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CN114426545B - Preparation method of alicyclic epoxy resin - Google Patents

Preparation method of alicyclic epoxy resin Download PDF

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CN114426545B
CN114426545B CN202011006779.XA CN202011006779A CN114426545B CN 114426545 B CN114426545 B CN 114426545B CN 202011006779 A CN202011006779 A CN 202011006779A CN 114426545 B CN114426545 B CN 114426545B
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catalyst
hours
hms
alicyclic
epoxy resin
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CN114426545A (en
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翁羽飞
周飞
奚军
蒋方红
许艾娜
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China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
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Sinopec Shanghai Petrochemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/60—Synthesis on support

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epoxy Compounds (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of alicyclic epoxy resin, which adopts titanium-silicon molecular sieve as catalyst, and in the presence of inert solvent, alicyclic diolefin and organic peroxide are reacted by catalytic oxidation to produce alicyclic epoxy resin. The process for preparing the alicyclic epoxy resin provided by the invention has the advantages of mild reaction conditions, high product yield, less waste liquid discharge, safe and simple process operation, and provides a green reaction process for synthesizing the alicyclic epoxy resin.

Description

Preparation method of alicyclic epoxy resin
Technical Field
The invention belongs to the technical field of catalytic oxidation synthesis of organic epoxy compounds and catalytic oxidation of olefins, and particularly relates to a method for preparing alicyclic epoxy resin by taking alicyclic diolefin raw materials, titanium-silicon molecular sieve as a catalyst and organic peroxide as an oxidant.
Background
Epoxy resins are generic terms of compounds that contain two epoxy groups in one molecule and that can form three-dimensional crosslinked network-like cured products in the presence of suitable chemical agents. The alicyclic epoxy resin generally does not contain strong ultraviolet chromophores such as aromatic rings, and the like, and when the alicyclic epoxy resin is exposed to a high-voltage electric arc, micromolecular volatile matters such as carbon dioxide, carbon monoxide, water and the like are generated by decomposition, and free carbon is not generated to form a conductive path, so that the alicyclic epoxy resin has excellent high-voltage leakage resistance. The excellent comprehensive performance makes the alicyclic epoxy resin widely applied in the fields of very large scale integrated circuit packaging, printed circuit board manufacturing, special photo-curing coating, high temperature resistant motor insulating materials and the like in recent years.
In the prior art, many cycloaliphatic epoxy resins, including dicyclopentadiene dioxide, are typically oxidized using peroxyacetic acid. The peracetic acid required by the reaction is usually prepared in situ by taking acetic acid and 50% -80% hydrogen peroxide as raw materials under the catalysis of concentrated sulfuric acid, so that the peracetic acid is high in process risk and small in production scale. The process has the defects that a large amount of acetic acid is excessive, equipment is severely corroded, the excessive acetic acid easily causes epoxide acidic ring opening to generate byproducts, the reaction products need to be washed for many times by alkaline water, the discharge amount of three wastes is large, and the like.
Disclosure of Invention
In order to solve the technical defects of the prior art for synthesizing alicyclic epoxy resin, the inventor discovers that dicyclopentadiene dioxide can be efficiently synthesized under the mild reaction process condition by adopting titanium-silicon molecular sieve catalyst and organic peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide and the like as oxidizing agents. Through experiments, the inventor also found that a series of alicyclic epoxy resins can be synthesized under the same conditions by substituting alicyclic diolefin with 6-18 carbon atoms for dicyclopentadiene.
The technical scheme of the invention is specifically introduced as follows:
The invention provides a preparation method of alicyclic epoxy resin, which comprises the following steps: taking alicyclic diolefin as a raw material, and organic peroxide as an oxidant, and in the presence of an inert solvent, carrying out catalytic oxidation reaction on the alicyclic diolefin, the organic peroxide and a titanium silicalite molecular sieve catalyst in a reactor under sufficient contact to generate alicyclic epoxy resin;
The titanium silicalite molecular sieve catalyst is a Ti-HMS molecular sieve catalyst with mesoporous characteristics, and comprises the following components: 0.10 to 10.65 percent of TiO 2, 39.68 to 62.90 percent of nano carbon fiber, 28.17 to 45.80 percent of SiO 2, 0.01 to 1.98 percent of magnesia, 0.44 to 6.93 percent of silicane matrix, and the UV-vis spectrogram of the titanium-silicon molecular sieve catalyst has a strong absorption peak at 220 nm;
The mol ratio of the alicyclic diolefin to the organic peroxide is 1.0:1.8-1.0:2.5, and the volume ratio of the alicyclic diolefin to the inert solvent is 1: 4-1: 30, the catalytic oxidation reaction temperature is preferably 30-150 ℃ and the pressure is 0-10 MPa (gauge pressure).
Further, the catalytic oxidation reaction temperature is 60-120 ℃, the pressure is 0.3-6.0 MPa (gauge pressure), and the molar ratio of the alicyclic diolefin to the organic peroxide is 1.0:2.0-1.0:2.2.
Furthermore, the catalytic oxidation reaction adopts an intermittent reaction process or a fixed bed continuous reaction process; by adopting a batch reaction process, the mass ratio of the catalyst to the alicyclic diolefin is 0.01: 100-20: 100, wherein the reaction time is 1-20 hours; and a fixed bed continuous reaction process is adopted, and the total material volume space velocity is 0.1-4.3 h -1.
Further, the catalytic oxidation reaction adopts a batch reaction process, and the mass ratio of the catalyst to the alicyclic diolefin is 0.5: 100-10: 100, the reaction time is 3-6 hours.
Further, the inert solvent is selected from any one of cyclohexane, normal hexane, heptane, octane, nonane, decane, undecane, benzene, toluene, ethylbenzene, methylethylbenzene, xylene, isopropylbenzene and petroleum ether.
Further, the organic peroxide is preferably cumene hydroperoxide, tert-butyl hydroperoxide or tert-amyl alcohol peroxide.
Further, the alicyclic diolefin is alicyclic diolefin with 6-18 carbon atoms in each molecule.
Further, the alicyclic diolefin having 6 to 18 carbon atoms per molecule is preferably any one of the following compounds: dicyclopentadiene, 2, 5-norbornadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 4-vinyl-1-cyclohexene, limonene, 3 '-bicyclo-hexene, 3' -bicyclo-pentene, spirobicyclo-hexene or spirobicyclo-pentene. The molecular structural formula of the compounds is shown as follows:
Further, the titanium silicalite molecular sieve catalyst is a Ti-HMS molecular sieve catalyst with mesoporous characteristics, and comprises the following components: 2.57 to 6.42 percent of TiO 2, 48.95 to 62.90 percent of nano carbon fiber, 28.17 to 38.87 percent of SiO 2, 0.01 to 0.83 percent of magnesia and 0.44 to 6.41 percent of silane matrix.
The preparation method of the titanium silicalite molecular sieve catalyst comprises the following steps:
a) Under inert atmosphere, dissolving a silicon source, a titanium source and a template agent in a mixed solvent of water and organic alcohol, stirring and crystallizing at room temperature for 0.5-10 hours, adding nano carbon fiber, continuously stirring for 10-72 hours, crystallizing at 150-200 ℃ for 1-7 days, and separating, washing and drying a crystallized product to obtain the Ti-HMS loaded by the nano carbon fiber;
b) Adding Ti-HMS loaded by nano carbon fibers into an aqueous solution containing any one or a mixture of Mg (OH) 2、MgO、MgCO3、4MgCO3.Mg(OH)2.5H2 O and dolomite (MgCO 3.CaCO3), stirring at room temperature for 10-48 hours, separating out solids, washing with water until the washing liquid is neutral, drying, and roasting at 300-1000 ℃ for 2-20 hours in an inert atmosphere to obtain a Ti-HMS catalyst matrix modified by a magnesium-containing compound and taking the nano carbon fibers as a carrier;
c) Treating Ti-HMS catalyst parent body with organosilicon solution at 25-300 deg.c for 0.5-100 hr; the usage amount of the organic silicon is 10% -70% of the weight of the Ti-HMS catalyst matrix; and then filtering and separating out a solid catalyst, washing the solid catalyst by using an inert solvent, and baking the solid catalyst for 10-24 hours in an environment with the pressure of 0.133-1.33 KPa and the temperature of 80-200 ℃ to prepare the magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst.
Further, in step a), the silicon source is one or two of orthosilicate or hydrocarbyl silicate; the titanium source is titanate; the template agent is organic amine with a general formula RNH 2, and R is chain alkyl with 6-18 carbon atoms; the molar ratio of RNH 2 to Si in the silicon source is 0.01-0.3:1, the molar ratio of Si in the silicon source to Ti in the titanium source is 5: 1-500:1, the mol ratio of water to silicon source is 4-20:1, the volume ratio of alcohol to silicon source is 1-4:1, and the mol ratio of nano carbon fiber to silicon source is 5-20:1.
Further, the titanate used is selected from any one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, and tetraisobutyl titanate.
Further, in the step a), the carbon nanofiber is formed by taking a carbon-containing gas source, preferably any one of CO and CH 4、C2H6、C3H8 as a reaction raw material, selecting any one single metal element or a plurality of element alloys of elements in the VIII group of the periodic table, more preferably Fe, co and Ni as a catalyst, and carrying out catalytic pyrolysis reaction by the carbon-containing gas source, wherein the catalytic growth temperature of the carbon nanofiber is 550-650 ℃.
Further, in the step b), the volume ratio of the nano carbon fiber loaded Ti-HMS to the magnesium compound aqueous solution is 1:1 to 1:3, the mole ratio of any one or a mixture of more than one of MgO, mg (OH) 2、MgCO3、4MgCO3.Mg(OH)2.5H2 O and dolomite to the silicon source used in the step a) is 0.01:100-7: 100; the roasting temperature is 400-800 ℃ and the roasting time is 3-8 hours.
Further, in step c), the organosilicon solution is used, and the organosilicon is selected from any one of halosilanes, silazanes or silylamines.
Further, in step c), the organic silicon is selected from any one of trimethylchlorosilane, triethylsilicon chloride, hexamethyldisilazane or N-trimethylsilylimidazole.
Further, in the step c), the organic silicon solution is used, and the solvent is selected from any one or a mixture of more than one of benzene, toluene, isopropylbenzene, ethylbenzene, cyclohexane, n-heptane, octane and dodecane.
Further, in step c), washing with an inert solvent, comprising: the solid catalyst is washed 3 times by toluene, benzene or alkane inert solvent, and the volume of the inert solvent used for each washing is 5-10 times of the volume of the solid catalyst.
Compared with the prior art, the invention has the following advantages:
the preparation method provided by the invention is used for synthesizing the alicyclic epoxy resin, has the advantages of good catalyst activity, long service life, high product yield, easiness in product separation and mild reaction conditions, can adopt a fixed bed continuous reaction process, greatly improves the safety of the reaction process, and provides a green and environment-friendly reaction process for industrially producing the alicyclic epoxy resin.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is further illustrated by the following examples, but the present invention is not limited to the examples. The yield definition of the cycloaliphatic epoxy resin product in this patent specification:
epoxy resin reaction yield = moles of epoxy resin in reaction product/moles of cycloaliphatic diolefin starting material participating in the reaction 100%.
Example 1: preparation of titanium silicalite molecular sieve catalysts
15.6 G of hexadecylamine is added into 110ml of water and 100ml of ethanol in turn in a reactor under the condition of room temperature and stirring; 65 g of ethyl orthosilicate and 0.12 g of ethyl titanate dissolved in 40 ml of ethanol are added into the solution, stirred for 50 minutes, crystallized for 10 hours, 18.7 g of nano carbon fiber is added, stirring is continued for 10 to 72 hours, the temperature of the reactor is increased, the reaction material is crystallized for 2 days at 200 ℃, the solid is obtained by filtering, the template agent in the catalyst is extracted by ethanol, and then the solution is washed by pure water until the eluent is neutral. And drying the washed solid at 110 ℃ for 15 hours to obtain the Ti-HMS taking the carbon nanofiber as the carrier.
Adding 3 times of pure water and 1.2 g of Mg (OH) 2 into Ti-HMS solid taking the carbon nanofiber as a carrier, stirring at room temperature for 48 hours, separating out the solid, washing with pure water until the water washing liquid is neutral, drying at 80 ℃ for 30 hours, and roasting at 450 ℃ in helium atmosphere for 18 hours to obtain Ti-HMS taking the carbon nanofiber as the carrier and modified by magnesium compound;
The prepared powder catalyst sample is pressed into tablets, crushed and screened, 50 g of particles with 20-50 meshes are taken and put into a reactor, then 15.5 g of trimethylchlorosilane and 200 ml of toluene are added into the reactor, the mixture is stirred, the reaction temperature is 120 ℃ for silanization for 12 hours, the reaction is stopped, the solid catalyst is taken out, the toluene is leached, and then the solid catalyst is dried for 30 hours in a vacuum system with the temperature of 90 ℃ and the system pressure of 0.133 KPa.
Examples 2 to 13: kettle type reactor for synthesizing alicyclic epoxy resin by catalytic oxidation
Titanium-silicon molecular sieve catalyst, organic peroxide and solvent are taken and fed into a 500ml reactor according to the process requirements, the influence of temperature, pressure, material proportion and reaction time on the yield of epoxy resin products is examined, the compositions of the catalysts used in examples 2-13 are shown in table 1 (the preparation method is referred to in example 1), the alicyclic diolefin and the organic peroxide are shown in table 2, and the experimental results are shown in table 3.
TABLE 1 catalyst mass percent composition
* And (3) injection: c represents a carbon nanofiber.
TABLE 2 olefin feed and peroxide for kettle reaction to epoxy resin synthesis
Examples Alicyclic diolefins Organic peroxides
2 Dicyclopentadiene Benzoyl peroxide
3 Melamine Tert-butyl hydroperoxide
4 2, 5-Norbornadiene Hydrogen peroxide tert-amyl alcohol
5 5-Vinyl-2-norbornene Cumene hydroperoxide
6 5-Ethylidene-2-norbornene Cumene hydroperoxide
7 5-Isopropenyl-2-norbornene Cumene hydroperoxide
8 4-Vinyl-1-cyclohexene Cumene hydroperoxide
9 Limonene Tert-butyl hydroperoxide
10 3, 3' -Bicyclohexene Tert-butyl hydroperoxide
11 3, 3' -Bicyclopentene Cumene hydroperoxide
12 Spirobicyclohexene Cumene hydroperoxide
13 Spirocyclic pentenes Cumene hydroperoxide
TABLE 3 kettle reaction process conditions for synthesizing epoxy resins
Examples 14 to 21: preparation of alicyclic epoxy resin by fixed bed catalytic oxidation reaction process
30 G of catalyst is filled into a 100 ml isothermal fixed bed reactor, organic peroxide is taken as an oxidant, reaction feed liquid is pumped into the reactor through a metering pump, the composition of the catalyst is shown in table 4, the used alicyclic diolefin raw materials and the organic peroxide are shown in table 5, the influence of temperature, pressure, material proportion and airspeed on the yield of reaction products is examined respectively, the experimental results are shown in table 6, and the epoxy resin structures corresponding to examples 2-21 are shown in table 7.
TABLE 4 catalyst mass percent composition
* And (3) injection: c represents a carbon nanofiber.
Table 5 olefin feedstock and peroxide for epoxy resin synthesis by fixed bed reaction process
Examples Alicyclic cycloolefin Organic peroxides
14 Dicyclopentadiene Cumene hydroperoxide
15 5-Vinyl-2-norbornene Cumene hydroperoxide
16 5-Isopropenyl-2-norbornene Cumene hydroperoxide
17 4-Vinyl-1-cyclohexene Hydrogen peroxide tert-amyl alcohol
18 Limonene Tert-butyl hydroperoxide
19 3, 3' -Bicyclopentene Cumene hydroperoxide
20 Spirobicyclohexene Cumene hydroperoxide
21 Spirocyclic pentenes Cumene hydroperoxide
Table 6 fixed bed reaction synthetic epoxy resin process conditions
TABLE 7 epoxy resin structure
While the preferred embodiments of the present application have been described in detail, the present application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.

Claims (5)

1. A method of preparing a cycloaliphatic epoxy resin comprising: taking alicyclic diolefin as a raw material, taking organic peroxide as an oxidant, and in an inert solvent, carrying out catalytic oxidation reaction on the alicyclic diolefin, the organic peroxide and a titanium silicalite molecular sieve catalyst in a reactor under sufficient contact to generate alicyclic epoxy resin;
The titanium silicalite molecular sieve catalyst is a Ti-HMS molecular sieve catalyst with mesoporous characteristics, and comprises the following components: 2.57 to 6.42 percent of TiO 2, 48.95 to 62.90 percent of nano carbon fiber, 28.17 to 38.87 percent of SiO 2, 0.01 to 0.83 percent of magnesia, and 0.44 to 6.41 percent of silane matrix; the UV-vis spectrogram of the catalyst has a strong absorption peak at 220 nm;
the catalytic oxidation reaction temperature is 30-150 ℃ and the pressure is 0-10 MPa; the molar ratio of the alicyclic diolefin to the organic peroxide is 1.0:2.0-1.0:2.5, and the volume ratio of the alicyclic diolefin to the inert solvent is 1: 4-1: 30;
the alicyclic diolefin is selected from any one of cyclopentadiene, 2, 5-norbornadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 4-vinyl-1-cyclohexene, limonene, 3 '-bicyclo-hexene, 3' -bicyclo-pentene, spirobicyclo-hexene and spirobicyclo-pentene;
the organic peroxide is selected from any one of cumene hydroperoxide, tert-butyl hydroperoxide and tert-amyl hydroperoxide;
the preparation method of the titanium silicalite molecular sieve catalyst comprises the following steps:
a) Under inert atmosphere, dissolving a silicon source, a titanium source and a template agent in a mixed solvent of water and organic alcohol, stirring and crystallizing at room temperature for 0.5-10 hours, adding nano carbon fiber, continuously stirring for 10-72 hours, crystallizing at 150-200 ℃ for 1-7 days, and separating, washing and drying a crystallized product to obtain the Ti-HMS loaded by the nano carbon fiber;
b) Adding Ti-HMS loaded by nano carbon fibers into an aqueous solution containing any one or a mixture of Mg (OH) 2、MgO、MgCO3、4MgCO3.Mg(OH)2.5H2 O and dolomite, stirring at room temperature for 10-48 hours, separating out solids, washing with water until the washing liquid is neutral, drying, and roasting at 300-1000 ℃ for 2-20 hours in an inert atmosphere to obtain a Ti-HMS catalyst matrix taking magnesium compound modified nano carbon fibers as a carrier;
c) Treating Ti-HMS catalyst parent body with organosilicon solution at 25-300 deg.c for 0.5-100 hr; the usage amount of the organic silicon is 10% -70% of the weight of the Ti-HMS catalyst matrix; and then filtering and separating out a solid catalyst, washing the solid catalyst by using an inert solvent, and baking the solid catalyst for 10-24 hours in an environment with the pressure of 0.133-1.33 KPa and the temperature of 80-200 ℃ to prepare the magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst.
2. The method according to claim 1, characterized in that: the catalytic oxidation reaction temperature is 60-120 ℃, the pressure is 0.3-6 MPa, and the molar ratio of alicyclic diolefin to organic peroxide is 1.0:2.0-1.0:2.2.
3. The method according to claim 1, characterized in that: the catalytic oxidation reaction adopts an intermittent reaction process or a fixed bed continuous reaction process; by adopting a batch reaction process, the mass ratio of the catalyst to the alicyclic diolefin is 0.01: 100-20: 100, wherein the reaction time is 1-20 hours; and a fixed bed continuous reaction process is adopted, and the total material volume space velocity is 0.1-4.3 h -1.
4. A method according to claim 3, characterized in that: the batch reaction process is adopted, and the mass ratio of the catalyst to the alicyclic diolefin is 0.5: 100-10: 100, the reaction time is 3-6 hours.
5. The method according to claim 1, characterized in that: the inert solvent is selected from any one of heptane, hexane, octane, nonane, decane, undecane, benzene, toluene, ethylbenzene, methylethylbenzene, xylene, isopropylbenzene and petroleum ether.
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