CN117603049A - Method and catalyst for preparing isononanoate - Google Patents

Abstract

The invention discloses a method for preparing isononanoate ester. This method uses cobalt salt as a catalyst, polyionic liquid as a ligand and carrier, diisobutylene, CO and fatty alcohol as reactants, and a hydrogen esterification reaction to obtain isononanoate ester. The present invention enables the cobalt salt catalyst and the polyionic liquid to form a complex in situ. After the diisobutylene hydroesterification reaction is completed, the complex can be separated from the reaction system through filtration, centrifugation, etc., thereby realizing the recycling of the catalyst. , which overcomes the existing shortcomings of difficulty in separation of the catalyst system and inability to be recycled when preparing isononanoate through the hydrogenation esterification of diisobutylene, and reduces the cost of the catalyst.

Description

A method and catalyst for preparing isononanoate ester

Technical field

The invention relates to a method for preparing isononanoate ester through hydrogen esterification reaction of diisobutylene.

Background technique

Isononanoic acid (3,5,5-trimethylhexanoic acid) is a C9 monocarboxylic acid with a branched structure and has a wide range of uses. It can be used to synthesize high-grade lubricants and coatings, and has important uses in microgels, surfactants, pharmaceutical intermediates, metal soaps and metal working fluids. It can also be used to modify alkyd resins, which can effectively improve yellowing resistance. Denaturation and impact resistance. Isononanoic acid is also used in cosmetics, stabilizers, tire adhesion additives and other fields. Among them, the isononanoate ester prepared by the reaction of isononanoic acid and ethylene glycol can be used as a plasticizer for PVC or polyvinyl butyral films and a coalescing agent for polymer dispersions; isononanoic acid and polyols such as neopentyl Isononanoate esters synthesized from glycol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or dipentaerythritol are a class of widely used lubricating oil esters. In addition, the corresponding vinyl ester of isononanoic acid is often used as a comonomer to improve the properties of polymers such as polyvinyl acetate, polyvinyl chloride, polystyrene, and polyacrylates.

Currently, the industrial preparation method of isononanoic acid usually uses 2-ethylhexanol as the initial raw material, and then synthesizes isononanoic acid through dehydration, hydroformylation, oxidation and other reaction processes (CN 104379543.A, CN 104520257 A, CN 108047027 A). This method has a long process route and low product yield; the synthesis process mostly uses homogeneous acid catalysis and high-pressure methods, has high equipment requirements, and has problems such as equipment corrosion and environmental pollution, which limits the large-scale industrial application of this process. In 1955, Koch et al. reported a two-step medium-pressure carbonylation method. Under the reaction temperature of 20-80°C, pressure ≤10MPa and the action of catalyst H ₂ SO ₄ , the reactants olefins, CO and acidic catalysts were coordinated to form a complex. , and then hydrolyzed to synthesize carboxylic acid (Progress in Chemical Industry, 1999, 6, 23-26 (36)). In 1988, Souma et al. (Journal of the Association of Synthetic Organic Chemistry, 1990, 48(2):93-101) developed a method for producing isononanoic acid by the Koch carbonylation process, using a carbonyl metal/strong acid catalyst system, which consumes a lot of acid and requires equipment. Serious corrosion and environmental pollution limit the development of this process.

In 2001, Chen Jing et al. reported the dicobalt octacarbonyl/pyridine-catalyzed hydrogen esterification reaction of diisobutylene to prepare isononanoate. The reaction was performed at 120°C and 6.0MPa for 12 hours. The conversion rate of diisobutylene and the selectivity of methyl isononanoate Reached 70.8% and 84.6% respectively (Fine Chemical Industry, 2001, 18(2):109-111). Methyl isononanoate is further hydrolyzed to form isononanoic acid. However, the catalyst system is difficult to separate and cannot be recycled and reused. To address this problem, the present invention loads ionic liquids onto polymers, metal cobalt salts and polyionic liquids form complexes in situ, and develops a polyionic liquid-supported metal cobalt salt-catalyzed hydrogen esterification reaction of diisobutylene to prepare isononanoate. This method realizes the separation and reuse of catalysts.

Contents of the invention

The purpose of the present invention is to overcome the existing defects of difficult separation and inability to recycle the catalyst system during the hydrogen esterification of diisobutylene to prepare isononanoate, and to provide a polyionic liquid in-situ loaded metal cobalt salt to catalyze diisobutylene hydrogen ester. Method for preparing isononanoate ester through chemical reaction.

The technical solutions adopted by the present invention to achieve the above objects are as follows:

A method for preparing isononanoate ester. The method uses cobalt salt as a catalyst, polyionic liquid as ligand and carrier, diisobutylene, CO and fatty alcohol as reactants, and hydrogen esterification reaction to obtain isonononanoate ester.

The cobalt salt forms a complex with the polyionic liquid in situ. After the diisobutylene hydroesterification reaction is completed, the complex can be separated from the reaction system by filtration, centrifugation, etc. to realize the recycling of the catalyst.

In the above method, the cobalt salt is selected from Co ₂ (CO) ₈ , CoCO ₃ , Co(acac) ₃ , Co(acac) ₂ .

In the above method, the usage amount of the cobalt salt is 2wt% to 6wt% of the total input amount.

In the above method, the polyionic liquid is selected from polyvinyl-3-hexylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-butylimidazole iodide salt-polyvinylpyridine -Polydivinylbenzene, polyvinyl-3-ethylimidazole iodide salt-Polyvinylpyridine-Polydivinylbenzene, polyvinyl-3-acetonitrile imidazole iodide salt-polyvinylpyridine-polyethylene Benzene.

In the above method, the amount of polyionic liquid used is 2wt% to 10wt% of the total input amount.

In the above method, the fatty alcohol is methanol.

In the above method, the mass ratio of diisobutylene and methanol is 1:(2~15).

In the above method, the reaction temperature is 140~160°C, the reaction time is 8~14h, and the CO pressure is 6~8MPa.

A catalyst system for preparing isononanoate ester by hydrogen esterification of diisobutylene, the catalyst system is composed of cobalt salt and polyionic liquid.

In the above catalyst system, the cobalt salt is selected from Co ₂ (CO) ₈ , CoCO ₃ , Co(acac) ₃ , Co(acac) ₂ .

In the above catalyst system, the polyionic liquid is selected from polyvinyl-3-hexylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-butylimidazole iodide salt-polyvinyl Pyridine-polydivinylbenzene, polyvinyl-3-ethylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-acetonitrile imidazole iodide salt-polyvinylpyridine-polydiethylene vinylbenzene.

The polyionic liquid is prepared by adding 1-vinyl-3-alkylimidazole iodide salt or 1-vinyl-3-acetonitrile imidazole iodide salt, 4-vinylpyridine, divinylbenzene and initiator in a solvent. Obtained by mixing and heating polymerization reaction.

The molar ratio of the 1-vinyl-3-alkylimidazole iodide salt or 1-vinyl-3-acetonitrile imidazole iodide salt, 4-vinylpyridine and divinylbenzene is 1:(1～2): 1.

The 1-vinyl-3-alkylimidazole iodide salt is selected from the group consisting of 1-vinyl-3-hexylimidazole iodide salt, 1-vinyl-3-butylimidazole iodide salt, and 1-vinyl-3-ethyl Imidazole iodide salt.

The initiator can be 2,2'-azobisisobutyronitrile, and the dosage is the total mass of 1-vinyl-3-alkyl (or acetonitrile) imidazole iodide salt, 4-vinylpyridine and divinylbenzene. 3wt%~4wt%.

The temperature of the polymerization reaction is 60°C to 90°C.

In the above catalyst system, the mass ratio of cobalt salt and polyionic liquid is 1:1 to 1:2, preferably 1:1 to 1:1.5.

The total feeding amount in the present invention refers to the sum of the feeding amounts of cobalt salt, polyionic liquid, diisobutylene and fatty alcohol.

Detailed ways

The technical solutions of the present invention will be further described in detail below with reference to examples.

The two isomers of diisobutene are 2,4,4-trimethylpentene-1 and 2,4,4-trimethylpentene-2. Among the commercially available diisobutene products used in the present invention, 2,4 , the content of 4-trimethylpentene-1 is 77.2%, the content of 2,4,4-trimethylpentene-2 is 22.4%, the reaction of diisobutene with CO and fatty alcohol to generate isononanoate is as follows :

Example 1

Preparation of polyvinyl-3-hexylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene (2:1): 9.16g (0.03mol) 1-vinyl-3-hexylimidazole iodide salt, 6.30g (0.06mol) 4-vinylpyridine, 3.90g (0.03mol) divinylbenzene, 0.62g (3.2wt%) 2,2'-azobisisobutyronitrile were added to 200mL of ethanol, and the mixture was heated at 90°C, N ₂ , stir for 48 h, then cool to room temperature, and let stand at room temperature for 12 h. The solid powder was collected by filtration, washed three times with ethanol and diethyl ether, and dried under vacuum for 12 hours. The polymer was referred to as: HVIMI-VPy–DVB (2:1).

Example 2

The preparation of polyvinyl-3-hexylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene (1:1) is the same as in Example 1. The reaction raw material 1-vinyl-3-hexylimidazole iodide salt 9.16g (0.03 mol), the dosage of 4-vinylpyridine is 3.15g (0.03mol), the dosage of divinylbenzene is 3.90g (0.03mol), the dosage of 2,2'-azobisisobutyronitrile is 0.52g (3.2wt%) , the abbreviation of the polymer is: HVIMI-VPy–DVB (1:1).

Example 3

The preparation of polyvinyl-3-butylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene (2:1) is the same as in Example 1, and the reaction raw material is 8.31g (0.03mol) 1-vinyl-3- Butylimidazole iodide salt, 6.30g (0.06mol) 4-vinylpyridine, 3.90g (0.03mol) divinylbenzene, 0.59g (3.2wt%) 2,2'-azobisisobutyronitrile, the polymerization The product abbreviation is: BVIMI-VPy–DVB(2:1).

Example 4

The preparation of polyvinyl-3-butylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene (1:1) is the same as in Example 1, and the reaction raw material is 8.31g (0.03mol) 1-vinyl-3- Butylimidazole iodide salt, 3.15g (0.03mol) 4-vinylpyridine, 3.90g (0.03mol) divinylbenzene, 0.49g (3.2wt%) 2,2'-azobisisobutyronitrile, the polymerization The product abbreviation is: BVIMI-VPy–DVB(1:1).

Example 5

The preparation of polyvinyl-3-ethylimidazole iodide-polyvinylpyridine-polydivinylbenzene (2:1) is the same as in Example 1, and the reaction raw material is 7.47g (0.03mol) 1-vinyl-3- Ethylimidazole iodide salt, 6.30g (0.06mol) 4-vinylpyridine, 3.90g (0.03mol) divinylbenzene, 0.57g (3.2wt%) 2,2'-azobisisobutyronitrile, the polymerization The product abbreviation is: EVIMI-VPy–DVB(2:1).

Example 6

The preparation of polyvinyl-3-ethylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene (1:1) is the same as in Example 1, and the reaction raw material is 7.47g (0.03mol) 1-vinyl-3- Ethylimidazole iodide salt, 3.15g (0.03mol) 4-vinylpyridine, 3.90g (0.03mol) divinylbenzene, 0.46g (3.2wt%) 2,2'-azobisisobutyronitrile, the polymerization The product abbreviation is: EVIMI-VPy–DVB(1:1).

Example 7

The preparation of polyvinyl-3-acetonitrile imidazole iodide salt-polyvinylpyridine-polydivinylbenzene (2:1) is the same as in Example 1, and the reaction raw material is 7.83g (0.03mol) 1-vinyl-3- Acetonitrile imidazole iodide salt, 6.30g (0.06mol) 4-vinylpyridine, 3.90g (0.03mol) divinylbenzene, 0.58g (3.2wt%) 2,2'-azobisisobutyronitrile, the polymerization The product abbreviation is: CNVIMI-VPy–DVB(2:1).

Example 8

Hydroesterification of diisobutylene:

In a 100mL reaction kettle equipped with a bottom tube and a filter, add 0.79g catalyst Co ₂ (CO) ₈ , 0.83g HVIMI-VPy–DVB (1:1), 3.74g diisobutylene, and 16.02g methanol in sequence. Replace with 1.5-2MPa CO three times, charge with CO until the pressure is 5.0MPa, heat to 150°C within 60 minutes, turn on stirring, and react at 8.0MPa for 12 hours. Cool to room temperature, press out the reaction liquid from the bottom tube through the filter, leave the catalyst in the reactor for reuse, and analyze the reaction liquid using gas chromatography. The conversion rate of diisobutylene was 88.0%, and the selectivity of methyl isononanoate was 91.4%.

Comparative example 1

The preparation of polyvinylpyridine-polydivinylbenzene (1:1) is the same as in Example 1. The reaction raw materials are 3.15g (0.03mol) 4-vinylpyridine, 3.90g (0.03mol) divinylbenzene, 0.23g (3.2wt%) 2,2'-azobisisobutyronitrile, the polymer is referred to as: VPy-DVB (1:1).

The polymer VPy-DVB (1:1) was used for the hydroesterification reaction of diisobutylene. The specific operation process was the same as in Example 8. The specific reaction conditions were 0.79g Co ₂ (CO) ₈ and 1.09g VPy-DVB (1 :1), 3.74g diisobutylene, 16.02g methanol, reacted at 150°C and 8.0MPa for 12 hours, the conversion rate of diisobutylene was 86.7%, and the selectivity of methyl isononanoate was 88.4%.

Example 9

During the reaction process of Example 8, Co ₂ (CO) ₈ and the polyionic liquid HVIMI-VPy–DVB (1:1) formed a complex in situ. After the reaction was completed, the reaction liquid was pressed out through the filter. The reactants are left in the reaction kettle, and the reactants are added to the reaction kettle again without any post-treatment to directly carry out the next hydroesterification reaction. The effect of each repeated use (reaction conditions are the same as in Example 8) is as shown in Table 1:

repeat times Diisobutylene conversion rate Methyl isononanoate selectivity 1 time 88.0% 91.4% 2 times 66.3% 92.2% 3 times 56.4% 85.4%

Examples 10 to 35

The operating procedures of Examples 10 to 35 are the same as those of Example 8. The specific reaction conditions are shown in Table 2, and the reaction results are shown in Table 3.

Table 2 Hydroesterification conditions of diisobutylene in each embodiment

Table 3 Diisobutylene conversion rate and methyl isononanoate selectivity for each embodiment

Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still The technical solutions described in the foregoing embodiments may be modified, or some of the technical features may be equivalently replaced. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims (7)

1. A method for preparing isononanoate, characterized in that: the method uses cobalt salt as a catalyst, polyionic liquid as a ligand and carrier, diisobutylene, CO and fatty alcohol as reactants, and hydrogen esterification reaction Isononanoate is obtained. 2. The method of claim 1, wherein the cobalt salt is selected from the group consisting of Co ₂ (CO) ₈ , Co(acac) ₃ , and Co(acac) ₂ . 3. The method according to claim 1 or 2, characterized in that: the dosage of the cobalt salt is 2wt%~6wt% of the total input amount. 4. The method of claim 1, wherein the polyionic liquid is selected from the group consisting of polyvinyl-3-hexylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene, polyvinyl-3- Butylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-ethylimidazole iodide salt-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-acetonitrile imidazole iodide Salt - polyvinylpyridine - polydivinylbenzene. 5. The method according to claim 1 or 4, characterized in that: the dosage of the polyionic liquid is 2wt%~10wt% of the total input amount. 6. The method of claim 1, wherein the fatty alcohol is methanol. 7. The method of claim 1, characterized in that: the reaction temperature is 140~160 ^° C, the reaction time is 8~14h, and the CO pressure is 6~8MPa.