Modified phenolic resin as well as preparation method and application thereof

Abstract

The invention discloses modified phenolic resin as well as a preparation method and application thereof, the modified phenolic resin is prepared by carrying out chemical modification treatment on phenolic resin, and the chemical modification treatment comprises sulfonation treatment, silane modification treatment, titanate modification treatment and further crosslinking treatment; the modified phenolic resin exists in the form of modified phenolic resin particles, the compressive strength of a single particle is more than 100N, and the hydrogen ion content of each gram of dry resin is more than 1.5 mmol; the swelling degree in methanol and methyl propionate is tested to be less than or equal to 5% at high temperature and high pressure; the modified phenolic resin is used as solid acid to be applied to carbonylation synthesis reaction, agglomeration and inactivation of precious metal Pd can be effectively reduced, loss of a catalyst is reduced, meanwhile, existence of the modified phenolic resin provides a necessary acid environment for a system to ensure activity of the catalyst, the modified phenolic resin is not prone to evaporation from the system due to the high-boiling-point characteristic of the modified phenolic resin, and the service life of the catalyst is prolonged. Therefore, the effect of the catalytic promoter can be continuously provided.

Description

Technical Field

[0001] This invention relates to the field of fine chemical technology, specifically to a modified phenolic resin, its preparation method, and its applications. Background Technology

[0002] Methyl methacrylate (MMA) is an important chemical product, mainly used in the production of PMMA, surface coatings, and PVC additives. It is widely used in the automotive, construction, medical, electronics, textile printing and dyeing, coatings, adhesives, leather processing chemicals, and resin processing industries, making it an indispensable chemical raw material for national economic development. Globally, the industrial production processes for MMA primarily utilize the acetone cyanohydrin (ACH) process, the isobutylene process, and the ethylene process. The ethylene process mainly involves the carbonyl synthesis reaction of ethylene, carbon monoxide (CO), and methanol under the action of a catalyst to produce methyl propionate. Methyl propionate then undergoes an aldol condensation reaction with formaldehyde to produce MMA. This process has the advantages of mild reaction conditions and low production costs. Methods for synthesizing methyl propionate have been widely reported in literature and patents. Relevant literature reports methods for synthesizing methyl propionate from ethylene, CO, and methanol under the catalysis of palladium, organophosphorus ligands, and acid additives.

[0003] However, in practice, existing preparation processes still have the following problems: 1. Deactivation and loss of palladium catalyst: During the reaction, metallic Pd easily adheres to the reactor wall and the agitator. The adhered metallic Pd tends to attract each other and cluster, forming "palladium black" over time (the formation of palladium black is essentially the irreversible reduction and aggregation of active centers). This not only leads to the loss of active centers of the homogeneous catalyst, but the adhered "palladium black" also acts as an adsorption surface, accelerating further aggregation and deactivation of palladium in the solution, reducing catalytic efficiency and increasing the cost of precious metals. 2. Acid loss problem: Commonly used liquid acid co-catalysts, such as methanesulfonic acid, easily form low-boiling-point esters with methanol in the reaction system, which are distilled off along with the product methyl propionate, affecting product quality; moreover, liquid acids easily form metal salts and are lost. In addition, the decrease in system acidity requires continuous replenishment of acid, increasing costs, etc.

[0004] It should be noted that the information disclosed in the background section above is only used for understanding the background of this application. Therefore, the background section of this invention may include background information about the problems or environment of this invention, and is not necessarily a description of prior art. Thus, the content included in the background section does not constitute an admission of prior art by the applicant. Summary of the Invention

[0005] The purpose of this invention is to overcome one or more shortcomings of the prior art and provide a novel modified phenolic resin.

[0006] Furthermore, the modified phenolic resin of the present invention can be used as an acid additive in the carbonyl synthesis reaction to prepare methyl propionate, which can simultaneously solve problems such as palladium deactivation and loss, and acid loss.

[0007] The present invention also provides a method for preparing modified phenolic resin.

[0008] The present invention also provides the application of the above-mentioned modified phenolic resin and the composite catalytic system containing the above-mentioned modified phenolic resin in carbonylation reactions, such as the application in the carbonyl synthesis reaction to prepare methyl propionate or its derivatives.

[0009] To achieve the above objectives, the present invention employs the following technical solution: A modified phenolic resin, wherein the modified phenolic resin is prepared by chemically modifying phenolic resin, the chemical modification treatment including sulfonation treatment, silane modification treatment and titanate modification treatment. The modified phenolic resin exists in the form of modified phenolic resin particles, and the compressive strength of a single particle of the modified phenolic resin is greater than or equal to 100N. The modified phenolic resin has a hydrogen ion content of greater than or equal to 1.5 mmol per gram of dry resin; and in methanol and / or methyl propionate at 100°C and 1.3 MPa, the swelling degree is less than or equal to 5% within a 6-month testing period.

[0010] In some embodiments of the present invention, the compressive strength of a single particle of the modified phenolic resin granules is 120-200N, and more specifically 140-180N.

[0011] In some embodiments of the present invention, the particle size of the modified phenolic resin particles is mainly 2-4 mm. For example, in an aggregate of modified phenolic resin particles, the modified phenolic resin particles with a particle size of 2-4 mm can account for more than 90% or even more than 95% of the total number.

[0012] In some embodiments of the present invention, the phenolic resin is used as a raw material in the form of phenolic resin particles for the chemical modification treatment.

[0013] In some embodiments of the present invention, the hydroxyl value of the phenolic resin is 100-250 mgKOH / g, for example, it can be 100 mgKOH / g, 110 mgKOH / g, 120 mgKOH / g, 130 mgKOH / g, 140 mgKOH / g, 150 mgKOH / g, 160 mgKOH / g, 170 mgKOH / g, 180 mgKOH / g, 190 mgKOH / g, 200 mgKOH / g, 210 mgKOH / g, 220 mgKOH / g, 230 mgKOH / g, 240 mgKOH / g, 250 mgKOH / g, etc.

[0014] In some embodiments of the present invention, the hydrogen ion content per gram of dry resin of the modified phenolic resin is 1.5-5.0 mmol, for example, it can be 1.5-3.5 mmol, 2.0-4.0 mmol, etc.

[0015] In some embodiments of the present invention, the swelling degree of the modified phenolic resin is 0-4%. The swelling degree can be 0 in a short time, and even over a period of up to six months, the swelling degree can still be less than 5%, or even 3%. For example, it can be 0, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, etc.

[0016] In some embodiments of the present invention, the chemical modification treatment further includes a crosslinking treatment, which includes a heat treatment step in nitrogen and / or an inert gas; further, the heat treatment temperature is 180-220°C, for example, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, etc.

[0017] In some embodiments of the present invention, the chemical modification treatment is carried out in the order of sulfonation treatment, silane modification treatment, titanate modification treatment and crosslinking treatment.

[0018] In some embodiments of the present invention, the sulfonation treatment includes sulfonating a sulfonating agent with a phenolic resin; furthermore, controlling the sulfonation reaction to be carried out at a temperature less than or equal to 5°C helps to avoid degradation or excessive oxidation of the resin skeleton.

[0019] In some embodiments of the present invention, the sulfonating agent includes one, two or more combinations selected from fuming sulfuric acid, concentrated sulfuric acid with a mass concentration of 90%-98.5%, and sulfur trioxide.

[0020] In some embodiments of the present invention, the silane modification treatment includes modifying the sulfonated phenolic resin with a silane coupling agent; further, the mass of the silane coupling agent is 0.1%-0.5% of the mass of the sulfonated phenolic resin.

[0021] In some embodiments of the present invention, the titanate modification treatment includes modifying the silane-modified phenolic resin with a titanate coupling agent; further, the mass of the titanate coupling agent is 0.5%-1% of the mass of the silane-modified phenolic resin.

[0022] Another technical solution provided by the present invention: a method for preparing modified phenolic resin, the preparation method comprising: (1) Sulfonation treatment: Phenolic resin particles are placed in an inert solvent, and a sulfonating agent is added to carry out a sulfonation reaction, while the temperature of the sulfonation reaction is controlled to be less than or equal to 5°C, to obtain a first intermediate. (2) Silane modification treatment: The first intermediate is added to an aqueous solution of a silane coupling agent to react and generate a second intermediate; (3) Titanate modification treatment: The second intermediate is reacted with a titanate coupling agent in a solvent under heating conditions to generate a third intermediate; (4) Crosslinking treatment: The third intermediate was heat-treated in a protective atmosphere to obtain a granular modified phenolic resin.

[0023] In some embodiments of the present invention, the phenolic resin particles of the desired particle size can be commercially available, or the phenolic resin particles can be prepared by dispersing an aqueous solution of phenol, formaldehyde, and an alkaline reagent in an organic solvent containing a stabilizer under stirring and at a temperature of 90-100°C (e.g., 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, etc.) to generate phenolic resin particles.

[0024] Further, the molar ratio of the phenol, formaldehyde, and alkaline reagent is 1:1-1.5:0.02-0.1. The values ​​in the range "1-1.5" can be 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, etc.; the values ​​in the range "0.02-0.1" can be 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, etc.

[0025] Furthermore, the alkaline reagent includes one, two, or more combinations selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and ammonia water.

[0026] Furthermore, the stabilizer comprises one, two or more combinations selected from polyvinyl alcohol (PVA), sodium benzenesulfonate, sodium stearate, and sodium octadecyl alcohol.

[0027] Furthermore, the mass of the stabilizer is 10%-20% of the mass of the phenol, for example, it can be 10%, 12%, 15%, 16%, 18%, 19%, etc.

[0028] Furthermore, the organic solvent includes one, two or more combinations selected from dichloroethanol, dichloro-2-propanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol and N-methylpyrrolidone (NMP).

[0029] Furthermore, the mass of the organic solvent fed is 50%-100% of the mass of the phenol, for example, it can be 50%, 60%, 70%, 80%, 90%, 100%, etc.

[0030] Furthermore, the stirring speed under the stirring conditions is 100-200 rpm.

[0031] In some embodiments of the present invention, the sulfonating agent includes one, two or more combinations selected from fuming sulfuric acid, concentrated sulfuric acid with a mass concentration of 90%-98.5%, and sulfur trioxide; Furthermore, the mass of the sulfonating agent is 50%-200% of the mass of the phenolic resin before sulfonation, for example, it can be 50%, 80%, 110%, 140%, 170%, 200%, etc.

[0032] In some embodiments of the present invention, the inert solvent in the sulfonation process includes dichloroethane and / or ethyl acetate. The use of an inert solvent helps with mass transfer and temperature control, and reduces local overheating.

[0033] Furthermore, the mass of the inert solvent is 150%-250% of the mass of the phenolic resin before sulfonation, for example, it can be 150%, 170%, 190%, 210%, 230%, 250%, etc.

[0034] Further, in step (1), after the feeding is completed, the reaction time is 1 to 3 hours, and after washing, the first intermediate is obtained.

[0035] In some embodiments of the present invention, in the sulfonation treatment, the sulfonation reaction is followed by washing with a detergent, the detergent comprising dilute sulfuric acid and deionized water.

[0036] Furthermore, the dilute sulfuric acid is an aqueous solution of sulfuric acid with a concentration of 0.1~0.5 mol / L, for example, the concentration can be 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, etc.

[0037] Furthermore, the mass of the dilute sulfuric acid is 5 to 20 times the mass of the phenolic resin before sulfonation, for example, it can be 5 times, 7 times, 9 times, 11 times, 15 times, 18 times, 20 times, etc.

[0038] Furthermore, the quality of the deionized water is not required; it is sufficient to wash the resin until it is neutral.

[0039] In some embodiments of the present invention, the mass concentration of the silane coupling agent aqueous solution is 0.5%-2.0%, for example, it can be 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2.0%, etc.; further, the silane coupling agent aqueous solution is formed by dispersing the silane coupling agent in water; even further, the silane coupling agent includes aminosilane coupling agents and / or epoxysilane coupling agents; even further, the mass of the silane coupling agent is 0.1%-0.5% of the mass of the first intermediate, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, etc.

[0040] According to some specific aspects of the present invention, the aminosilane coupling agent includes KH-550 (γ-aminopropyltriethoxysilane) and KH-792 (N-β-aminoethyl-γ-aminopropyltrimethoxysilane).

[0041] According to some specific aspects of the present invention, the epoxy silane coupling agent includes γ-glycidoxypropyltrimethoxysilane, etc.

[0042] According to some specific aspects of the invention, the silane coupling agent comprises 3-(phenylamino)propyltrimethoxysilane (silane coupling agent Y-9669).

[0043] Furthermore, in step (2), the reaction time is 0.5 to 2 hours.

[0044] In some embodiments of the present invention, the titanate coupling agent comprises one, two or more combinations selected from tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, n-butyl titanate, tetraisobutyl titanate, di(acetylacetonyl)diisopropyl titanate, isopropoxytris(dioctyl phosphate) titanate, isopropyltrioleoyloxy titanate, and triisostearate isopropyl titanate; furthermore, the mass of the titanate coupling agent is 0.5%-1% of the mass of the second intermediate, for example, it can be 0.5%, 0.6%, 0.7%, 0.8%, 1.0%, etc.

[0045] In some embodiments of the present invention, during the titanate modification treatment, the heating conditions are controlled to carry out the reaction at 50-90°C. Further, the reaction is carried out in a protective atmosphere, which is formed by introducing nitrogen and / or an inert gas. Even further, the heating conditions are controlled to carry out the reaction at 50-75°C.

[0046] In some embodiments of the present invention, the titanate coupling agent is added by adding a titanate coupling agent solution. Further, the mass concentration of the titanate coupling agent solution is 1%-10%, and more specifically, 2%-8%. According to a specific aspect of the present invention, a titanate coupling agent solution with a mass concentration of 5% can be used.

[0047] Furthermore, a titanate coupling agent solution is prepared by dispersing the titanate coupling agent in a solvent.

[0048] Furthermore, the solvent in the titanate coupling agent solution is a mixture of water and alcohol, preferably, water and alcohol are mixed at a mass ratio of 1:4-6. According to one specific aspect of the invention, water and alcohol are mixed at a mass ratio of 1:5.

[0049] Furthermore, the alcohol can be ethanol or the like.

[0050] In some embodiments of the present invention, in the titanate modification treatment, the titanate coupling agent is added dropwise to a solvent in which the second intermediate is dispersed. Further, the solvent includes toluene and xylene, and can be used alone or in combination with one or more of ethyl acetate, butyl acetate, cyclohexyl acetate, ethyl propionate, methyl propionate, methyl ethyl ketone, cyclohexanone, cyclopentanone, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide. Even further, the mass of the solvent added is 50%-200% of the mass of the second intermediate, for example, 50%, 100%, 150%, 200%, etc.

[0051] Furthermore, in step (3), the reaction time is 2 to 5 hours.

[0052] In some embodiments of the present invention, the temperature of the heat treatment is 180-220°C.

[0053] Furthermore, in step (4), the reaction time is 2 to 5 hours.

[0054] Another technical solution provided by the present invention: a composite catalytic system, the composite catalyst system comprising: Group VIII metals or their compounds; Phosphorus-containing ligands and / or nitrogen-containing ligands; The modified phenolic resin described above, or the modified phenolic resin prepared by the method described above.

[0055] In some embodiments of the present invention, the Group VIII metal or its compounds include one, two or more combinations selected from tris(dibenzylacetone)palladium, dichlorodiamminepalladium, dinitrosodiamminepalladium, [Rh(COD)Cl]2, [Ir(COD)Cl]2, tetratetraphenylphosphine palladium, palladium dichloride, acetylated palladium, palladium acetate, dichloro(1,5-cyclooctadiene)palladium, bis(diphenylmethyleneacetone)palladium, bis(triphenylphosphine)palladium dichloride, and bis(acetonitrile)dichloropalladium.

[0056] In some embodiments of the present invention, the phosphorus-containing ligand comprises a selection from N,N-bis(di-tert-butylphosphine)-ethylenediamine, N,N-bis(diisopropylphosphine)-ethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-dimethylethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-diethylethylenediamine, N,N-bis(di-tert-butylphosphine)-N,N-diisopropylethylenediamine, bis(diisopropylphosphino)o-xylene, bis(di-tert-butylphosphino)o-xylene, bis(cyclohexylphosphino)o-xylene, 1, One, two, or a combination of 1'-bis(diphenylphosphino)ferrocene, 1,1'-bis(diisopropylphosphino)ferrocene, 1,1'-bis(diisobutylphosphino)ferrocene, 1,1'-bis(dipropylphosphino)ferrocene, 1,1'-bis(dicyclohexylphosphino)ferrocene, 1,1'-bis(isopropylcyclohexylphosphino)ferrocene, 1,1'-bis(di-tert-butylphosphino)ferrocene, 1,2-bis-(di-tert-butylphosphinomethyl)benzene, and 1,2-bis-(di-tert-pentylphosphinomethyl)benzene.

[0057] In some embodiments of the present invention, the nitrogen-containing ligand comprises one, two or more combinations selected from (1,3-bis(2-pyridyl))benzene, 1,3-bis(dimethylaminomethyl)benzene, 1,3-bis(methylethylaminomethyl)benzene; 1,3-bis(diethylaminomethyl)benzene, 1,3-bis(diphenylaminomethyl)benzene, 1,3-bis(dicyclohexylaminomethyl)benzene; 1,3-bis(dibenzylaminomethyl)benzene, 5,5'-divinyl-2,2'-bipyridine, and 4,4'-divinyl-2,2'-bipyridine.

[0058] In some embodiments of the present invention, the mass ratio of the group VIII metal or its compound, the phosphorus-containing ligand and / or nitrogen-containing ligand and the modified phenolic resin is 1:1-5:10-100.

[0059] Furthermore, in this invention, the numerical range "1-5" can be 1, 1.2, 1.5, 1.8, 2.0, 2.2, 2.5, 2.8, 3.0, 3.2, 3.5, 3.8, 4.0, 4.2, 4.5, 4.8, 5.0, etc.

[0060] Furthermore, in this invention, the numerical range "10-100" can be 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 50, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55; 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, etc.

[0061] Another technical solution provided by the present invention is: a modified phenolic resin as described above, or a modified phenolic resin prepared by the preparation method of the modified phenolic resin as described above, or the application of the composite catalytic system as described above in carbonylation reaction.

[0062] Furthermore, the carbonylation reaction includes the carbonylation of an olefin to synthesize methyl propionate or a derivative thereof.

[0063] Furthermore, when applied in carbonylation reactions, the modified phenolic resin of the present invention serves as a solid acid catalyst.

[0064] Another technical solution provided by the present invention: a method for preparing methyl propionate or its derivatives, the method comprising: reacting carbon monoxide, olefin and alkyl alcohol in the presence of the above-described composite catalytic system to generate methyl propionate or its derivatives.

[0065] Furthermore, the olefin may be ethylene, propylene, butene, etc.

[0066] Furthermore, the alkyl alcohol can be methanol, ethanol, propanol, etc.

[0067] In some embodiments of the present invention, when it is necessary to prepare methyl propionate, ethylene is selected as the olefin and methanol is selected as the alkyl alcohol.

[0068] Furthermore, when methyl propionate is to be prepared, the olefin shown is mixed with carbon monoxide at a molar ratio of 3.5-5.0:1 and then introduced into the system. Even further, when methyl propionate is to be prepared, the olefin shown is mixed with carbon monoxide at a molar ratio of 3.9-4.2:1 and then introduced into the system.

[0069] Furthermore, when preparing methyl propionate, the stirring speed is 100-1000 r / min, the reaction pressure is 1.0-1.5 MPa, the reaction temperature is 50-70℃, and the reaction time is 60-240 min. Even further, when preparing methyl propionate, the stirring speed is 400-600 r / min, the reaction pressure is 1.1-1.3 MPa, the reaction temperature is 55-65℃, and the reaction time is 100-150 min.

[0070] Due to the application of the above-mentioned technical solution, the present invention has the following advantages compared with the prior art: This invention innovatively provides a novel modified phenolic resin that can be used as an acid auxiliary in carbonyl synthesis reactions to prepare methyl propionate or its derivatives, and can simultaneously solve problems such as palladium deactivation and loss, and acid loss.

[0071] Furthermore, the modified phenolic resin of the present invention possesses high acidity, excellent mechanical strength, and solvent swelling resistance. It can serve as a novel solid acid catalyst that effectively prevents the deactivation and loss of Pd catalyst, solving the problem of deactivation and loss of palladium catalyst due to agglomeration and adhesion in the ethylene carbonylation reaction. It provides a stable and non-leaking acidic environment, avoiding product quality and replenishment problems caused by liquid acid. Attached Figure Description

[0072] Figure 1 This is a schematic diagram illustrating the presence and elimination of Pd black in this invention; Figure 2 This is a schematic diagram illustrating the generation and attachment of Pd clusters in this invention; Figure 3This is a schematic diagram illustrating the desorption of Pd clusters by modified phenolic resin in this invention. Figure 4 This is a schematic diagram illustrating how modified phenolic resin causes Pd clusters to split in this invention. Detailed Implementation

[0073] This invention provides a novel solid acid catalyst—modified phenolic resin—that combines high acidity, excellent mechanical strength, solvent swelling resistance, and effectively prevents Pd catalyst deactivation and loss, as well as a method for preparing the modified phenolic resin and its applications. For example, it can be used to prepare a composite catalytic system, which can be used as a catalyst in carbonylation reactions. The carbonylation reaction can be used to synthesize methyl propionate or its derivatives from olefin carbonylation reactions.

[0074] Furthermore, the present invention provides a method for preparing a modified phenolic resin, the method comprising: (1) Preparation of phenolic resin particles: A suspension polymerization method is used to disperse an aqueous solution of phenol, formaldehyde, and an alkaline catalyst in an oil phase (organic solvent, such as glycerol, NMP, etc.) in the presence of a stabilizer (such as PVA), and then react with the solution under stirring at 90-100°C to form phenolic resin particles. In the preparation process, for example, the stabilizer can be dispersed in the oil phase first, and then the aqueous solution can be added to the oil phase under stirring conditions for further reaction. Furthermore, the above method can be used to produce a three-dimensional network of phenolic resin; (2) Sulfonation treatment: The obtained phenolic resin particles were placed in an inert solvent, and a sulfonating agent (such as fuming sulfuric acid) was slowly added to carry out the sulfonation reaction. After the reaction, the mixture was washed with dilute acid and deionized water until the washing solution was neutral. The purpose of washing was to remove residual sulfonating agent and byproducts. (3) Silane modification treatment: Sulfonated phenolic resin particles are impregnated in a solution containing a silane coupling agent, such as an aqueous solution, for surface modification. The main function is to use the silanol groups resulting from the hydrolysis of the silane coupling agent to undergo a condensation reaction with the residual hydroxyl groups on the resin surface (derived from the hydrolysis of phenolic or sulfonic acid groups), forming a dense, hydrophobic organosilicon film / network on the particle surface. This prevents methanol molecules from penetrating into the particle interior, greatly inhibiting swelling and thus improving the resin's adhesion and water resistance. Silane coupling agents include aminosilane coupling agents and / or epoxysilane coupling agents, etc. (4) Titanate modification treatment: Under the protection of a protective gas, silane-modified phenolic resin particles are dispersed in a solvent, and then a titanate coupling agent is added. The reaction is carried out under heating conditions, and the unreacted titanate coupling agent and solvent are removed after the reaction. The addition of titanium helps improve the temperature resistance of the resin and resist the damage to the resin structure under high temperature environment; The titanate coupling agent is added by adding a titanate coupling agent solution, wherein the solvent in the titanate coupling agent solution is a mixture of water and alcohol. (5) Crosslinking treatment: The phenolic resin particles modified with titanate were heat-treated at 180~220℃ under an inert atmosphere to promote the formation of a hydrophobic network on the surface and further cross-linking of the resin skeleton, thereby obtaining modified phenolic resin.

[0075] The present invention also provides a method for synthesizing methyl propionate, which employs a composite catalytic system composed of group VIII metals and their compounds (e.g., palladium catalysts), phosphorus-containing ligands, and the above-mentioned modified phenolic resin.

[0076] The reaction system is carried out in a stirred reactor. The gas phase reaction feedstock is a mixture of carbon monoxide and ethylene, and the liquid phase reaction feedstock is a methanol solution containing a composite catalytic system.

[0077] The presence and adhesion forms of Pd black in the reactor are as follows: Figure 1 As shown in the left figure, the analysis suggests that metal-metal (Pd-Pd) bonding is much easier and more stable than metal-vessel wall (Pd-glass / stainless steel) bonding, which greatly reduces the thermodynamic driving force requirements of the deposition process. Furthermore, when a porous palladium black deposit forms on the vessel wall surface, it alters the hydrodynamic boundary layer near the reactor wall. This rough deposit may generate micro-eddies or act as a "filter," more effectively capturing and retaining solutions containing deactivated palladium species flowing through it, increasing the effective collision frequency. This results in more metallic Pd adhering to the reactor wall and agitator, reducing catalytic efficiency and increasing the cost of precious metals. The reactor condition after being detached by the solid acid-modified phenolic resin of this invention is as follows: Figure 1 As shown in the right figure; Furthermore, during the reaction, as the reaction proceeds, Pd particles collide and adhere to each other, gradually forming Pd black. This black then comes into contact with the stirring paddle and reactor walls due to the stirring action, thus adhering to the surfaces of the stirring paddle and reactor (e.g., ...). Figure 2 As shown), the solid acid-modified phenolic resin of this invention also collides with the stirring paddle and reactor wall in the reactor. When the solid acid comes into contact with the Pd black adhering to the stirring paddle and reactor wall, it helps to knock it off the adhesion point (e.g. Figure 3As shown in the diagram, this effect is similar to mechanical grinding and cleaning. In the reaction vessel, the solid acid particles of this invention possess sufficient kinetic energy under stirring, especially at high speeds. These solid particles frequently collide and rub against the reaction vessel wall, the stirring paddle, and each other, physically scraping away the fine palladium nuclei formed on the vessel wall or not yet firmly bonded. This removes the palladium nuclei at the initial stage of formation, preventing them from becoming "seeds" for accelerated deposition. Even if a small amount of palladium begins to deposit, it will be worn away by the constantly moving particles, preventing the formation of a continuous and firm palladium layer. Furthermore, this mutual friction and collision phenomenon on the particle surface also prevents the palladium adsorbed thereon from agglomerating and growing, breaking it down into fine particles, thus ensuring the specific surface area of ​​the catalyst and sometimes even exposing some still-active sites. Therefore, when the solid acid co-catalyst of this invention has high strength and high stability, it can become an effective "cleaning ball" during stirring, continuously impacting and peeling off the attached Pd black, allowing it to redisperse into the reaction liquid to participate in the catalytic cycle. This inhibits the agglomeration and deactivation of Pd from the source, improving the utilization rate of precious metals and the long-term stability of the reaction.

[0078] Furthermore, the solid acid-modified phenolic resin of this invention, in addition to dispersing Pd black, can also complex with it, causing the Pd atoms on the surface to detach from the Pd black and re-transform into active Pd atoms to continue participating in the reaction (e.g. Figure 4 (As shown).

[0079] Furthermore, the solid acid-modified phenolic resin of this invention can also solve the problem of acid loss. In this invention, by firmly anchoring sulfonic acid groups on the highly cross-linked phenolic backbone in the form of covalent bonds and performing surface hydrophobic treatment, the modified phenolic resin of this invention completely avoids the problem of traditional liquid acid additive loss, ensuring the stability of the acidity of the reaction system and improving product quality. At the same time, it reduces operating costs and the difficulty of separation and purification. Furthermore, acid recycling is possible: solid acids can be easily separated and reused multiple times, while liquid acids are generally lost as metal salts; catalyst costs are reduced; although the initial input cost of solid acids may be higher, their reusability can significantly reduce the catalyst cost per reaction, which is particularly advantageous for large-scale production. Furthermore, the surface area of ​​the reactor wall and agitator is fixed and relatively small. However, the total specific surface area of ​​the large number of added solid acid particles far exceeds that of the reactor wall and agitator. When a deactivated palladium species forms in the solution and seeks surface attachment, the probability of it colliding with the surface of solid particles is far greater than the probability of it colliding with the distant reactor wall. Therefore, the vast majority of deactivated palladium is "intercepted" by these solid particles and adsorbed onto their surfaces, forming active palladium hydrogen, catalyzing the reaction. This is equivalent to "transferring" the deposition of deactivated palladium from the limited reactor wall to the vast particle surface, allowing it to continue to function.

[0080] The above-described solution will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are used to illustrate the basic principles, main features, and advantages of the present invention, and the present invention is not limited to the scope of the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are generally the conditions in conventional experiments. Unless otherwise specified in the following embodiments, all raw materials are commercially available or prepared by conventional methods in the art.

[0081] Example 1: This example provides a modified phenolic resin and its preparation method, the preparation method comprising: 1) Preparation of phenolic resin particles: 94 g of phenol (1 mol), 107 g of formaldehyde aqueous solution (mass concentration of 35%, 1.25 mol), and 500 g of NaOH aqueous solution (0.1 mol / L) were dispersed in 50 g of glycerol containing 15 g of stabilizer PVA (molecular weight of approximately 75,000) under stirring at 150 r / min; the stirring temperature was 95℃ and the stirring time was 2 h, resulting in yellow phenolic resin particles.

[0082] 2) Sulfonation treatment: At 0℃, 110 g of phenolic resin particles prepared according to the above method were added to 200 g of dichloroethane, followed by the slow addition of 100 g of fuming sulfuric acid (containing 20% ​​SO3 by mass). The reaction temperature was kept below 5℃ during the reaction. After the addition was completed, the reaction was continued at 5℃ for 1 h. The resin was then filtered and washed with 1 L of 0.1 mol / L sulfuric acid, followed by washing with deionized water until the pH of the washing solution was neutral.

[0083] 3) Silanization modification treatment: At room temperature, the sulfonated phenolic resin particles (based on the mass of step 2) are added to 100g of aqueous solution containing 0.5% silane coupling agent KH550 and stirred for 1h, and the solvent is removed by filtration.

[0084] 4) Titanate modification treatment: Under nitrogen protection, silanized modified phenolic resin particles (based on the mass of step 3) were placed in 100g xylene, and 10g tetraethyl titanate solution (mass concentration of 5%, solvent is water and ethanol mixed in a mass ratio of 1:5) was slowly added dropwise; the reaction system temperature was controlled at 60℃, and the reaction was carried out at this temperature for 3h, followed by 2h at 100℃ and 0.05MPa pressure to remove unreacted titanate coupling agent and solvent.

[0085] 5) Crosslinking treatment: The phenolic resin particles modified with titanate were subjected to high-temperature heat treatment at 200℃ under nitrogen protection for 3 hours to obtain modified phenolic resin A, with a total yield of about 25%.

[0086] Example 2: This example provides a modified phenolic resin and its preparation method, the preparation method comprising: 1) Preparation of phenolic resin particles: 94 g of phenol (1 mol), 107 g of formaldehyde aqueous solution (mass concentration of 35%, 1.25 mol), and 500 g of KOH aqueous solution (0.1 mol / L) were dispersed in 50 g of glycerol containing 15 g of stabilizer PVA (molecular weight of approximately 75,000) under stirring at 150 r / min; the stirring temperature was 95℃ and the stirring time was 2 h, resulting in yellow phenolic resin particles.

[0087] 2) Sulfonation treatment: At 0℃, 111 g of phenolic resin particles prepared according to the above method were added to 200 g of dichloroethane, followed by the slow addition of 100 g of fuming sulfuric acid (containing 20% ​​SO3 by mass). The reaction temperature was kept below 5℃ during the reaction. After the addition was completed, the reaction was continued at 5℃ for 1 h. The resin was then filtered and washed with 1 L of 0.1 mol / L sulfuric acid, followed by washing with deionized water until the pH of the washing solution was neutral.

[0088] 3) Silanization modification treatment: At room temperature, the sulfonated phenolic resin particles (based on the mass of step 2) are added to 100g of aqueous solution containing 0.5% silane coupling agent KH550 and stirred for 1h, and the solvent is removed by filtration.

[0089] 4) Titanate modification treatment: Under nitrogen protection, silanized modified phenolic resin particles (based on the mass of step 3) were placed in 100g xylene, and 10g tetraisobutyl titanate solution (mass concentration of 5%, solvent is water and ethanol mixed in a mass ratio of 1:5) was slowly added dropwise; the reaction system temperature was controlled at 60℃, and the reaction was carried out at this temperature for 3h, followed by 2h at 100℃ and 0.05MPa pressure to remove unreacted titanate coupling agent and solvent.

[0090] 5) Crosslinking treatment: The phenolic resin particles modified with titanate were subjected to high-temperature heat treatment at 200℃ under nitrogen protection for 3 hours to obtain modified phenolic resin B, with a total yield of about 27%.

[0091] Example 3: This example provides a modified phenolic resin and its preparation method, the preparation method comprising: 1) Preparation of phenolic resin particles: 94 g of phenol (1 mol), 107 g of formaldehyde aqueous solution (mass concentration of 35%, 1.25 mol), and 500 g of ammonia (0.1 mol / L) were dispersed in 50 g of glycerol containing 15 g of stabilizer PVA (molecular weight of approximately 75,000) under stirring at 150 r / min; the stirring temperature was 95℃ and the stirring time was 2 h, resulting in yellow phenolic resin particles.

[0092] 2) Sulfonation treatment: At 0℃, 109 g of phenolic resin particles prepared according to the above method were added to 200 g of dichloroethane, followed by the slow addition of 100 g of fuming sulfuric acid (containing 20% ​​SO3 by mass). The reaction temperature was kept below 5℃ during the reaction. After the addition was completed, the reaction was continued at 5℃ for 1 h. The resin was then filtered and washed with 1 L of 0.1 mol / L sulfuric acid, followed by washing with deionized water until the pH of the washing solution was neutral.

[0093] 3) Silanization modification treatment: At room temperature, the sulfonated phenolic resin particles (based on the mass of step 2) are added to 100g of aqueous solution containing 0.5% silane coupling agent Y-9669 and stirred for 1h. The solvent is then removed by filtration.

[0094] 4) Titanate modification treatment: Under nitrogen protection, silanized modified phenolic resin particles (based on the mass of step 3) were placed in 100g xylene, and 20g tetraethyl titanate solution (mass concentration of 5%, solvent is water and ethanol mixed in a mass ratio of 1:5) was slowly added dropwise; the reaction system temperature was controlled at 60℃, and the reaction was carried out at this temperature for 3h, followed by 2h at 100℃ and 0.05MPa pressure to remove unreacted titanate coupling agent and solvent.

[0095] 5) Crosslinking treatment: The phenolic resin particles modified with titanate were subjected to high-temperature heat treatment at 200℃ under nitrogen protection for 3 hours to obtain modified phenolic resin C, with a total yield of about 23%.

[0096] Example 4: This example provides a modified phenolic resin and its preparation method, the preparation method comprising: 1) Preparation of phenolic resin particles: 94 g of phenol (1 mol), 107 g of formaldehyde aqueous solution (mass concentration of 35%, 1.25 mol), and 500 g of NaOH aqueous solution (0.1 mol / L) were dispersed in 50 g of glycerol containing 15 g of sodium benzenesulfonate stabilizer under stirring at 150 r / min; the stirring temperature was 95℃ and the stirring time was 2 h to obtain yellow phenolic resin particles.

[0097] 2) Sulfonation treatment: At 0℃, 110 g of phenolic resin particles prepared according to the above method were added to 200 g of dichloroethane, followed by the slow addition of 100 g of fuming sulfuric acid (containing 20% ​​SO3 by mass). The reaction temperature was kept below 5℃ during the reaction. After the addition was completed, the reaction was continued at 5℃ for 1 h. The resin was then filtered and washed with 1 L of 0.1 mol / L sulfuric acid, followed by washing with deionized water until the pH of the washing solution was neutral.

[0098] 3) Silanization modification treatment: At room temperature, the sulfonated phenolic resin particles (based on the mass of step 2) are added to 100g of aqueous solution containing 1% by mass of silane coupling agent KH550 and stirred for 1h. The solvent is then removed by filtration.

[0099] 4) Titanate modification treatment: Under nitrogen protection, silanized modified phenolic resin particles (based on the mass of step 3) were placed in 100g xylene, and 10g tetraethyl titanate solution (mass concentration of 5%, solvent is water and ethanol mixed in a mass ratio of 1:5) was slowly added dropwise; the reaction system temperature was controlled at 60℃, and the reaction was carried out at this temperature for 3h, followed by 2h at 100℃ and 0.05MPa pressure to remove unreacted titanate coupling agent and solvent.

[0100] 5) Crosslinking treatment: The titanate-modified phenolic resin particles were subjected to high-temperature heat treatment at 200℃ under nitrogen protection for 3 hours to obtain modified phenolic resin D, with a total yield of approximately 24%.

[0101] Example 5: This example provides a modified phenolic resin and its preparation method, the preparation method comprising: 1) Preparation of phenolic resin particles: 94 g of phenol (1 mol), 107 g of formaldehyde aqueous solution (mass concentration of 35%, 1.25 mol), and 500 g of NaOH aqueous solution (0.1 mol / L) were dispersed in 50 g of N-methylpyrrolidone (NMP) containing 15 g of stabilizer PVA (molecular weight of approximately 75,000) under stirring at 150 r / min; the stirring temperature was 95℃ and the stirring time was 2 h, resulting in yellow phenolic resin particles.

[0102] 2) Sulfonation treatment: At 0℃, 112 g of phenolic resin particles prepared according to the above method were added to 200 g of ethyl acetate, followed by the slow addition of 100 g of fuming sulfuric acid (containing 20% ​​SO3 by mass). The reaction temperature was kept below 5℃ during the reaction. After the addition was completed, the reaction was continued at 5℃ for 1 h. The resin was then filtered and washed with 1 L of 0.1 mol / L sulfuric acid, followed by washing with deionized water until the pH of the washing solution was neutral.

[0103] 3) Silanization modification treatment: At room temperature, the sulfonated phenolic resin particles (based on the mass of step 2) are added to 100g of aqueous solution containing 0.5% silane coupling agent KH550 and stirred for 1h, and the solvent is removed by filtration.

[0104] 4) Titanate modification treatment: Under nitrogen protection, silanized modified phenolic resin particles (based on the mass of step 3) were placed in 100g xylene, and 10g tetraethyl titanate solution (mass concentration of 5%, solvent is water and ethanol mixed in a mass ratio of 1:5) was slowly added dropwise; the reaction system temperature was controlled at 60℃, and the reaction was carried out at this temperature for 3h, followed by 2h at 100℃ and 0.05MPa pressure to remove unreacted titanate coupling agent and solvent.

[0105] 5) Crosslinking treatment: The phenolic resin particles modified with titanate were subjected to high-temperature heat treatment at 200℃ under nitrogen protection for 3 hours to obtain modified phenolic resin E with a total yield of about 26%.

[0106] The particle size, strength, acidity, and swelling resistance of the modified phenolic resins obtained in Examples 1-5 were tested, and the specific results are shown in Tables 1 and 2.

[0107] The testing methods for each indicator are as follows: (a) Particle size test: The proportion of particles with a diameter of 3±1mm was confirmed by sieving. 1. Sampling shall be carried out in accordance with the provisions of GB / T 5475; 2. Place the sample in a 100mL graduated cylinder and tap it until the resin volume is constant at 100mL; 3. Take a sample sieve with a pore size corresponding to the upper limit particle size (4 mm pore size) and sieve the sample in the sample tray A. Move the sample sieve back and forth and left and right. Pay attention to the shaking force during operation to prevent the sample from jumping out from the upper edge of the sample sieve. 4. During the sieving process, the screen should be cleaned in time according to the degree of clogging. When cleaning the screen, place the sample on the test sieve in the sample tray B, turn the test sieve over and use a brush to gently sweep the sample particles in the mesh into the sample tray B. 5. Continue sieving the sample in sample tray B into sample tray A, and repeat the operation according to the procedures specified in 3 and 4 above until no more resin particles pass through the screen after cleaning. Then the sieving is considered complete. 6. Collect the sieved sample from sample tray A into a graduated cylinder, tap it until the resin volume is constant, and record the volume as V1; 7. Take a test sieve with a pore size corresponding to the lower limit particle size (2mm pore size), sieve the resin collected by the graduated cylinder in steps 4, 5, and 6, and move the test sample back and forth and left and right, while preventing the sample from jumping out from the upper edge of the test sieve. 8. Sieve the sample according to steps 4, 5, and 6. Record the volume as V2.

[0108] The particle size range for dry sieving is calculated using the following formula: P = (V1 - V2) / 100 × 100%.

[0109] (ii) Strength test: Use a strength tester to test at least 30 particles and record the average and minimum values.

[0110] 1. Take a certain amount (100 pieces) of intact particle sample; 2. Place each sample on a particle strength testing instrument to test its compressive strength and record the results statistically. 3. Summarize and statistically analyze the recorded data to calculate the average compressive strength, in N / piece; 4. Repeat the above operation 3 times to ensure there are no random errors.

[0111] (iii) Acid value test: The total acid content (mmol H+ / g dry resin) was determined by titration.

[0112] 1. Weigh 1g of resin and place it in a mixed solvent of ethanol (20mL) and toluene (10mL), and stir thoroughly; 2. Add 10 mL of deionized water to hydrolyze, and stir for 20 min; 3. Titrate with 0.1 mol / L KOH ethanol standard solution, using phenolphthalein as an indicator, until the solution turns pink and does not fade for 15 seconds; 4. Acid value X = (V1 - V0) × C × 56.1 / m, where V1 and V0 are the final and blank values ​​of the titration volume, respectively, C is the KOH concentration (approximately 0.1 mol / L), and m is the sample mass (1g). 5. Repeat the above operation 3 times and take the average value.

[0113] (iv) Resistance to swelling with methanol and methyl propionate (MP): Accelerated swelling test: Immerse the dried and weighed granules in methanol and methyl propionate at 100°C and 1.3 MPa. Periodically remove the granules (e.g., after 7 days, 14 days, 30 days, 2 months, 4 months, and 6 months), quickly wipe off the surface liquid (to avoid the influence of solvent evaporation), weigh immediately (Wt), and calculate the degree of swelling.

[0114] Swelling degree = (Wt-W0) / W0×100%, where W0 is the initial weight.

[0115] Table 1

[0116] Table 2

[0117] As shown in Table 2, the granular modified phenolic resin of the present invention exhibited a swelling degree of <5% and tended to be stable throughout the entire accelerated testing period (6 months), with no significant change in particle shape.

[0118] Application Example 1: This example provides a method for preparing methyl propionate, the method comprising: In a 2L autoclave, 1000g (31.25 mol) of methanol, 91.57mg (0.10 mmol) of tris(dibenzylacetone)dipalladium, 0.50 mmol (197.28 mg) of bidentate phosphine ligand (DTBPX, chemical name 1,2-bis(di-tert-butylphosphine)methylbenzene), and 2g of modified phenolic resin A from Example 1 were added. A mixture of ethylene and carbon monoxide in a molar ratio of 4:1 (CO flow rate 1.2 L / min) was introduced, and the reaction was carried out at a stirring speed of 500 r / min, a reaction pressure of 1.2 MPa, and a reaction temperature of 60°C for 120 minutes.

[0119] After the reaction was completed, an appropriate amount of the reaction mixture was weighed and subjected to GC chromatography analysis. The conversion and selectivity were calculated using carbon monoxide, as well as the yield of the product methyl propionate. The results are shown in Table 3.

[0120] Application Example 2: This example provides a method for preparing methyl propionate, which is basically the same as in Example 1, except that the modified phenolic resin A in Example 1 is replaced with the modified phenolic resin B in Example 2.

[0121] Application Example 3: This example provides a method for preparing methyl propionate, which is basically the same as in Example 1, except that the modified phenolic resin A in Example 1 is replaced with the modified phenolic resin C in Example 3.

[0122] Application Example 4: This example provides a method for preparing methyl propionate, which is basically the same as in Example 1, except that the modified phenolic resin A in Example 1 is replaced with the modified phenolic resin D in Example 4.

[0123] Application Example 5: This example provides a method for preparing methyl propionate, which is basically the same as in Example 1, except that the modified phenolic resin A in Example 1 is replaced with the modified phenolic resin E in Example 5.

[0124] Application Example 6: This example provides a method for preparing methyl propionate, which is basically the same as in Example 1, except that the amount of modified phenolic resin A added in Example 1 is adjusted to 4g.

[0125] Application Example 7: This example provides a method for preparing methyl propionate, which is basically the same as in Example 1, except that the amount of modified phenolic resin A added in Example 1 is adjusted to 1g.

[0126] Application Comparative Example 1: Purchase commercially available strong acid polystyrene-based cation exchange resin (Amberlyst-15), sieve it to a particle size of 2-4 mm, and replace the modified phenolic resin A in Application Example 1. All other conditions are the same as in Application Example 1.

[0127] Application Comparative Example 2: Methanesulfonic acid (6 mmol) was used as an acid co-catalyst in the reaction system, replacing the modified phenolic resin A in Application Example 1, and the other conditions were the same as in Application Example 1.

[0128] Table 3

[0129] Stability test: The modified phenolic resins of Examples 1-5 and Amberlyst-15 of Comparative Example 1 were used as acid additives. The reaction was repeated 120 times under the same conditions as in Example 1 (the catalyst was separated and reused by filtration). The composition of the reaction solution was analyzed by GC, and the integrity of the catalyst particles was examined. Specific results are shown in Table 4.

[0130] Table 4

[0131] The Pd content in the reaction solution was determined by ICP.

[0132] After the reaction, the modified phenolic resin particles of this invention remained intact without breakage, and sieve analysis showed that particles of 3±1mm still accounted for more than 95%. The average strength of a single particle remained above 145N. In contrast, the resin in Comparative Example 1 swelled and partially broke. Furthermore, after repeated large-scale reactions, the conversion rate and yield of Comparative Example 1 decreased significantly, requiring the addition of acid.

[0133] In summary, this invention can effectively reduce the aggregation and deactivation of Pd and reduce catalyst loss. At the same time, the presence of modified phenolic resin provides the necessary acidic environment for the system to ensure the activity of the catalyst. The high boiling point of the modified phenolic resin makes it difficult for it to evaporate from the system, thus continuously providing the effect of a catalytic promoter.

[0134] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

[0135] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A modified phenol-formaldehyde resin, characterized by, The modified phenolic resin is prepared by chemical modification treatment of a phenolic resin, the chemical modification treatment comprising sulfonation treatment, silane modification treatment and titanate modification treatment; The modified phenolic resin exists in the form of modified phenolic resin particles, and the single-particle compressive strength of the modified phenolic resin particles is greater than or equal to 100 N; The hydrogen ion content of the modified phenolic resin is greater than or equal to 1.5 mmol per gram of dry resin, and the swelling degree is less than or equal to 5% in methanol and / or methyl propionate at 100°C and 1.3 MPa within a test period of 6 months.

2. The modified phenolic resin according to claim 1, characterized in that, The single-particle compressive strength of the modified phenolic resin particles is 120-200 N, and more preferably 140-180 N; And / or, the particle size of the modified phenolic resin particles is 2-4 mm; And / or, the phenolic resin is subjected to the chemical modification treatment in the form of phenolic resin particles as raw material; And / or, the hydroxyl value of the phenolic resin is 100-250 mgKOH / g; And / or, the hydrogen ion content of the modified phenolic resin is 1.5-5.0 mmol per gram of dry resin; And / or, the swelling degree of the modified phenolic resin is 0-4%.

3. The modified phenolic resin according to claim 1, characterized in that, The chemical modification treatment further comprises crosslinking treatment, and the crosslinking treatment comprises a step of heat treatment in nitrogen and / or inert gas; further, the temperature of the heat treatment is 180-220°C; More preferably, in the chemical modification treatment, the sulfonation treatment, the silane modification treatment, the titanate modification treatment and the crosslinking treatment are sequentially performed in this order; And / or, the sulfonation treatment comprises sulfonation reaction of a sulfonating agent with the phenolic resin; further, the sulfonation reaction is controlled to be performed at a temperature less than or equal to 5°C, and the sulfonating agent comprises one, a combination of two or more selected from fuming sulfuric acid, concentrated sulfuric acid with a mass concentration of 90%-98.5%, and sulfur trioxide; And / or, the silane modification treatment comprises modification treatment of the sulfonated phenolic resin with a silane coupling agent; further, the feeding mass of the silane coupling agent is 0.1%-0.5% of the mass of the sulfonated phenolic resin; And / or, the titanate modification treatment comprises modification treatment of the silane-modified phenolic resin with a titanate coupling agent; further, the feeding mass of the titanate coupling agent is 0.5%-1% of the mass of the silane-modified phenolic resin.

4. A method for producing a modified phenol-formaldehyde resin, characterized by, The preparation method comprises: (1) Sulfonation treatment: phenolic resin particles are placed in an inert solvent, a sulfonating agent is added for sulfonation reaction, and the temperature of the sulfonation reaction is controlled to be less than or equal to 5°C, to obtain a first intermediate; (2) Silane modification treatment: the first intermediate is added into an aqueous silane coupling agent solution for reaction to generate a second intermediate; (3) Titanate modification treatment: the second intermediate is reacted with a titanate coupling agent in a solvent under heating to generate a third intermediate; (4) Crosslinking treatment: the third intermediate is subjected to heat treatment in a protective atmosphere to obtain modified phenolic resin in the form of particles.

5. The method of preparing a modified phenol formaldehyde resin according to claim 4, characterized in that, The phenolic resin particles are prepared by dispersing phenol, formaldehyde and an aqueous solution of an alkaline reagent in an organic solvent containing a stabilizer under stirring and at a temperature of 90-100℃, and reacting to form the phenolic resin particles; Further, the molar ratio of the phenol, the formaldehyde and the alkaline reagent is 1:1-1.5:0.02-0.1; Further, the alkaline reagent comprises one, a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia water; Further, the stabilizer comprises one, a combination of two or more selected from polyvinyl alcohol, sodium benzenesulfonate, sodium stearate and sodium octadecylate; Further, the mass of the stabilizer is 10%-20% of the mass of the phenol; Further, the organic solvent comprises one, a combination of two or more selected from 2-chloroethanol, 1-chloro-2-propanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol and N-methylpyrrolidone; Further, the stirring speed of the stirring condition is 100-200rpm.

6. The method of preparing a modified phenol-formaldehyde resin according to claim 4, characterized by, The sulfonating agent comprises one, a combination of two or more selected from fuming sulfuric acid, concentrated sulfuric acid with a mass concentration of 90%-98.5% and sulfur trioxide; And / or, the inert solvent comprises dichloroethane and / or ethyl acetate; And / or, the mass concentration of the silane coupling agent aqueous solution is 0.5%-2.0%, further, the silane coupling agent aqueous solution is formed by dispersing a silane coupling agent in water, further, the silane coupling agent comprises an amino silane coupling agent and / or an epoxy silane coupling agent; still further, the mass of the silane coupling agent is 0.1%-0.5% of the mass of the first intermediate; And / or, the titanate coupling agent comprises one, a combination of two or more selected from tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, n-butyl titanate, tetraisobutyl titanate, di(acetylacetonato)diisopropyl titanate, isopropoxytri(dioctyl phosphate) titanate, isopropyl trioleoyloxy titanate and isopropyl triisostearoyloxy titanate; further, the mass of the titanate coupling agent is 0.5%-1% of the mass of the second intermediate; And / or, in the titanate modification treatment, the heating condition is controlled to allow the reaction to proceed at 50-90℃, further, the reaction is allowed to proceed in a protective atmosphere formed by introducing nitrogen and / or inert gas; And / or, in the titanate modification treatment, the titanate coupling agent is added dropwise to the solvent in which the second intermediate is dispersed; And / or, in the titanate modification treatment, the titanate coupling agent is added by adding a titanate coupling agent solution, and the solvent in the titanate coupling agent solution is a mixed solvent of water and alcohol; And / or, the temperature of the heat treatment is 180-220℃.

7. A composite catalyst system characterized in that, The composite catalyst system comprises: a group VIII metal or a compound thereof; a phosphorus-containing ligand and / or a nitrogen-containing ligand; The modified phenolic resin according to any one of claims 1-3, or the modified phenolic resin prepared by the method according to any one of claims 4-6.

8. The composite catalytic system according to claim 7, characterized in that, The Group VIII metal or the compound thereof includes one, a combination of two or more selected from the group consisting of tris(dibenzylideneacetone)dipalladium, dichlorodiaminopalladium, dinitosopalladium, [Rh(COD)Cl]2, [Ir(COD)Cl]2, tetrakis(triphenylphosphine)palladium, palladium dichloride, palladium acetylacetonate, palladium acetate, dichloro(1,5-cyclooctadiene)palladium, bis(dibenzylideneacetone)palladium, bis(triphenylphosphine)palladium dichloride, bis(acetonitrile)palladium dichloride; and / or, The phosphorus-containing ligand includes one, a combination of two or more selected from the group consisting of N,N-bis(di-tert-butylphosphino)-ethylenediamine, N,N-bis(diisopropylphosphino)-ethylenediamine, N,N-bis(di-tert-butylphosphino)-N,N-dimethylethylenediamine, N,N-bis(di-tert-butylphosphino)-N,N-diethylethylenediamine, N,N-bis(di-tert-butylphosphino)-N,N-diisopropylethylenediamine, bis(diisopropylphosphino)benzene, bis(di-tert-butylphosphino)benzene, bis(cyclohexylphosphino)benzene, 1,1'-bis(diphenylphosphino)ferrocene, 1,1'-bis(diisopropylphosphino)ferrocene, 1,1'-bis(diisobutylphosphino)ferrocene, 1,1'-bis(dipropylphosphino)ferrocene, 1,1'-bis(dicyclohexylphosphino)ferrocene, 1,1'-bis(isopropylcyclohexylphosphino)ferrocene, 1,1'-bis(di-tert-butylphosphino)ferrocene, 1,2-bis-(di-tert-butylphosphinomethyl)benzene, 1,2-bis-(di-tert-amylphosphinomethyl)benzene; and / or, The nitrogen-containing ligand includes one, a combination of two or more selected from the group consisting of (1,3-di(2-pyridyl))benzene, 1,3-bis(dimethylaminomethyl)benzene, 1,3-bis(methyl ethylaminomethyl)benzene, 1,3-bis(diethylaminomethyl)benzene, 1,3-bis(diphenylaminomethyl)benzene, 1,3-bis(dicyclohexylaminomethyl)benzene; 1,3-bis(dibenzylaminomethyl)benzene, 5,5'-divinyl-2,2'-bipyridine, 4,4'-divinyl-2,2'-bipyridine; and / or, The ratio of the mass of the Group VIII metal or the compound thereof, the phosphorus-containing ligand and / or the nitrogen-containing ligand and the modified phenolic resin is 1:1-5:10-100.

9. Use of the modified phenolic resin according to any one of claims 1-3, or the modified phenolic resin prepared by the method according to any one of claims 4-6, or the composite catalytic system according to any one of claims 7-8 in a carbonylation reaction.

10. A method for preparing methyl propionate or a derivative thereof, characterized by, The method includes: allowing carbon monoxide, an olefin and an alkyl alcohol to react in the presence of the composite catalytic system according to claim 7 or 8 to generate methyl propionate or a derivative thereof.

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