Unlock instant, AI-driven research and patent intelligence for your innovation.

Hydroformylation catalyst composition and method for preparing hydroxybutyraldehyde through hydroformylation reaction of allyl alcohol

A technology of hydroformylation catalyst and composition, which is applied in the direction of carbon monoxide reaction preparation, catalytic reaction, organic compound/hydride/coordination complex catalyst, etc., which can solve the problem of catalyst oil solubility and product separation difficulties, and the high temperature performance of rhodium catalyst Poor, can not use higher olefin carbonylation and other problems, to achieve the effect of improving catalytic conversion rate and conversion rate, strong catalytic activity and stability, strong Π electron accepting ability

Pending Publication Date: 2022-02-01
WANHUA CHEM GRP CO LTD
View PDF11 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the positive and negative ratio of the product is designed to be 7-10, and it is difficult to maintain a low level in actual operation, and the actual adjustment range is limited, which is not enough for flexible production to meet market demand
[0004] In addition, taking the oil-soluble carbonyl rhodium phosphine catalyst with triphenylphosphine as the ligand as an example, the defects of this type of catalyst include: ① the rhodium catalyst has poor high-temperature performance and cannot be used for the carbonylation of advanced olefins; The catalytic effect of olefins is good, but the activity to internal olefins is poor; ③In order to increase the normal isomerization ratio of the product, the amount of triphenylphosphine needs to be added in a large excess; ④The catalyst is oil-soluble and the product separation is also difficult, making the post-treatment more complicated ; ⑤ Rhodium is rare as a precious metal resource, expensive, and its recycling cost is relatively high
[0005] The method for preparing hydroxybutyraldehyde by allyl alcohol hydroformylation described in the patent CN102428062A has a low product yield and poor economy; and a kind of catalytic reaction system for producing 4-hydroxybutyraldehyde described in the patent CN101522602A and CN101652179A, although The product yield has been improved, but the obtained product has a very high ratio of 4-hydroxybutyraldehyde: 2-methyl-3-hydroxypropanal, it is difficult to achieve a stable product ratio adjustment, and 2-methyl-3 Efficient Production of -Hydroxypropionaldehyde

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Hydroformylation catalyst composition and method for preparing hydroxybutyraldehyde through hydroformylation reaction of allyl alcohol
  • Hydroformylation catalyst composition and method for preparing hydroxybutyraldehyde through hydroformylation reaction of allyl alcohol
  • Hydroformylation catalyst composition and method for preparing hydroxybutyraldehyde through hydroformylation reaction of allyl alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0054] Add 179g of the raw material 2-hydroxybenzyl alcohol derivative (1mol) (the structure is shown in the following formula 1-1) into 600ml of dichloromethane and mix evenly. mol) catalyzed reaction, after stirring for 2 hours, a quinone intermediate was obtained, and then 166.16 g of triethyl phosphite (1 mol) was added to the system, and the cyclization reaction occurred overnight at 60° C. (12 hours), and the reaction progress was monitored by pointing a plate. After the reaction was completed, the solvent dichloromethane was removed by rotary distillation, and eluted by column chromatography to obtain 168 g of oxygen-containing heterocyclic phosphoric acid ester. First Ligand A 1 , the structure is shown in the following formula 1-2.

[0055]

[0056] The yield was 80%. NMR data support is as follows:

[0057] 1 H NMR (400MHz, CDCl 3 ,TMS):δ0.89(t,J=8Hz,3H),2.28(s,3H),3.41-3.72(m,1H),3.87-4.14(m,1H),7.06-7.12(m,3H) ,7.16-7.19(m,2H),7.21-7.28(m,3H),7.33-7.41(m,4...

Embodiment 2

[0059] Add 193g of the raw material 2-phenol hydroxybenzyl alcohol derivative (1mol) (the structure is shown in the following formula 2-1) into 500ml of chloroform and mix evenly. ) catalyzed reaction, and after stirring for 2 hours, 166.16 g of triethyl phosphite (1 mol) was added to the system, and the cyclization reaction occurred overnight at 50° C. (20 hours), and the reaction progress was monitored by pointing a plate. After the reaction was completed, the solvent chloroform was removed by rotary distillation, and eluted by column chromatography to obtain 183.68 g of oxygen-containing heterocyclic phosphate, referred to as the first ligand A 2 , the structure is shown in the following formula 2-2.

[0060]

[0061] The yield was 82%. NMR data support is as follows:

[0062] 1 H NMR (400MHz, CDCl 3 ,TMS):δ0.90(td,J=8,0.48Hz,3H),2.34(s,3H),2.27(s,3H),3.39-3,49(m,1H),3.86-3.94(m ,1H),6.91(d,J=8Hz,1H),6.95(s,1H),7.06(d,J=8Hz,1H),7.19(t,J=8Hz,1H),7.26(t,J= 8Hz, 2H), ...

Embodiment 3

[0064] Add 277g of the raw material 2-phenol hydroxybenzyl alcohol derivative (1mol) (the structure is shown in the following formula 3-1) into 800ml of benzene and mix evenly. ) catalyzed reaction, and after stirring for 2 hours, 166.16 g of triethyl phosphite (1 mol) was added to the system, and the cyclization reaction occurred overnight at 70° C. (10 hours), and the reaction progress was monitored by pointing a plate. After the reaction was completed, the solvent benzene was removed by rotary distillation, and eluted by column chromatography to obtain 249.48 g of oxygen-containing heterocyclic phosphate. First Ligand A 3 , the structure is shown in the following formula 3-2.

[0065]

[0066] The yield was 81%. NMR data support is as follows:

[0067] 1 H NMR (400MHz, CDCl 3 ,TMS):δ1.35(td,J=8,0.56Hz,3H),2.27(s,3H),2.30(s,3H),3.38-3.48(m,1H),3.85-3.95(m,1H ), 7.00(t, J=8Hz, 2H), 7.08(d, J=8Hz, 1H), 7.21(t, J=8Hz, 1H), 7.27(t, J=8Hz, 2H), 7.32-7.38( m,5H),7.53(d,J...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a hydroformylation catalyst composition and a method for preparing hydroxybutyraldehyde through hydroformylation reaction of allyl alcohol. The catalyst composition comprises a solvent and a complex formed in the solvent, wherein the complex comprises a first ligand, a second ligand and a metal active component; the metal active component is rhodium; and the first ligand is a composition of one or more of phosphine-containing ligands as shown in a structural formula I in the specification. According to the catalyst composition disclosed by the invention, a large normal / isomeric ratio adjustment range of a product in the process of producing aldehyde through the hydroformylation reaction of allyl alcohol can be realized, a lower low normal / isomeric ratio is realized, and meanwhile, the selectivity and the stability of the catalyst under the working condition of the low normal / isomeric ratio are improved.

Description

technical field [0001] The invention belongs to the technical field of catalysts, in particular to a hydroformylation catalyst composition and its application in the preparation of hydroxybutyraldehyde by hydroformylation of allyl alcohol. Background technique [0002] The hydroformylation reaction of allyl alcohol is of great industrial significance, and its reaction products include 4-hydroxybutyraldehyde and 2-methyl-3-hydroxypropanal. Among them, 4-hydroxybutyraldehyde can be used for hydrogenation to produce 1,4-butanediol. 1,4-butanediol is an important basic organic chemical and fine chemical raw material with a wide range of uses. It can be used as a raw material to derive many A high value-added fine chemical product; 2-methyl-3-hydroxypropanal, as a reaction by-product, generally enters the subsequent hydrogenation process together as a by-product of 1,4-butanediol hydrogenation 2-methyl-1 , 3-propanediol exists and has received less attention from industry. Howe...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07C45/50C07C47/19
CPCB01J31/2414B01J31/185C07C45/50B01J2231/321B01J2531/822C07C47/19
Inventor 梁健姜海林方子来赵孟雨刘运海黎源
Owner WANHUA CHEM GRP CO LTD