. After the temperature of the kettle rises to 125-class 135 ℃, propylene oxide is introduced according to the molar ratio of methyl dodecanoate to propylene oxide of 1: 1, then ethylene oxide is introduced according to the molar ratio of methyl dodecanoate to ethylene oxide of 1: 9, and the rest of the reaction procedures are the same as those in example 4, so that the water-soluble product with the viscosity ratio of C11H23CO (OCH2CH2)9OCH3 reduced is obtained.
Example 10 Synthesis of polyoxyethylene (9) cocoate methyl ester catalyzed by aluminum-magnesium inorganic Complex catalyst
75g of methyl cocoate and 1.0g of aluminum-magnesium inorganic composite catalyst are added into a 0.5L autoclave, and 134g of ethylene oxide is introduced after the autoclave temperature is raised to 135-145 ℃. The temperature was 60 ℃ during the evacuation, and the rest of the reaction sequence was the same as in example 4. The product was a light yellow clear liquid with a cloud point of 50 ℃.
Claims (2)
1. An Al-Mg inorganic compound catalyst is characterized in that aluminum oxide and/or aluminum salt and magnesium oxide and/or magnesium salt are used as raw materials, at least one of the raw materials is aluminum oxide or magnesium oxide, and the prepared Al-Mg inorganic compound with the Al/Mg molar ratio of 1: 0.1-12 is prepared by the following steps: mixing and grinding the raw materials according to a certain molar ratio, adding the mixture into 1L of deionized water, fully dispersing the mixture to ensure that the adding amount of the raw materials in the deionized water is 0.1-0.3mol/L, then adding 0.08-0.1mol of sodium hydroxide and 0.01-0.015mol of sodium carbonate while stirring, heating to 50-70 ℃, continuously stirring for 24-48 hours, filtering, and drying in an oven until weight loss does not occur, wherein the aluminum salt is one or more of nitrate, hydrochloride, phosphate and sulfate of aluminum, and the magnesium salt is one or more of nitrate, hydrochloride, phosphate and sulfate of magnesium.
2. A method for preparing double-end-capped alkoxylated carboxylic alkyl ester ether by using the catalyst of claim 1 in a one-step embedded catalyst is characterized in that the reaction formula is shown as follows,
wherein R is the chain length C1-C22R' is a chain length C1-C22Alkyl of (A) is-CH2CH2-or
Using carboxylic acid alkyl ester and epoxy alkane as raw material, adding the catalyst into autoclave, adding cover, uniformly screwing screw bolt, connecting alkylene oxide metering tank and autoclave, stirring themVacuum pumping at 20-80 deg.C for 5-60min to remove water and other low boiling point substances, and adding N2Replacing residual air in the kettle for 3 times, introducing alkylene oxide and keeping the system pressure at 0.3-0.4MPa after the temperature of the kettle rises to 100-150 ℃, continuing to react for 30-60min, cooling, releasing pressure and removing the product.
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| CN101219952B (en) * | 2007-11-27 | 2010-06-09 | 江南大学 | Method for synthesizing polyoxyalkylene monoether-acrylate with one-step method of acrylic ester compounds |
| CN101293953B (en) * | 2008-05-26 | 2012-02-15 | 江南大学 | Method for synthesizing poly-dihydric alcohol monoether acrylic ester macromer |
| CN103920480B (en) * | 2014-04-19 | 2015-12-30 | 江苏怡达化学股份有限公司 | An a kind of step embeds the magnesium-aluminum-zirconium solid catalyst of synthesis alkoxyl alcohol ether-ether |
| CN104117350A (en) * | 2014-07-26 | 2014-10-29 | 江苏怡达化学股份有限公司 | Magnesium-aluminum solid catalyst for synthesizing ethoxyethyl acrylate through one step |
| CN104130126A (en) * | 2014-07-26 | 2014-11-05 | 常州大学 | Method for synthesizing ethoxyethyl acrylate through alkoxylation |
| CN107159177B (en) * | 2017-06-05 | 2020-01-10 | 浙江皇马新材料科技有限公司 | Preparation and application method of alkaline composite oxide catalyst |
| CN109317187B (en) * | 2018-11-19 | 2021-08-03 | 江苏钟山化工有限公司 | Catalyst for synthesis of fatty acid ester alkoxylates and application thereof |
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