CN-122010692-A - Method for contact reaction of epoxy compound and hydroxy compound

Abstract

The invention relates to a method for the contact reaction of an epoxy compound and a hydroxyl compound. The method comprises the step of carrying out contact reaction on an epoxy compound and a hydroxyl compound under the condition of a catalyst, wherein the catalyst comprises a resin matrix and quaternary ammonium salt groups grafted on the resin matrix, and hydrocarbon groups grafted on the quaternary ammonium salt groups and the resin matrix are alkylene chains. By adopting the method to contact and react the epoxy compound and the hydroxyl compound, the conversion rate of the epoxy compound can reach more than 95 percent and the selectivity of the dialkyl glycol compound can reach more than 90 percent under relatively mild reaction conditions.

Inventors

• YU FENGPING
• WANG JIAHUA
• GE JUNWEI
• WANG YI
• ZHOU JIPENG
• HE WENJUN

Assignees

• 中国石油化工股份有限公司
• 中石化（上海）石油化工研究院有限公司

Dates

Publication Date

20260512

Application Date

20241111

Claims (10)

1. 1. A method for contact reaction of an epoxy compound and a hydroxyl compound is characterized in that the method comprises the contact reaction of the epoxy compound and the hydroxyl compound under the condition of a catalyst; The catalyst comprises a resin matrix and quaternary ammonium salt groups grafted on the resin matrix, wherein the quaternary ammonium salt groups are grafted on the resin matrix through alkylene chains.
2. 2. The process according to claim 1, wherein the resin matrix of the catalyst comprises at least two polystyrene segments, the polystyrene segments being linked by a crosslinker structural unit comprising ester groups and/or phenylene groups, and/or The total mass of the polystyrene segments is 20wt% to 95wt%, preferably 70wt% to 95wt%, of the total mass of the resin matrix, and the total mass of the cross-linking agent structural units is 5wt% to 80wt%, preferably 5wt% to 30wt%, of the total mass of the resin matrix.
3. 3. The method according to claim 1 or 2, wherein, The quaternary ammonium salt groups in the catalyst being grafted to the resin matrix via a C3-C5 alkylene chain, and/or The hydrocarbyl groups of the quaternary ammonium salt groups are each independently selected from alkyl groups, preferably C1-C6 alkyl groups, and/or The anions of the quaternary ammonium salt groups in the catalyst are at least one of bicarbonate ions, hydroxide ions, bisulfide ions, formate ions, acetate ions and citrate ions.
4. 4. A method according to any one of claim 1 to 3, wherein, The contact reaction is carried out in a fixed bed reactor, and/or The catalyst is packed in the reactor in at least three beds, and/or The average particle size of the catalyst packed in each bed in the reactor is gradually increased from layer to layer in the flow direction of the epoxy compound, and the increasing range is 0.1-0.5 mm/layer.
5. 5. The process according to claim 1 to 4, wherein, based on the total mass of the catalyst, The content of the resin matrix is 30-80%, preferably 40-70%, the content of the quaternary ammonium salt group is 15-65%, preferably 30-50%, the content of the alkylene chain is 5-20%, preferably 10-20%; preferably, the mass ratio of resin matrix to quaternary ammonium salt groups is 0.8-4.5:1, preferably 0.8-3:1.
6. 6. The method according to any one of claims 1 to 5, wherein the catalyst is prepared by a process comprising the steps of: (1) Preparing a resin matrix, namely mixing a styrene monomer and a crosslinking monomer in a solvent in the presence of an initiator to carry out copolymerization reaction; (2) The resin groups are subjected to an ammonification reaction and an ion exchange reaction in sequence.
7. 7. The method of claim 6, wherein, The styrene monomer is 1- (4-haloalkyl) -4-vinylbenzene, preferably the haloalkyl in 1- (4-haloalkyl) -4-vinylbenzene is bromoalkyl, and/or The crosslinking monomer is selected from at least one of di-alkenyl benzene, multi-alkenyl benzene and multi-unsaturated acid alcohol ester, preferably di-alkenyl benzene and/or multi-alkenyl benzene, and/or The initiator is at least one selected from benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide and cumene hydroperoxide, and/or The conditions of the copolymerization reaction comprise that the polymerization reaction temperature is 60-100 ℃ and/or the polymerization reaction time is 8-24 hours, preferably, the copolymerization reaction is firstly carried out for 1-3 hours at 65-75 ℃, then the polymerization reaction is carried out for 2-6 hours at 80-85 ℃, and finally the polymerization reaction is carried out for 3-6 hours at 90-98 ℃.
8. 8. The process according to any one of claims 1 to 7, wherein the epoxide compound is a 0-4 alkyl and/or aryl substituted alkylene oxide, preferably the alkylene oxide is ethylene oxide, Preferably, the alkyl is a C 1 -C 6 alkyl and the aryl is a C 6 -C 10 aryl.
9. 9. The method according to any one of claims 1-8, wherein the hydroxyl compound is selected from at least one of ethylene glycol, diethylene glycol and triethylene glycol, preferably ethylene glycol.
10. 10. The method of any one of claims 1-9, wherein the contacting reaction conditions comprise: At a temperature of 40-180 ℃, preferably 70-110 ℃, and/or A pressure of 0.1 to 10.0MPa, preferably 0.8 to 2.5MPa, and/or The molar ratio of hydroxyl compound to alkylene oxide is (1-50): 1, preferably (10-15): 1, and/or The liquid space velocity is 0.1-6.0h -1 , preferably 0.5-4.0h -1 .

Description

Method for contact reaction of epoxy compound and hydroxy compound Technical Field The invention relates to a method for the contact reaction of an epoxy compound and a hydroxyl compound. Background Diethylene glycol (DEG) is a colorless, odorless, transparent, hygroscopic, viscous liquid readily soluble in polar solvents such as water, alcohols, acetone, diethyl ether, ethylene glycol, and the like, and has chemical properties similar to Ethylene Glycol (EG). Diethylene glycol can be directly used as solvent such as nitrocellulose, resin, grease, printing ink and the like, natural gas dehydration desiccant, aromatic separation extractant, textile lubricant, softener and finishing agent, can also be used as antifreezing agent component in brake fluid and compressor lubricating oil, and can also be used for preparing cleaning agent. As a byproduct in the process of producing ethylene glycol by an ethylene oxide hydration method, the yield of diethylene glycol is limited by the running condition of an ethylene glycol device, and the amount of the diethylene glycol serving as a byproduct is generally 8-10% of the yield of ethylene glycol. The current ethylene oxide/ethylene glycol production technology is mature, and the technology is mainly provided by DOW, SD, SHELL and other large chemical enterprises. The main process is that ethylene oxide and excessive water react in a tubular reactor at 150-200 ℃ and 1.5-2.5 MPa, ethylene glycol is prepared by direct liquid phase hydration, and meanwhile, diethylene glycol, triethylene glycol and polyethylene glycol are byproducts. The molar ratio of the main products in the industrial production is approximately EG: DEG: TEG=100:10:1. And cooling the ethylene glycol solution obtained by the reaction through a heat exchanger, then pumping the ethylene glycol solution to evaporate and concentrate, and obtaining pure ethylene glycol, diethylene glycol, triethylene glycol and other components respectively after multi-effect evaporation. With the increase of the downstream demand of diethylene glycol, the productivity, yield and demand of diethylene glycol will all be on the rise. CN215538513U discloses a molecular distillation recovery device for polyethylene glycol as a byproduct of ethylene glycol process, which can make the interior of the molecular distillation device obtain very high vacuum degree, reduce the heating time of polyethylene glycol and heavy components in the material, shorten the distance between the heating surface and the condensing surface, avoid further polymerization or deterioration of heavy components in the material, and improve the recovery rate of polyethylene glycol. CN112321397a discloses a new method for increasing the production of triethylene glycol by a EOEG device, a pipeline for recycling diethylene glycol or a pipeline for recycling crude diethylene glycol and triethylene glycol mixed liquid is added to the original process, so that the recycled diethylene glycol or crude diethylene glycol and triethylene glycol mixed liquid enters a hydration reactor to be hydrated with ethylene oxide to generate triethylene glycol, the concentration of diethylene glycol in the hydration reactor is increased, and the purpose of increasing the production of triethylene glycol is achieved. The method for producing diethylene glycol is limited by the productivity of EOEG devices, and the yield of diethylene glycol can be regulated only in a certain range, so that the production problem of diethylene glycol is not fundamentally solved. Disclosure of Invention The invention aims to solve the problems of low efficiency (less direct products and more byproducts) and high temperature need to be adopted in the direct reaction of the epoxy compound and the hydroxyl compound in the prior art, and provides a method for the contact reaction of the epoxy compound and the hydroxyl compound, which has the characteristics of high efficiency, mild reaction conditions and high raw material utilization rate. In order to achieve the above object, the present invention provides a method for contact-reacting an epoxy compound with a hydroxyl compound, which comprises the step of contact-reacting an epoxy compound with a hydroxyl compound in the presence of a catalyst comprising a resin substrate and quaternary ammonium salt groups grafted to the resin substrate, the quaternary ammonium salt groups being grafted to the resin substrate via alkylene chains. Through the technical scheme, the invention has the following advantages: by adopting the method to contact and react the epoxy compound with the hydroxyl compound, the conversion rate of the epoxy compound can reach more than 95 percent and the selectivity of a direct reaction product can reach more than 90 percent under relatively mild reaction conditions. Drawings FIG. 1 is an infrared spectrum of Cat-A2. Detailed Description The endpoints and any values of the ranges disclosed herein are not limited to the precise range