CN117603049A - Method and catalyst for preparing isononanoate - Google Patents

Method and catalyst for preparing isononanoate Download PDF

Info

Publication number
CN117603049A
CN117603049A CN202311600155.4A CN202311600155A CN117603049A CN 117603049 A CN117603049 A CN 117603049A CN 202311600155 A CN202311600155 A CN 202311600155A CN 117603049 A CN117603049 A CN 117603049A
Authority
CN
China
Prior art keywords
polyvinyl
catalyst
isononanoate
reaction
diisobutylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311600155.4A
Other languages
Chinese (zh)
Inventor
宋河远
丁梦姣
田昭雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Jiaotong University
Original Assignee
Lanzhou Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Jiaotong University filed Critical Lanzhou Jiaotong University
Priority to CN202311600155.4A priority Critical patent/CN117603049A/en
Publication of CN117603049A publication Critical patent/CN117603049A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a method for preparing isononanoate. According to the method, cobalt salt is used as a catalyst, polyion liquid is used as a ligand and a carrier, diisobutylene, CO and fatty alcohol are used as reactants, and isononanoate is obtained through a hydroesterification reaction. According to the invention, the cobalt salt catalyst and the polyion liquid form a complex in situ, after diisobutylene hydrogen esterification reaction is finished, the complex can be separated from a reaction system in a filtering and centrifuging mode, so that the catalyst can be recycled, the defects that the catalyst system is difficult to separate and cannot be recycled when the conventional diisobutylene hydrogen esterification reaction is used for preparing isononanoate are overcome, and the catalyst cost is reduced.

Description

Method and catalyst for preparing isononanoate
Technical Field
The invention relates to a method for preparing isononanoate through diisobutenyl hydroesterization.
Background
Isononanoic acid (3, 5-trimethylhexanoic acid) is a structurally branched C9 monocarboxylic acid, which has a wide range of uses. Can be used for synthesizing high-grade lubricating oil and paint, and has important application in microgel, surfactant, medical intermediate, metal soap, metal processing liquid and the like; can also be used for modifying alkyd resin, and can effectively improve yellowing resistance and impact resistance. Isononanoic acid is also used in the fields of cosmetics, stabilizers, tire adhesion aids, and the like. Wherein isononanoic acid ester prepared by reacting isononanoic acid with ethylene glycol can be used as a plasticizer of PVC or polyvinyl butyral film and a coalescing agent of polymer dispersion; isononanoic acid esters synthesized with polyols such as neopentyl glycol, trimethylol propane, ditrimethylol propane, pentaerythritol or dipentaerythritol are a wide variety of lubricating oil esters. In addition, the corresponding vinyl esters of isononanoic acid are commonly used as comonomers to improve the properties of polymers such as polyvinyl acetate, polyvinyl chloride, polystyrene and polyacrylates.
Currently, the industrial isononanoic acid preparation method generally adopts 2-ethylhexanol as an initial raw material, and the isononanoic acid is synthesized through the reaction processes of dehydration, hydroformylation, oxidation and the like (CN 104379543.A, CN 104520257A, CN 108047027A). The method has long process route and low product yield; the synthesis process mostly adopts homogeneous acid catalysis and high-pressure method, has high equipment requirement, has the problems of equipment corrosion, environmental pollution and the like, and limits the large-scale industrial application of the process. In 1955, koch et al reported a two-step medium pressure carbonylation process at a reaction temperature of 20 to 80℃and a pressure of 10MPa or less and catalyst H 2 SO 4 Under the action of the catalyst, the reactant olefin and CO coordinate with an acid catalyst to form a complex, and then the complex is hydrolyzed to synthesize carboxylic acid (chemical engineering progress, 1999,6,23-26 (36)). In 1988 Souma et al (society of organic Synthesis chemistry, 1990,48 (2): 93-101) developed a method for producing isononanoic acid by Koch carbonylation process, which was limited in development by the use of a metal carbonyl/strong acid catalyst system, which consumed large amounts of acid, serious equipment corrosion and environmental pollution.
In 2001, chen Jing et al reported that octacarbonyl cobalt/pyridine catalyzed diisobutenyl ester was prepared by the reaction of diisobutenyl ester at 120℃under 6.0MPa for 12 hours, with diisobutenyl conversion and methyl isononanoate selectivity reaching 70.8% and 84.6%, respectively (fine chemical, 2001,18 (2): 109-111). The methyl isononanoate is further hydrolyzed to form isononanoic acid. However, the catalyst system is difficult to separate and cannot be recovered and reused. Aiming at the problem, the invention loads the ionic liquid onto the polymer, and the metal cobalt salt and the polyionic liquid form a complex in situ, so that a method for preparing isononanoate through the diisobutylene hydrogen esterification reaction catalyzed by the polyionic liquid loaded with the metal cobalt salt is developed, and the separation and the reuse of the catalyst are realized.
Disclosure of Invention
The invention aims to overcome the defects that a catalyst system is difficult to separate and cannot be recycled when the existing diisobutenyl hydrogen esterification reaction is used for preparing isononanoate, and provides a method for preparing isononanoate by catalyzing diisobutenyl hydrogen esterification reaction through polyion liquid in-situ supported metal cobalt salt.
The technical scheme adopted by the invention for achieving the purpose is as follows:
the method uses cobalt salt as a catalyst, polyion liquid as a ligand and a carrier, diisobutylene, CO and fatty alcohol as reactants, and the isononanoate is obtained through a hydroesterization reaction.
The cobalt salt and the polyion liquid form a complex in situ, and after diisobutylene hydrogen esterification reaction is finished, the complex can be separated from a reaction system by means of filtration, centrifugation and the like, so that the catalyst can be recycled.
In the above method, the cobalt salt is selected from Co 2 (CO) 8 、CoCO 3 、Co(acac) 3 、Co(acac) 2 。
In the method, the dosage of the cobalt salt is 2-6wt% of the total feeding amount.
In the above method, the polyionic liquid is selected from the group consisting of polyvinyl-3-hexylimidazole iodisalt-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-butylimidazole iodisalt-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-ethylimidazole iodisalt-polyvinylpyridine-polydivinylbenzene, and polyvinyl-3-acetonitrile imidazole iodisalt-polyvinylpyridine-polydivinylbenzene.
In the method, the dosage of the polyionic liquid is 2-10 wt% of the total feeding amount.
In the above method, the fatty alcohol is methanol.
In the above method, the mass ratio of diisobutylene to methanol is 1 (2-15).
In the method, the reaction temperature is 140-160 ℃, the reaction time is 8-14 h, and the CO pressure is 6-8 MPa.
A catalyst system for diisobutenyl hydrogen esterification to prepare isononanoate, which consists of cobalt salt and polyion 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 the group consisting of polyvinyl-3-hexylimidazole iodides-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-butylimidazole iodides-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-ethylimidazole iodides-polyvinylpyridine-polydivinylbenzene, polyvinyl-3-acetonitrile imidazole iodides-polyvinylpyridine-polydivinylbenzene.
The polyionic liquid is obtained by mixing, heating and polymerizing 1-vinyl-3-alkyl imidazole iodized salt or 1-vinyl-3-acetonitrile imidazole iodized salt, 4-vinyl pyridine, divinylbenzene and an initiator in a solvent.
The molar ratio of the 1-vinyl-3-alkyl imidazole iodized salt or the 1-vinyl-3-acetonitrile imidazole iodized salt, the 4-vinyl pyridine and the divinylbenzene is 1 (1-2): 1.
The 1-vinyl-3-alkyl imidazole iodized salt is selected from 1-vinyl-3-hexyl imidazole iodized salt, 1-vinyl-3-butyl imidazole iodized salt and 1-vinyl-3-ethyl imidazole iodized salt.
The initiator can be 2,2' -azobisisobutyronitrile, and the dosage is 3-4wt% of the total mass of 1-vinyl-3-alkyl (or acetonitrile) imidazole iodized salt, 4-vinyl pyridine and divinylbenzene.
The temperature of the polymerization reaction is 60-90 ℃.
In the catalyst system, the mass ratio of the cobalt salt to the polyionic liquid is 1:1-1:2, preferably 1:1-1:1.5.
The total feeding amount of the invention refers to the sum of feeding amounts of cobalt salt, polyion liquid, diisobutylene and fatty alcohol.
Detailed Description
The technical scheme of the invention is further described in detail below by combining examples.
The two isomers of diisobutylene were 2, 4-trimethylpentene-1 and 2, 4-trimethylpentene-2, the content of 2, 4-trimethylpentene-1 in the commercial diisobutylene product used in the present invention was 77.2%, the content of 2, 4-trimethylpentene-2 was 22.4%, and the diisobutylene reacted with CO and fatty alcohol to give isononanoate as follows:
example 1
Preparation of polyvinyl-3-hexylimidazole iodate-polyvinylpyridine-polydivinylbenzene (2:1): 9.16g (0.03 mol) of 1-vinyl-3-hexylimidazole iodized salt, 6.30g (0.06 mol) of 4-vinylpyridine, 3.90g (0.03 mol) of divinylbenzene, 0.62g (3.2 wt%) of 2,2' -azobisisobutyronitrile were added to 200mL of ethanol at 90℃N 2 Stirring under protected conditions for 48h, then cooling to room temperature, and standing at room temperature for 12h. The solid powder is collected by filtration, washed three times with ethanol and diethyl ether in sequence, dried in vacuum for 12 hours for later use, and the polymer is abbreviated as: HVIMI-VPy-DVB (2:1).
Example 2
Preparation of polyvinyl-3-hexylimidazole iodate-polyvinylpyridine-polydivinylbenzene (1:1) As in example 1, the reaction starting material 1-vinyl-3-hexylimidazole iodate 9.16g (0.03 mol), 4-vinylpyridine in an amount of 3.15g (0.03 mol), divinylbenzene in an amount of 3.90g (0.03 mol), and 2,2' -azobisisobutyronitrile in an amount of 0.52g (3.2 wt%), the polymer was abbreviated as: HVIMI-VPy-DVB (1:1).
Example 3
Preparation of polyvinyl-3-butylimidazolium iodide-polyvinylpyridine-polydivinylbenzene (2:1) As in example 1, the starting materials were 8.31g (0.03 mol) of 1-vinyl-3-butylimidazolium iodide, 6.30g (0.06 mol) of 4-vinylpyridine, 3.90g (0.03 mol) of divinylbenzene, 0.59g (3.2 wt%) of 2,2' -azobisisobutyronitrile, which polymer was abbreviated as: BVIMI-VPy-DVB (2:1).
Example 4
Preparation of polyvinyl-3-butylimidazolium iodide-polyvinylpyridine-polydivinylbenzene (1:1) As in example 1, the starting materials were 8.31g (0.03 mol) of 1-vinyl-3-butylimidazolium iodide, 3.15g (0.03 mol) of 4-vinylpyridine, 3.90g (0.03 mol) of divinylbenzene, 0.49g (3.2 wt%) of 2,2' -azobisisobutyronitrile, which polymer was abbreviated as: BVIMI-VPy-DVB (1:1).
Example 5
Preparation of polyvinyl-3-ethylimidazolium iodide-polyvinylpyridine-polydivinylbenzene (2:1) As in example 1, 7.47g (0.03 mol) of 1-vinyl-3-ethylimidazolium iodide, 6.30g (0.06 mol) of 4-vinylpyridine, 3.90g (0.03 mol) of divinylbenzene, 0.57g (3.2 wt%) of 2,2' -azobisisobutyronitrile were used as starting materials, which was abbreviated as: EVIMI-VPy-DVB (2:1).
Example 6
Preparation of polyvinyl-3-ethylimidazolium iodide-polyvinylpyridine-polydivinylbenzene (1:1) As in example 1, 7.47g (0.03 mol) of 1-vinyl-3-ethylimidazolium iodide, 3.15g (0.03 mol) of 4-vinylpyridine, 3.90g (0.03 mol) of divinylbenzene, 0.46g (3.2 wt%) of 2,2' -azobisisobutyronitrile were used as starting materials, which was abbreviated as: EVIMI-VPy-DVB (1:1).
Example 7
Preparation of polyvinyl-3-acetonitrile-imidazole-iodide-polyvinylpyridine-polydivinylbenzene (2:1) As in example 1, 7.83g (0.03 mol) of 1-vinyl-3-acetonitrile-imidazole-iodide, 6.30g (0.06 mol) of 4-vinylpyridine, 3.90g (0.03 mol) of divinylbenzene, 0.58g (3.2 wt%) of 2,2' -azobisisobutyronitrile were used as the starting materials, and the polymer was abbreviated as: CNVIMI-VPy-DVB (2:1).
Example 8
Hydroesterification of diisobutylene:
into a 100mL reactor equipped with a bottom tube and a filter, 0.79g of catalyst Co was added in sequence 2 (CO) 8 0.83g HVIMI-VPy-DVB (1:1), 3.74g diisobutylene, 16.02g methanol. Replacing 3 times with CO of 1.5-2MPa, charging CO to 5.0MPa, heating to 150deg.C in 60min, stirring, and reacting at 8.0MPa for 12 hr. Cooling to room temperature, extruding the reaction liquid from the bottom inserting tube through a filter, and keeping the catalyst in a reaction kettle for repeated use, wherein the reaction liquid is analyzed by gas chromatography.The diisobutylene conversion was 88.0% and the methyl isononanoate selectivity was 91.4%.
Comparative example 1
Preparation of polyvinylpyridine-polydivinylbenzene (1:1) the same as in example 1 was carried out starting from 3.15g (0.03 mol) of 4-vinylpyridine, 3.90g (0.03 mol) of divinylbenzene, 0.23g (3.2 wt%) of 2,2' -azobisisobutyronitrile, which polymer was abbreviated as: VPy-DVB (1:1).
The polymer VPy-DVB (1:1) was used for the hydroesterfication of diisobutylene, in the same manner as in example 8, under the same reaction conditions of 0.79g Co 2 (CO) 8 1.09g of VPy-DVB (1:1), 3.74g of diisobutylene, 16.02g of methanol, and the reaction is carried out for 12 hours at 150 ℃ and 8.0MPa, the diisobutylene conversion rate is 86.7%, and the selectivity of methyl isononanoate is 88.4%.
Example 9
During the reaction of example 8, co 2 (CO) 8 Forming a complex with a polyion liquid HVIMI-VPy-DVB (1:1) in situ, after the reaction is finished, extruding a reaction solution through a filter, leaving the complex in a reaction kettle, adding reactants into the reaction kettle again without any post treatment to directly carry out the next hydroesterification reaction, and repeating the use each time (the reaction conditions are the same as those of example 8) as shown in the table 1:
number of repetitions Diisobutylene conversion 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 procedure of examples 10 to 35 was the same as in 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 of the examples
TABLE 3 diisobutylene conversion and methyl isononanoate selectivity for the examples
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A process for preparing isononanoate, characterized by: according to the method, cobalt salt is used as a catalyst, polyion liquid is used as a ligand and a carrier, diisobutylene, CO and fatty alcohol are used as reactants, and isononanoate is obtained through a hydroesterification reaction.
2. The method of claim 1, wherein: the cobalt salt is selected from Co 2 (CO) 8 、Co(acac) 3 、Co(acac) 2 。
3.A method according to claim 1 or 2, characterized in that: the dosage of the cobalt salt is 2-6wt% of the total feeding amount.
4. The method of claim 1, wherein: the polyionic liquid is selected from polyvinyl-3-hexyl imidazole iodized salt-polyvinyl pyridine-polydivinylbenzene, polyvinyl-3-butyl imidazole iodized salt-polyvinyl pyridine-polydivinylbenzene, polyvinyl-3-ethyl imidazole iodized salt-polyvinyl pyridine-polydivinylbenzene, polyvinyl-3-acetonitrile imidazole iodized salt-polyvinyl pyridine-polydivinylbenzene.
5. The method of claim 1 or 4, wherein: the dosage of the polyionic liquid is 2-10 wt% of the total feeding amount.
6. The method of claim 1, wherein: the fatty alcohol is methanol.
7. The method of claim 1, wherein: the reaction temperature is 140-160 DEG o C, the reaction time is 8-14 h, and the CO pressure is6~8MPa。
CN202311600155.4A 2023-11-28 2023-11-28 Method and catalyst for preparing isononanoate Pending CN117603049A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311600155.4A CN117603049A (en) 2023-11-28 2023-11-28 Method and catalyst for preparing isononanoate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311600155.4A CN117603049A (en) 2023-11-28 2023-11-28 Method and catalyst for preparing isononanoate

Publications (1)

Publication Number Publication Date
CN117603049A true CN117603049A (en) 2024-02-27

Family

ID=89954380

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311600155.4A Pending CN117603049A (en) 2023-11-28 2023-11-28 Method and catalyst for preparing isononanoate

Country Status (1)

Country Link
CN (1) CN117603049A (en)

Similar Documents

Publication Publication Date Title
CN109453815B (en) Organic phosphine-containing polymer carrier-loaded rhodium-based catalyst, and preparation and application thereof
CN109761811B (en) Preparation method of carboxylic ester
CN107417492A (en) A kind of method of controlled degradation recovery pet material
CN114522736B (en) Multiphase hydroformylation method of vinyl ester compound
CN104667977B (en) The catalyst system of hydroformylation of propene producing butyladehyde a kind of and use its method
US9260367B2 (en) Methods of converting polyols
CN107602369B (en) Preparation method of acrylic acid or acrylic ester
CN111111774A (en) Organic phosphine-containing polymer carrier loaded rhodium and heteropoly acid catalyst, preparation and application thereof
CN111574378B (en) Method for efficiently synthesizing dihydroxy ethyl terephthalate without catalysis
CN114849786A (en) Imidazole sulfonic acid ionic liquid based palladium-phosphine complex catalyst for synthesizing methyl propionate by ethylene methyl hydrogen esterification
CN117603049A (en) Method and catalyst for preparing isononanoate
CN111100000B (en) Method for synthesizing 3-methyl hydroxypropionate by cobalt catalysis
CN106431926B (en) The method for synthesizing 3- hydroxy propionate
CN110605145B (en) Catalyst for methyl hydrogen esterification reaction and method for preparing isononanoic acid
CN109678709B (en) Efficient preparation of methyl 3-hydroxypropionate
CN111875637B (en) Phosphine ligand and synthesis method and application thereof
CN108212150B (en) Rhodium-loaded liquid metal solution catalyst and preparation and application thereof
CN114315728A (en) Imidazole ionic liquid and application thereof in alcoholysis polymerization of 2, 5-furandicarboxylic acid ester
CN115108877B (en) Preparation method of 9, 10-dihydro anthracene
CN111039765A (en) Method for preparing 3-alkoxy propionaldehyde
CN107497494B (en) Catalyst composition for synthesizing methyl propionate from ethylene and synthesis method thereof
CN113402374B (en) Reaction system for preparing propionic acid by ethanol liquid-phase carbonyl synthesis
KR101593782B1 (en) Catalysts for polymerizing diene and diene polymerizaton method
CN114874078B (en) Synthesis method of propylene glycol phenyl ether with high isomer content
CN114436844B (en) Synthesis method of methyl glycolate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination