CN108484533A - A kind of epoxy monomer of the mesomorphic unit containing arylate structural and preparation method thereof - Google Patents
A kind of epoxy monomer of the mesomorphic unit containing arylate structural and preparation method thereof Download PDFInfo
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- CN108484533A CN108484533A CN201810373605.3A CN201810373605A CN108484533A CN 108484533 A CN108484533 A CN 108484533A CN 201810373605 A CN201810373605 A CN 201810373605A CN 108484533 A CN108484533 A CN 108484533A
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- 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
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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Abstract
The invention belongs to high-molecular organic material technical fields, disclose a kind of epoxy monomer of the mesomorphic unit containing arylate structural.Invention additionally discloses the preparation methods of this monomer：O-allyl phenol and acid binding agent, paraphthaloyl chloride are dissolved in solvent respectively, paraphenylene terephthalamide's solutions of chlorine is slowly added dropwise in o-allyl phenol and acid binding agent solution and is reacted, first ice bath reaction, after react at room temperature, removal of impurities, washing, it is dry, obtain two (o-allyl base) terephthalates；Two (o-allyl base) terephthalates are dissolved in solvent, oxidant reaction is added, are extracted, it is dry, obtain the epoxy monomer of the mesomorphic unit containing arylate structural.The preparation method reaction of the present invention is mild, easily operated, and possibility is provided for industrialized realization.Epoxide resin material prepared by the present invention has excellent performance, in the preferable application prospect in the fields such as Aeronautics and Astronautics, electrician and microelectronics.
Description
Technical field
The invention belongs to high-molecular organic material technical field, more particularly to the epoxy of a kind of mesomorphic unit containing arylate structural
Resin monomer and preparation method thereof.
Background technology
Epoxy resin hot solids are due to excellent comprehensive performance, in Aeronautics and Astronautics, electrical, machinery, chemical industry, micro- electricity
The every field such as son have very extensive application.Moreover, outstanding feature of the epoxy resin in terms of performance and synthesis, whether
As structural material or as functional material, huge application prospect is adequately recognized.
With the development of microelectronics science and technology, to material, more stringent requirements are proposed for the fast development of electronic component, tradition
Epoxy resin has been insufficient for demand in modern microelectronic field.In recent years, rigid rod epoxy resin has obtained people
Extensive concern.They typically exhibit Mesomorphic behavior, referred to as liquid crystalline epoxy (LCERs), with traditional bisphenol-A epoxy tree
Lipid phase ratio, LCERs contains rigid mesomorphic unit more, and in its solidification process, liquid crystal microcell, which occurs to be orientated, forms self-reinforced structure,
So as to improve the toughness of solidfied material, and assign material some new Physical and mechanical properties, it is high in conjunction with itself intensity, modulus is big,
High temperature resistant and the small feature of linear expansion coefficient have wide answer in high-performance microelectronics encapsulation and nonlinear optical material
Use foreground.In addition, liquid crystalline epoxy also has advantage in terms of structure design, work(can be introduced by the structure design of epoxy monomer
Energy property mesogenic groups, to achieve the purpose that improve its performance.
Therefore, design synthesizing new high-performance, functionalization liquid crystalline epoxy are increasingly becoming the important component of epoxy resin
And research direction.
Invention content
The primary purpose of the present invention is that epoxy monomer and its preparation of a kind of mesomorphic unit containing arylate structural of offer
Method.
The purpose of the invention is achieved by the following technical solution：
A kind of epoxy monomer of the mesomorphic unit containing arylate structural, the epoxy monomer are two (2- (epoxy second
Alkane -2- methylene) phenyl) terephthalate, chemical structural formula is as shown in formula one：
A kind of preparation method of the epoxy monomer of the mesomorphic unit containing arylate structural, includes the following steps：
(1) o-allyl phenol and acid binding agent, paraphthaloyl chloride are dissolved in solvent respectively, paraphthaloyl chloride is molten
Liquid, which is slowly added dropwise in o-allyl phenol and acid binding agent solution, to react, first ice bath reaction, rear to react at room temperature, and cleans, washs, does
It is dry, obtain two (o-allyl base) terephthalates；
(2) two (o-allyl base) terephthalates are dissolved in solvent, oxidant reaction is added, extracted, it is dry,
Obtain the epoxy monomer of the mesomorphic unit containing arylate structural.
Preferably, in step (1), the solvent is dichloromethane, chloroform, tetrahydrofuran, one in ethyl acetate
Kind；Acid binding agent described in step (1) is triethylamine, one kind in pyridine；O-allyl phenol described in step (1), to benzene
Dimethyl chloride, acid binding agent molar ratio be (2.2~2.5)：1：(2.5~3).
Preferably, in step (1), the time for adding is 40min；The ice bath reaction time is 2h, and the room temperature is anti-
For for 24 hours between seasonable；The room temperature is 20~30 DEG C.
Preferably, in step (1), the removal of impurities is to filter removal of impurities；The washing is that deionized water is washed 3 times, with anhydrous
Ethyl alcohol washs 3 times；The drying is dried in vacuo for 24 hours at 55 DEG C.
Preferably, in step (2), the solvent is dichloromethane, chloroform, tetrahydrofuran, one in ethyl acetate
Kind；Two (o-allyl base) terephthalate and the molar ratio of oxidant are 1：(2.5~3)；The oxidant
For metachloroperbenzoic acid.
Preferably, in step (2), the reaction temperature is 40 DEG C, and the reaction time is 72 hours.
Preferably, in step (2), the extraction, dry process is that solution uses Na successively2SO3Aqueous solution, Na2CO3Water
Solution and saturation NaCl aqueous solution extractions, organic layer are removed water with desiccant dryness, are filtered to get filtrate, and are rotated filtrate, are used isopropanol
Recrystallization, 50 DEG C of vacuum drying obtain product.
Preferably, the Na2SO3The mass fraction of aqueous solution is 10%, Na2CO3The mass fraction of aqueous solution is 10%,
The drier is one kind in anhydrous sodium sulfate and anhydrous magnesium sulfate.
Advantages of the present invention and advantageous effect
(1) present invention is prepared for the asphalt mixtures modified by epoxy resin of the mesomorphic unit containing arylate structural using the chemical reaction of two steps is concisely and efficiently
Alicyclic monomer.
(2) the more traditional commercial epoxy resin of the epoxide resin material of the invention prepared is shown superior hot
Can, there is larger potential using value and preferable application prospect in fields such as Aeronautics and Astronautics, electricians.
(3) preparation method reaction of the present invention is mild, easily operated, and possibility is provided for industrialized realization.
Description of the drawings
Fig. 1 is two (2- (ethylene oxide -2- methylene) phenyl) terephthalates1H NMR。
Fig. 2 is the infrared spectrum of two (2- (ethylene oxide -2- methylene) phenyl) terephthalates.
Fig. 3 is the solidification of two (2- (ethylene oxide -2- methylene) phenyl) terephthalates and curing agent sulfanilamide (SN) (SAA)
The DSC of product schemes.
Fig. 4 is the solidification of two (2- (ethylene oxide -2- methylene) phenyl) terephthalates and curing agent sulfanilamide (SN) (SAA)
The TGA of product schemes.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Material involved in the following example can be obtained from commercial channel.
Embodiment 1
A kind of preparation method of the epoxy resin of mesomorphic unit containing arylate structural, includes the following steps：
(1) under condition of ice bath, 2.95g (22mmol) o-allyl phenol is dissolved in 40mL dichloromethane, 2.53g is added
Then 2.03g (10mmol) paraphthaloyl chloride is dissolved in 20mL dichloromethane by (25mmol) triethylamine as acid binding agent,
40min is added dropwise in the dichloromethane solution of o-allyl phenol, first 2h is reacted in ice bath, after reacted under the conditions of 20 DEG C
For 24 hours, stop reaction, filter the quaternary ammonium salt for removing and being generated in reaction process, then washed 3 times with deionized water, then with anhydrous second
Alcohol washs 3 times.It is dried in vacuo at 55 DEG C and obtains powdery product for 24 hours.Yield is 89%.
(2) 3.98g (10mmol) two (o-allyl base) terephthalate is dissolved in 40mL dichloromethane, is added
4.31g (25mmol) metachloroperbenzoic acid reacts 72h at 40 DEG C, stops reaction, is then filtered to remove the m-chloro that reaction is precipitated
Benzoic acid, filtrate use 10%Na successively2SO3Aqueous solution, 10%Na2CO3Aqueous solution and saturation NaCl aqueous solution extractions, organic layer
It is dried and is removed water with anhydrous sodium sulfate, filtered to get filtrate, revolving removes solvent, recrystallisation from isopropanol, and 50 DEG C of vacuum drying are produced
Object.Yield is 76%.
Embodiment 2
A kind of preparation method of the epoxy resin of mesomorphic unit containing arylate structural, includes the following steps：
(1) under condition of ice bath, 3.09g (23mmol) o-allyl phenol is dissolved in 40mL chloroforms, 2.73g is added
Then 2.03g (10mmol) paraphthaloyl chloride is dissolved in 20mL chloroforms by (27mmol) triethylamine as acid binding agent,
40min is added dropwise in the chloroform soln of o-allyl phenol, first 2h is reacted in ice bath, after reacted under the conditions of 25 DEG C
For 24 hours, stop reaction, filter the quaternary ammonium salt for removing and being generated in reaction process, then washed 3 times with deionized water, then with anhydrous second
Alcohol washs 3 times.It is dried in vacuo at 55 DEG C and obtains powdery product for 24 hours.Yield is 88%.
(2) 3.98g (10mmol) two (o-allyl base) terephthalate is dissolved in 40mL chloroforms, is added
4.66g (27mmol) metachloroperbenzoic acid reacts 72h at 40 DEG C, stops reaction, is then filtered to remove the m-chloro that reaction is precipitated
Benzoic acid, filtrate use 10%Na successively2SO3Aqueous solution, 10%Na2CO3Aqueous solution and saturation NaCl aqueous solution extractions, organic layer
It is dried and is removed water with anhydrous sodium sulfate, filtered to get filtrate, revolving removes solvent, recrystallisation from isopropanol, and 50 DEG C of vacuum drying are produced
Object.Yield is 78%.
Embodiment 3
A kind of preparation method of the epoxy resin of mesomorphic unit containing arylate structural, includes the following steps：
(1) under condition of ice bath, 3.35g (25mmol) o-allyl phenol is dissolved in 40mL tetrahydrofurans, 3.04g is added
Then 2.03g (10mmol) paraphthaloyl chloride is dissolved in 20mL tetrahydrofurans by (30mmol) triethylamine as acid binding agent,
40min is added dropwise in the tetrahydrofuran solution of o-allyl phenol, first 2h is reacted in ice bath, after reacted under the conditions of 25 DEG C
For 24 hours, stop reaction, filter the quaternary ammonium salt for removing and being generated in reaction process, then washed 3 times with deionized water, then with anhydrous second
Alcohol washs 3 times.It is dried in vacuo at 55 DEG C and obtains powdery product for 24 hours.Yield is 85%.
(2) 3.98g (10mmol) two (o-allyl base) terephthalate is dissolved in 40mL tetrahydrofurans, is added
5.18g (30mmol) metachloroperbenzoic acid reacts 72h at 40 DEG C, stops reaction, is then filtered to remove the m-chloro that reaction is precipitated
Benzoic acid, filtrate use 10%Na successively2SO3Aqueous solution, 10%Na2CO3Aqueous solution and saturation NaCl aqueous solution extractions, organic layer
It is dried and is removed water with anhydrous sodium sulfate, filtered to get filtrate, revolving removes solvent, recrystallisation from isopropanol, and 50 DEG C of vacuum drying are produced
Object.Yield is 78%.
Embodiment 4
A kind of preparation method of the epoxy resin of mesomorphic unit containing arylate structural, includes the following steps：
(1) under condition of ice bath, 3.35g (25mmol) o-allyl phenol is dissolved in 40mL ethyl acetate, 2.37g is added
Then 2.03g (10mmol) paraphthaloyl chloride is dissolved in 20mL ethyl acetate by (30mmol) pyridine as acid binding agent,
40min is added dropwise in the ethyl acetate solution of o-allyl phenol, first 2h is reacted in ice bath, after reacted under the conditions of 30 DEG C
For 24 hours, stop reaction, filter the quaternary ammonium salt for removing and being generated in reaction process, then washed 3 times with deionized water, then with anhydrous second
Alcohol washs 3 times.It is dried in vacuo at 55 DEG C and obtains powdery product for 24 hours.Yield is 86%.
(2) 3.98g (10mmol) two (o-allyl base) terephthalate is dissolved in 40mL ethyl acetate, is added
5.18g (30mmol) metachloroperbenzoic acid reacts 72h at 40 DEG C, stops reaction, is then filtered to remove the m-chloro that reaction is precipitated
Benzoic acid, filtrate use 10%Na successively2SO3Aqueous solution, 10%Na2CO3Aqueous solution and saturation NaCl aqueous solution extractions, organic layer
It is dried and is removed water with anhydrous magnesium sulfate, filtered to get filtrate, revolving removes solvent, recrystallisation from isopropanol, and 50 DEG C of vacuum drying are produced
Object.Yield is 79%.
Embodiment 5
A kind of preparation method of the epoxy resin of mesomorphic unit containing arylate structural, includes the following steps：
(1) under condition of ice bath, 2.95g (22mmol) o-allyl phenol is dissolved in 40mL tetrahydrofurans, 1.98g is added
Then 2.03g (10mmol) paraphthaloyl chloride is dissolved in 20mL tetrahydrofurans by (25mmol) pyridine as acid binding agent,
40min is added dropwise in the tetrahydrofuran solution of o-allyl phenol, first 2h is reacted in ice bath, after reacted under the conditions of 30 DEG C
For 24 hours, stop reaction, filter the quaternary ammonium salt for removing and being generated in reaction process, then washed 3 times with deionized water, then with anhydrous second
Alcohol washs 3 times.It is dried in vacuo at 55 DEG C and obtains powdery product for 24 hours.Yield is 89%.
(2) 3.98g (10mmol) two (o-allyl base) terephthalate is dissolved in 40mL dichloromethane, is added
4.83g (28mmol) metachloroperbenzoic acid reacts 72h at 40 DEG C, stops reaction, is then filtered to remove the m-chloro that reaction is precipitated
Benzoic acid, filtrate use 10%Na successively2SO3Aqueous solution, 10%Na2CO3Aqueous solution and saturation NaCl aqueous solution extractions, organic layer
It is dried and is removed water with anhydrous magnesium sulfate, filtered to get filtrate, revolving removes solvent, recrystallisation from isopropanol, and 50 DEG C of vacuum drying are produced
Object.Yield is 76%.
The epoxy monomer that above-described embodiment obtains obtains crosslinked asphalt mixtures modified by epoxy resin with curing agent sulfanilamide (SN) (SAA) crosslinking curing
Fat, it is 185 DEG C to measure its glass transition temperature with DSC, and by thermogravimetric analysis, 5% thermal degradation temperature is 344 DEG C, is had
Good thermal stability.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (9)
1. a kind of epoxy monomer of mesomorphic unit containing arylate structural, which is characterized in that the epoxy monomer is two (2-
(ethylene oxide -2- methylene) phenyl) terephthalate, chemical structural formula is as shown in formula one：
2. a kind of preparation method of the epoxy monomer of mesomorphic unit containing arylate structural, which is characterized in that include the following steps：
(1) o-allyl phenol and acid binding agent, paraphthaloyl chloride are dissolved in solvent respectively, paraphenylene terephthalamide's solutions of chlorine is delayed
Slow be added dropwise in o-allyl phenol and acid binding agent solution is reacted, first ice bath reaction, rear to react at room temperature, and is cleaned, is washed, dry,
Obtain two (o-allyl base) terephthalates；
(2) two (o-allyl base) terephthalates are dissolved in solvent, oxidant reaction is added, extracted, it is dry, it obtains
The epoxy monomer of the mesomorphic unit containing arylate structural.
3. preparation method according to claim 2, which is characterized in that in step (1), the solvent be dichloromethane, three
Chloromethanes, tetrahydrofuran, one kind in ethyl acetate；Acid binding agent described in step (1) is triethylamine, one kind in pyridine；
O-allyl phenol described in step (1), paraphthaloyl chloride, acid binding agent molar ratio be (2.2~2.5)：1：(2.5~3).
4. preparation method according to claim 2, which is characterized in that in step (1), the time for adding is 40min；Institute
It is 2h to state the ice bath reaction time, and the room temperature reaction time is for 24 hours；The room temperature is 20~30 DEG C.
5. preparation method according to claim 2, which is characterized in that in step (1), the removal of impurities is to filter removal of impurities；Institute
It is that deionized water is washed 3 times to state washing, is washed 3 times with absolute ethyl alcohol；The drying is dried in vacuo for 24 hours at 55 DEG C.
6. preparation method according to claim 2, which is characterized in that in step (2), the solvent be dichloromethane, three
Chloromethanes, tetrahydrofuran, one kind in ethyl acetate；Two (o-allyl base) terephthalate and oxidant rub
You are than being 1：(2.5~3)；The oxidant is metachloroperbenzoic acid.
7. preparation method according to claim 2, which is characterized in that in step (2), the reaction temperature is 40 DEG C,
Reaction time is 72 hours.
8. preparation method according to claim 2, which is characterized in that in step (2), the extraction, dry process is,
Solution uses Na successively2SO3Aqueous solution, Na2CO3Aqueous solution and saturation NaCl aqueous solution extractions, organic layer are removed with desiccant dryness
Water filters to get filtrate, and rotates filtrate, with recrystallisation from isopropanol, 50 DEG C of vacuum drying obtain product.
9. preparation method according to claim 8, which is characterized in that the Na2SO3The mass fraction of aqueous solution is 10%,
Na2CO3The mass fraction of aqueous solution is 10%, and the drier is one kind in anhydrous sodium sulfate and anhydrous magnesium sulfate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113979902A (en) * | 2021-10-21 | 2022-01-28 | 中国科学院深圳先进技术研究院 | High-dielectric compound and preparation method thereof, epoxy high-dielectric material and preparation method thereof, and semiconductor device |
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| CN103664834A (en) * | 2013-11-14 | 2014-03-26 | 中国科学院深圳先进技术研究院 | Thermal degradation epoxy resin monomer and preparation method and bottom fillers thereof |
| CN107216442A (en) * | 2017-07-24 | 2017-09-29 | 贵阳学院 | A kind of epoxy resin of low linear expansion coefficient and preparation method thereof |
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2018
- 2018-04-24 CN CN201810373605.3A patent/CN108484533A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103664834A (en) * | 2013-11-14 | 2014-03-26 | 中国科学院深圳先进技术研究院 | Thermal degradation epoxy resin monomer and preparation method and bottom fillers thereof |
| CN107216442A (en) * | 2017-07-24 | 2017-09-29 | 贵阳学院 | A kind of epoxy resin of low linear expansion coefficient and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| JINTAO WAN 等: "Anovel biobased epoxy resin with high mechanical stiffness and low flammability: synthesis,characterization and properties", 《J.MATER.CHEM.A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113979902A (en) * | 2021-10-21 | 2022-01-28 | 中国科学院深圳先进技术研究院 | High-dielectric compound and preparation method thereof, epoxy high-dielectric material and preparation method thereof, and semiconductor device |
| CN113979902B (en) * | 2021-10-21 | 2022-07-22 | 中国科学院深圳先进技术研究院 | High-dielectric compound and preparation method thereof, epoxy high-dielectric material and preparation method thereof, and semiconductor device |
| WO2023065489A1 (en) * | 2021-10-21 | 2023-04-27 | 中国科学院深圳先进技术研究院 | High dielectric compound and preparation method therefor, epoxy high dielectric material and preparation method therefor, and semiconductor device |
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Application publication date: 20180904 |