CN109232480A - A kind of acid controlled degradation type cycloaliphatic epoxy resin and preparation method thereof - Google Patents
A kind of acid controlled degradation type cycloaliphatic epoxy resin and preparation method thereof Download PDFInfo
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- CN109232480A CN109232480A CN201811193514.8A CN201811193514A CN109232480A CN 109232480 A CN109232480 A CN 109232480A CN 201811193514 A CN201811193514 A CN 201811193514A CN 109232480 A CN109232480 A CN 109232480A
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- 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
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
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- 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
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- 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
- C08G59/24—Di-epoxy compounds carbocyclic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
A kind of acid controlled degradation type cycloaliphatic epoxy resin and preparation method thereof, belongs to new material technology field, epoxy resin is formed by connecting by alicyclic ring or epoxy group alicyclic ring by acetal bonds completely, and chemical structural formula isPreparation method includes: that alicyclic olefin methanol and acid catalyst are added in organic solvent, hexahydrobenzaldehyde, deicer is added at a temperature of -15-15 DEG C, the reaction was continued 6-48 hours obtains intermediate；Epoxidation reagent solution, lye are added drop-wise in midbody solution at a temperature of -25-25 DEG C, control reaction system PH is 7-8, and reaction obtains product in 6-24 hours.It is in the lower liquid of viscosity under obtained epoxy resin at room temp, the product after anhydride-cured is degradable in organic or inorganic acid, and degradation speed is controllable with the Strength Changes of acid.Epoxy resin provided by the invention is as adhesive for Electronic Packaging or carbon fibre composite field, it can be achieved that the recycling and reusing of the precious materials such as noble metal or carbon fiber.
Description
Technical field
The present invention relates to a kind of acetal radical liquid alicyclic epoxy resins and preparation method thereof, and in particular to a kind of room temperature is
Liquid, sour controlled degradation type bifunctionality acetal radical alicyclic ring epoxide resin and preparation method thereof, are used for integrated circuit, light-emitting diodes
It manages (LED) optoelectronic device packaging material or is used for carbon fiber/epoxy resin complex matrix resin material, belong to new material skill
Art field.
Background technique
Cycloaliphatic epoxy resin is because of glass transition temperature with higher, lower viscosity and preferable UV resistant energy
Power, and it is widely used in the fields such as coating, high voltage insulating materials, diluent, electronic component and printed circuit plate coating.But
It is, since epoxy resin will form insoluble not molten three-dimensional net structure after crosslinking curing, to cause solidfied material recycling and reusing tired
Difficulty increases epoxy resin use cost, therefore degradable epoxy comes into being.
General common degradable alicyclic ring epoxide resin is thermal degradation type, and thermally labile base is contained in its molecular structure
Group, such as secondary ester, tertiary ester structure, carbamate, structural carbonate, phosphate, phosphite ester structure, secondary ether, tertiary ether structure.
CN201210022622.5 discloses the thermal degradation cycloaliphatic epoxy resin of a kind of phosphate ester-containing structure, when temperature is arrived at 240 DEG C
It may be implemented to degrade rapidly when between 300 DEG C.CN201310407848.1, which is disclosed, contains sulfite structure in a kind of molecule
Thermal degradation type alicyclic ring epoxide resin, after other epoxy resin co-curings, product is degraded rapidly between 180 DEG C to 390 DEG C.But
It is which kind of above-mentioned structure whether to be contained, the degradation temperature of thermal degradation type epoxy resin is generally relatively high, in certain fields
Using being restricted.
Chemical degradation type epoxy resin is the degradable asphalt mixtures modified by epoxy resin of one kind in molecule containing the structure sensitive to chemical reagent
Rouge, it is auxiliary under chemical reagent effect to realize degradation at relatively low temperatures, thus thermal degradation asphalt mixtures modified by epoxy resin can be made up
The deficiency of rouge.The designs such as Buchwalter have synthesized the difunctional epoxy resin in three kinds of molecular structures containing acetal groups,
Since acetal groups can hydrolyze generation aldehyde in acid condition, so this epoxy resin may be implemented to degrade.GB 865340,
JP 2013056990 discloses the alicyclic ring epoxide resin in several molecules containing acetal groups, but does not all analyze its degradation
Performance.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of sour controlled degradation bifunctionality acetal radical alicyclic epoxy
Resin and preparation method thereof, from molecule angle, design has synthesized the bifunctionality rouge containing acetal groups in a kind of molecule
After ring epoxy resin, with acid anhydrides crosslinking curing, its degradation property is tested, experiment shows this kind of epoxy resin in different acidity
Lower degradation time is adjustable.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of acid controlled degradation type cycloaliphatic epoxy resin, the sour controlled degradation type cycloaliphatic epoxy resin completely by
Alicyclic ring or epoxy group alicyclic ring are formed by connecting by acetal bonds, and chemical structural formula is as follows:
A kind of preparation method of acid controlled degradation type cycloaliphatic epoxy resin, synthetic route are as follows:
Specific step is as follows:
The first step, synthesis of alicyclic alkene acetal
Alicyclic olefin methanol and acid catalyst are added in organic solvent A, the mixed solution A of 1-3M is made into, in -15-
Hexahydrobenzaldehyde is added dropwise in above-mentioned mixed solution A at a temperature of 15 DEG C, wherein alicyclic olefin methanol, cyclohexyl first
Aldehyde and acid catalyst molar ratio are 2-5:1:0.1-1；The deicer of solvent quality score 5%-30% is added, with this condition
The reaction was continued 6-48 hours, and midbody product alicyclic olefin acetal is made.
The acid catalyst is p-methyl benzenesulfonic acid, methane sulfonic acid, sulfamic acid, the concentrated sulfuric acid, hydrogen chloride, phosphoric acid, dense nitre
The mixture of one or more of acid directlys adopt solid acid, ion exchange resin；The deicer be calcium sulfate,
The mixture of one or more of molecular sieve, copper sulphate；The organic solvent A be n-hexane, hexamethylene, methylene chloride,
The mixture of one or both of tetrahydrofuran, benzene, toluene.
Second step, the epoxidation of alicyclic olefin acetal
Alicyclic olefin acetal made from step (1) is added in organic solvent B and obtains B mixed solution.At -25-25 DEG C
At a temperature of epoxidation reagent solution, lye are added dropwise in above-mentioned mixed solution B, control reaction system PH is 7-8, wherein alicyclic ring
The molar ratio of race's alkene acetal and epoxidation reagent is 1:2-6, and the reaction was continued 6-24 hours under mechanical stirring obtains alicyclic contracting
Formaldehyde epoxy resin.
The epoxidation reagent be Peracetic acid, peroxide propiolic acid, benzoyl hydroperoxide, metachloroperbenzoic acid, to nitre
Base benzoyl hydroperoxide, nitroperoxybenzoic or ammonium persulfate-sodium bisulfate；The organic solvent B be methylene chloride, acetone,
The mixture of one or more of organic ether, chlorohydrocarbon, dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate.
Bifunctionality alicyclic ring epoxide resin prepared by the present invention can be consolidated in the presence of anhydride curing agent, curing accelerator
Change, solidification temperature is 80-200 DEG C, wherein anhydride group and the molar ratio of epoxy resin epoxide epoxy group group are in anhydride curing agent
0.8-1.0, curing accelerator account for the 0.1%-1.0% of overall quality.
The anhydride curing agent is phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl
The mixing of one or more of tetrabydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride
Object；The curing accelerator is one of tertiary amine and its esters, imidazoles, quaternary ammonium salt, imidazolines, nano-titanium dioxide
Or two or more mixture.
Alicyclic ring epoxide resin prepared by the present invention can be in acid/organic solvent/aqueous systems or acid/organic solvent system
Degradation, depending on degradation time is because of system acidity and temperature, temperature is selected in room temperature to system reflux temperature.
The acid be methane sulfonic acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, hydrochloric acid, sulfuric acid, oxalic acid, formic acid, it is a kind of in acetic acid or
Two kinds of mixture；The organic solvent is tetrahydrofuran, methylene chloride, chloroform, acetone, dioxane, acetic acid second
The mixture of one or more of ester, ethyl alcohol, methanol.
For alicyclic ring epoxide resin prepared by the present invention after anhydride-cured, solidfied material degradation time is adjustable, and degradation time spectrum is
A few minutes were to several days or longer.
Epoxy resin prepared by the present invention can be used for integrated circuit, LED encapsulation, coating, adhesive material.
Relatively low temperature degradation, control degradation body may be implemented the beneficial effects of the invention are as follows the epoxy resin of preparation
System is acid or organic solvent type, and degradation time is adjustable, on the one hand can meet integrated circuit, optoelectronic packaging device, valuable
Carbon-fiber composite material recycling disassembly and the demand for repairing operating procedure, on the other hand also to judging acid rain corrosion to epoxy resin
Guidance is made in influence as coating, protective layer.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of acetal radical alicyclic ring epoxide resin.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of acetal radical alicyclic ring epoxide resin.
Fig. 3 is acetal radical alicyclic ring epoxide resin solidfied material or else with the degradation curve in degradation system.
Specific embodiment:
Describe specific implementation case of the invention in detail below with reference to technical solution:
The infrared spectroscopy of prepared acetal radical alicyclic ring epoxide resin U.S.'s NEXUS EURO determination of infrared spectroscopy (figure
1), nuclear magnetic resonance spectroscopy measures (Fig. 2) with 500MHz nuclear magnetic resonance chemical analyser Bruker AVANCE III, solidfied material acid degradation
Behavior foundation is residual mass/initial mass.
1 bifunctionality alicyclic ring epoxide resin solidfied material acid degradation behavior of table
Embodiment 1
The preparation of bifunctionality acetal radical alicyclic ring epoxide resin:
(1) at ice-water bath condition DEG C, 42.064g is added in the 250ml three-necked flask for being equipped with mechanical stirring, thermometer
3- cyclohexene -1- methanol, 25g 5A molecular sieve, 2.375g p-methyl benzenesulfonic acid monohydrate, 187.5ml n-hexane are added dropwise
14.021g hexahydrobenzaldehyde terminates reaction after being stirred to react 6h, and product is first washed with 15%NaOH aqueous solution, then spent again
Ion water washing is to neutrality, and with anhydrous magnesium sulfate drying, filtering, concentration, vacuum distillation obtains midbody product, yield 65%.
(2) 45g ammonium persulfate-sodium bisulfate, 0.06g ethylenediamine tetra-acetic acid adapted 240ml deionized water dissolving are prepared into ring
Oxidising agent solution.Under the conditions of ice-water bath, equipped with mechanical stirring, thermometer, constant pressure funnel 1000ml four-hole bottle in,
10.515g midbody product, crown ether -6 0.9g 18- is added, each 90ml of methylene chloride, acetone adds above-mentioned epoxidation reagent
Solution is separately taking lye regulation system PH range between 7-8 in epoxidation process, persistently stir 6h and terminate reaction, filtering will
Water phase is extracted with dichloromethane, and merges organic phase, then organic phase is washed with deionized, with anhydrous magnesium sulfate is dry, filtering,
Concentration, obtains final product, yield 81%.
Infrared spectroscopy (cm-1): 2979,2923,2852,1450,1435,1343,1259,1129,1078,1045,891,
810,787.Nuclear magnetic resonance spectroscopy (CDCl3/TMS, ppm): 3.94 (d, 1H, O-CH-O), 2.89-3.36 (m, 8H, O-CH2-,
O-CH-on epoxide ring),0.68-2.13(m,25H,-CH2-,-CH-).
Embodiment 2
The preparation of bifunctionality acetal radical alicyclic ring epoxide resin:
Under the conditions of (1) -15 DEG C, 28.043g 3- ring is added in the 500ml three-necked flask for being equipped with mechanical stirring, thermometer
Hexene -1- methanol, 37.5g calcium sulfate, 2.403g methane sulfonic acid, 375ml toluene are added dropwise 14.021g hexahydrobenzaldehyde, stir
Reaction is terminated after mixing reaction 24, product is first washed with 15%NaOH aqueous solution, is then washed with deionized again to neutrality, with nothing
Water magnesium sulfate is dry, filtering, is concentrated, and vacuum distillation obtains midbody product, yield 58%.
(2) 57.2g metachloroperbenzoic acid is dissolved with 200ml methylene chloride and is configured to epoxidation reagent solution.-25℃
Under the conditions of, equipped with mechanical stirring, thermometer, constant pressure funnel 500ml four-hole bottle in, be added 38.5g midbody product,
Above-mentioned epoxidation reagent solution is added, lye regulation system PH range is separately being taken persistently to stir in epoxidation process between 7-8
12h terminates reaction, and filtrate is used 20%NaSO by filtering3Aqueous solution washes twice, and liquid separation organic phase washs 2 with 10% sodium bicarbonate
It is secondary, then be washed with deionized water to neutrality, with anhydrous magnesium sulfate drying, filtering, concentration, obtain final product, yield 85%.
Embodiment 3
The preparation of bifunctionality acetal radical alicyclic ring epoxide resin:
Under the conditions of (1) 15 DEG C, 70.106g3- hexamethylene is added in the 500ml three-necked flask for being equipped with mechanical stirring, thermometer
14.021g hexahydrobenzaldehyde is added dropwise in alkene -1- methanol, 50g copper sulphate, 12.136g sulfamic acid, 187.5ml benzene, stirring
Reaction is terminated after reaction 48, product is first washed with 15%NaOH aqueous solution, is then washed with deionized again to neutrality, use is anhydrous
Magnesium sulfate is dry, filtering, is concentrated, and vacuum distillation obtains midbody product, yield 52%.
(2) 72g dissolves nitroperoxybenzoic with 200ml n,N-Dimethylformamide and is configured to epoxidation reagent
Solution.Under the conditions of 25 DEG C, equipped with mechanical stirring, thermometer, constant pressure funnel 500ml four-hole bottle in, be added 38.5g in
Mesosome product, is added above-mentioned epoxidation reagent solution, separately taken in epoxidation process lye regulation system PH range 7-8 it
Between, lasting stirring terminates reaction for 24 hours, and filtrate is used 20%NaSO by filtering3Aqueous solution washes twice, 10% carbon of liquid separation organic phase
Sour hydrogen sodium washs 2 times, then is washed with deionized water to neutrality, with anhydrous magnesium sulfate drying, filtering, concentration, obtains final product, yield
83%.
Embodiment 4--- solidification
Alicyclic ring epoxide resin made from embodiment 1 and methylhexahydrophthalic anhydride, 2-ethyl-4-methylimidazole are mixed
Homogeneous transparent solution is made in conjunction, and epoxide epoxy group group and anhydride group molar ratio are 1:0.8, and imidazoles is the 0.5% of gross mass, will
The epoxy composite is heated to 125 DEG C and solidifies 2 hours, and 165 DEG C solidify 4 hours, and 190 DEG C solidify 4 hours, obtain cured product.
Embodiment 5--- solidification
Alicyclic ring epoxide resin made from embodiment 1 and methylhexahydrophthalic anhydride, benzyl dimethylamine are mixed
Homogeneous transparent solution, epoxide epoxy group group and anhydride group molar ratio are 1:0.95, and curing accelerator is the 0.8% of gross mass,
The epoxy composite is heated to 100 DEG C to solidify 2 hours, 150 DEG C solidify 6 hours, and 190 DEG C solidify 2 hours, obtain solidification and produce
Object.
Embodiment 6--- solidification
Alicyclic ring epoxide resin made from embodiment 1 and methyl tetrahydrophthalic anhydride, 2-ethyl-4-methylimidazole are mixed
Homogeneous transparent solution is made in conjunction, and epoxide epoxy group group and anhydride group molar ratio are 1:0.85, and curing accelerator is gross mass
0.2%, which is heated to 130 DEG C and is solidified 2 hours, 170 DEG C solidify 6 hours, and 200 DEG C solidify 2 hours, consolidate
Change product.
Embodiment 7--- degradation
Methane sulfonic acid/tetrahydrofuran/aqueous systems are prepared, wherein organic phase (tetrahydrofuran) and water volume ratio are 4:1, methyl
Sulfonic acid concentrations are 0.5mol/L.The solidfied material that Example 4 obtains is made the sample having a size of 10 × 6 × 2mm and is placed in above-mentioned drop
Temperature rising reflux in enzymatic hydrolysis system, record degradation 50% and degradable required time, the results are shown in Table 1.
Embodiment 8
With embodiment 4, degradation system is 0.5M methane sulfonic acid/ethanol/water for epoxy curing compound preparation, maintains organic phase (second
Alcohol) and water volume ratio, other embodiments it is same.It is tested, the results are shown in Table 1.
Embodiment 9
Epoxy curing compound preparation is 2.0M oxalic acid/tetrahydrofuran/water with embodiment 4, degradation system, is tested, as a result
It is shown in Table 1.
Embodiment 10
Epoxy curing compound preparation is 2.0M oxalic acid/ethanol/water with embodiment 4, degradation system, is tested, be the results are shown in Table
1。
Embodiment 11
Epoxy curing compound preparation is 2.0M acetic acid/tetrahydrofuran/water with embodiment 4, degradation system, is tested, as a result
It is shown in Table 1.
Embodiment 12
Epoxy curing compound preparation is 2.0M acetic acid/ethanol/water with embodiment 4, degradation system, is tested, be the results are shown in Table
1。
Embodiment described above only expresses embodiments of the present invention, and but it cannot be understood as to the invention patent
Range limitation, it is noted that for those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.
Claims (10)
1. a kind of acid controlled degradation type cycloaliphatic epoxy resin, which is characterized in that the sour controlled degradation type alicyclic epoxy
Resin is formed by connecting by alicyclic ring or epoxy group alicyclic ring by acetal bonds completely, and chemical structural formula is as follows:
2. a kind of preparation method of sour controlled degradation type cycloaliphatic epoxy resin described in claim 1, which is characterized in that described
Ring race epoxy resin synthetic route it is as follows:
Preparation step is as follows:
The first step, synthesis of alicyclic alkene acetal
Alicyclic olefin methanol and acid catalyst are added in organic solvent A, the mixed solution A of 1-3M is made into, at -15-15 DEG C
At a temperature of hexahydrobenzaldehyde is added dropwise in above-mentioned mixed solution A, wherein alicyclic olefin methanol, hexahydrobenzaldehyde and
Acid catalyst molar ratio is 2-5:1:0.1-1；The deicer for adding solvent quality score 5%-30%, continues with this condition
Alicyclic olefin acetal is made in reaction 6-48 hours；
Second step, the epoxidation of alicyclic olefin acetal
Alicyclic olefin acetal made from step (1) is added in organic solvent B and obtains B mixed solution；In -25-25 DEG C of temperature
Lower that epoxidation reagent solution, lye are added dropwise in above-mentioned mixed solution B, control reaction system PH is 7-8, wherein alicyclic alkene
The molar ratio of hydrocarbon acetal and epoxidation reagent is 1:2-6, and the reaction was continued 6-24 hours under mechanical stirring obtains alicyclic acetal ring
Oxygen resin.
3. a kind of preparation method of sour controlled degradation type cycloaliphatic epoxy resin according to claim 2, which is characterized in that
Acid catalyst described in the first step is p-methyl benzenesulfonic acid, methane sulfonic acid, sulfamic acid, the concentrated sulfuric acid, hydrogen chloride, phosphoric acid, concentrated nitric acid
One or more of mixture or directly adopt solid acid, ion exchange resin；Deicer described in the first step is sulphur
The mixture of one or more of sour calcium, molecular sieve, copper sulphate.
4. a kind of preparation method of sour controlled degradation type cycloaliphatic epoxy resin according to claim 2 or 3, feature exist
In, epoxidation reagent described in second step be Peracetic acid, peroxide propiolic acid, benzoyl hydroperoxide, metachloroperbenzoic acid, to nitre
Base benzoyl hydroperoxide, nitroperoxybenzoic or ammonium persulfate-sodium bisulfate.
5. a kind of preparation method of sour controlled degradation type cycloaliphatic epoxy resin according to claim 2 or 3, feature exist
In organic solvent A described in the first step is one of n-hexane, hexamethylene, methylene chloride, tetrahydrofuran, benzene, toluene or two
The mixture of kind；Organic solvent B described in second step is methylene chloride, acetone, organic ether, chlorohydrocarbon, dimethyl sulfoxide, N, N- diformazan
The mixture of one or more of base formamide, ethyl acetate.
6. a kind of preparation method of sour controlled degradation type cycloaliphatic epoxy resin according to claim 4, which is characterized in that
Organic solvent A described in the first step is one or both of n-hexane, hexamethylene, methylene chloride, tetrahydrofuran, benzene, toluene
Mixture；Organic solvent B described in second step is methylene chloride, acetone, organic ether, chlorohydrocarbon, dimethyl sulfoxide, N, N- dimethyl
The mixture of one or more of formamide, ethyl acetate.
7. a kind of curing method of sour controlled degradation type cycloaliphatic epoxy resin described in claim 1, which is characterized in that described
Sour controlled degradation type cycloaliphatic epoxy resin can solidify in the presence of anhydride curing agent, curing accelerator, solidification temperature is
80-200 DEG C, wherein the molar ratio of anhydride group and epoxy resin epoxide epoxy group group is 0.8-1.0, solidification in anhydride curing agent
Promotor accounts for the 0.1%-1.0% of overall quality.
8. a kind of preparation method of sour controlled degradation type cycloaliphatic epoxy resin according to claim 7, which is characterized in that
The anhydride curing agent is phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydro neighbour's benzene
The mixture of one or more of dicarboxylic acid anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride；Described
Curing accelerator be one or both of tertiary amine and its esters, imidazoles, quaternary ammonium salt, imidazolines, nano-titanium dioxide with
On mixture.
9. a kind of curing method of sour controlled degradation type cycloaliphatic epoxy resin described in claim 1, which is characterized in that described
Sour controlled degradation type cycloaliphatic epoxy resin can be dropped in acid/organic solvent/aqueous systems or acid/organic solvent system
Solution, depending on degradation time is because of system acidity and temperature.
10. a kind of preparation method of sour controlled degradation type cycloaliphatic epoxy resin according to claim 9, feature exist
In, the acid be methane sulfonic acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, hydrochloric acid, sulfuric acid, oxalic acid, formic acid, in acetic acid it is one or two kinds of
Mixture；The organic solvent is tetrahydrofuran, methylene chloride, chloroform, acetone, dioxane, ethyl acetate, second
The mixture of one or more of alcohol, methanol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111505035A (en) * | 2020-04-16 | 2020-08-07 | 西安交通大学 | Preparation and nondestructive recovery method of mosaic sample |
| CN112920379A (en) * | 2021-03-26 | 2021-06-08 | 蓝赛夫(上海)电子材料有限公司 | Epoxy resin monomer and intermediate thereof, preparation method, epoxy resin and recovery method |
| CN115124748A (en) * | 2022-07-28 | 2022-09-30 | 海南联塑科技实业有限公司 | Method for inhibiting degradation of plastic and precipitating micro plastic and application |
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Application publication date: 20190118 |