CN110105540A - A kind of preparation method of glycidyl ester type self curable epoxy resin - Google Patents
A kind of preparation method of glycidyl ester type self curable epoxy resin Download PDFInfo
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- CN110105540A CN110105540A CN201910380628.1A CN201910380628A CN110105540A CN 110105540 A CN110105540 A CN 110105540A CN 201910380628 A CN201910380628 A CN 201910380628A CN 110105540 A CN110105540 A CN 110105540A
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- epoxy resin
- ester type
- glycidyl ester
- phthalic acid
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
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Abstract
The present invention provides a kind of high-efficiency synthesis method of glycidyl ester type self curable epoxy resin, problem longer, more than waste liquid amount that this method solve the synthesis cycles for preparing glycidyl ester type self curable epoxy resin at present.Step of the invention is as follows: dihydroxy phthalic acid and tetramethylammonium hydroxide pentahydrate being added into enough epoxychloropropane, stirring is warming up to dihydroxy phthalic acid and dissolves in epoxychloropropane, keeps heating stirring to dihydroxy phthalic acid fully reacting.It is cooled to room temperature to product, distilled water is added repeatedly to wash extraction, stratification, lower layer obtains product.The present invention can prepare glycidyl ester type self curable epoxy resin under normal pressure, confirm that carboxyl is fully completed conversion in reactant dihydroxy phthalic acid through infrared detection, there are a large amount of phenolic hydroxyl groups and epoxy groups in product, have the characteristic for heating self-curing.It is placed on room temperature under confined conditions, the glycidyl ester type self curable epoxy resin of preparation can be stable storage 9 months or more.
Description
Technical field
The present invention relates to a kind of preparation methods of glycidyl ester type self curable epoxy resin.
Background technique
Self curable epoxy resin can realize epoxy group and active hydrogen reaction in material by heating, avoid curing agent performance
Influence to material self performance, and it is relatively fewer to the synthesis patent of glycidyl ester type self curable epoxy resin.The U.S. is special
Sharp US5663240A discloses a kind of epoxide function acrylic copolymer and polycarboxylic acids powdery paints preparation method: using 50%~
The glycidyl function ethylene unsaturated monomers of 75% mass fraction, with 35%~50% mass fraction without epoxy group can
The monomer or monomer mixture of the ethylene of copolymerization polymerize, and prepare function epoxy copolymer, then by 10%~40% mass fraction
Multi-carboxylic acid cross-linking agent and 60%~90% function epoxy copolymer are with epoxy group and carboxyl than being prepared into for the ratio of 1:0.8~1
Glycidyl ester type epoxy resin to Tg range at 25 DEG C~70 DEG C；Patent EP458296-A, JP4028712-A,
JP4128279-A,EP458296-A3,US5242996-A,EP458296-B1,DE69117581-E；, JP2613120-B2 mentions
A kind of epoxy resin modified using unsaturated acetylene is gone out, which has the characteristics that self-curing and nothing distribute；Japan Patent
JP54063189-A, JP87059132-B are copolymerized Chloroprene monomer and glycidyl monomer in thioacetic acid environment, system
Standby to obtain the chloroprene polymer with self-curing characteristic, the self-curing neoprene and other high molecular materials have well
Compatibility and reactivity, and have good chelating Forming ability, be the toughener of thermosetting resin or plastic resin etc.；Day
This patent JP76029200-B is prepared for having first ethylenic linkage or glycidol ether and vinylpyridine or vinylquinoline
Copolymer, the copolymer are mixed with conven-tional adjuvants as plasticizer, can get powdered or granular material, which is not having
Self-curing forming, the material have that good stability of the dimension, chemical resistance be good, machine at 100 DEG C in the case where curing agent
The advantages that tool intensity is high.
Above-mentioned route is relatively fewer to the glycidyl ester type epoxy resin research of phenolic hydroxyl group and epoxy systems, except in patent
Except the process route referred to is outer, a kind of glycidyl ester type self curable epoxy resin that the period is about 6h has also been reported in document
Synthesis path: used under the conditions of 100 DEG C molar ratio for DHTA, ECH of 1:35:0.06, tetrabutylammonium iodide react, cooling
NaOH solution is added dropwise afterwards, and the reaction was continued obtains the self curable epoxy resin containing phenolic hydroxyl group.The synthetic route synthesis cycle is relatively
Long, waste liquid amount is more to be unfavorable for producing and using.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of prior art route, a kind of glycidyl ester type cured epoxy tree is provided
The preparation method of rouge, this method green high-efficient.
The purpose of the present invention is achieved through the following technical solutions: a kind of preparation of glycidyl ester type self curable epoxy resin
Method includes the following steps:
(1) dihydroxy phthalic acid and tetramethylammonium hydroxide pentahydrate, dihydroxy benzenes two are added into epoxy solvent
Formic acid and epoxy solvent molar ratio are 1:17.5~35, and tetramethylammonium hydroxide pentahydrate accounts for dihydroxy phthalic acid quality
10%~15%, 80~100 DEG C at a temperature of be stirred to react 1~3h and obtain product, the product naturally cools to room temperature.
(2) standing is divided after product and water after cooling in step (1) sufficiently being washed concussion according to the mass ratio of 2~3:1
Layer takes lower layer for product, without black floating material in repeated washing to sample, obtains epoxy solvent and glycidyl ester type self-curing
The mixture of epoxy resin.
(3) mixture that step (2) obtains is placed in 70~140 DEG C, devolatilization under vacuum environment, removed after epoxy solvent
To glycidyl ester type self curable epoxy resin product.
Further, the structural formula of dihydroxy phthalic acid described in step (1) are as follows:
Further, the structural formula of epoxy solvent used in step (1) are as follows:
Wherein R is alkyl or phenyl, and X is chlorine atom, bromine atom or iodine atom.
Further, dihydroxy phthalic acid and epoxy solvent molar ratio are 1:17.5, tetramethyl hydrogen in the step (1)
Amine-oxides pentahydrate accounts for the 12% of dihydroxy phthalic acid quality.
The beneficial effects of the present invention are: method of the invention can be carried out under normal pressure and reaction temperature is lower, reaction
Mild condition and preparation time is shorter.In addition to this, compared to preparation path reported in the literature, this method considerably reduces original
The usage amount of one of material epoxy solvent, industrial production cost reduce, and wastewater flow rate is remarkably decreased, and have the advantages that green high-efficient.This hair
Bright process route only needs once to match charging before the reaction, and post-processing is simple, and whole preparation and purifying technique only need to be
It is completed in single stirred tank with stirring and decompression, equipment investment and maintenance expenditure are lower.
Detailed description of the invention
Fig. 1 is the composition principle of self curable epoxy resin
Fig. 2 is the gel permeation chromatography spectrogram of glycidyl ester type self curable epoxy resin.
Fig. 3 is the infrared spectrum of glycidyl ester type self curable epoxy resin.
Fig. 4 is the differential scanning calorimeter test spectrogram of glycidyl ester type self curable epoxy resin.
Specific embodiment
The present invention is strong organic base using tetramethylammonium hydroxide pentahydrate, epoxy solvent under the action of strong organic base
Open loop efficiency is higher, and the rate reacted with dihydroxy phthalic acid carboxylic group is relatively fast, so as to shorten glycidyl ester type
The reaction time of self curable epoxy resin.Moreover, tetramethylammonium hydroxide pentahydrate makes epoxy solvent open loop product
Dehydrochlorination re-forms epoxy group, participates in reaction again, and the utilization rate for greatly improving epoxy solvent thus can
The dosage of epoxy solvent when reducing production makes the reduction of industrial production cost, and wastewater flow rate is remarkably decreased, high-efficiency environment friendly.Fig. 1 with 2,
For 5- dihydric para-phthalic acid and epoxychloropropane are as reactant, illustrate with tetramethylammonium hydroxide pentahydrate work
The reaction principle of self curable epoxy resin is synthesized for catalyst.
Combined with specific embodiments below, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member makes various changes or modifications the present invention, and such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Embodiment 1
A kind of preparation method of glycidyl ester type self curable epoxy resin, includes the following steps:
(1) addition 2,5-Dihydroxyterephthalic acid and tetramethylammonium hydroxide pentahydrate into epoxychloropropane, 2,
5- dihydric para-phthalic acid and epoxychloropropane molar ratio are 1:17.5, and tetramethylammonium hydroxide pentahydrate accounts for 2,5- dihydroxy
The 12% of base terephthalic acid (TPA) quality, 90 DEG C at a temperature of be stirred to react 2h and obtain product, the product naturally cools to room
Temperature.
(2) product and water after cooling in step (1) are sufficiently washed to stratification after shaking according to the mass ratio of 2:1,
Taking lower layer is product, and repeated washing repeatedly, obtains the mixture of epoxy solvent Yu glycidyl ester type self curable epoxy resin.
(3) mixture that step (2) obtains is placed in devolatilization under 80 DEG C of vacuum environments, is shunk after removing epoxy solvent
Glycerol ester type self curable epoxy resin product.
Fig. 2 is gel permeation chromatogram, and self curable epoxy resin molecular weight distribution is as shown in table 1, more points of dimer peak
Dissipating property coefficient is 1.04, and molecular weight distribution is relatively narrow, and the polydispersity coefficient of four poly- peak bodies is 1.18, has certain molecular weight
The dispersion of distribution.The distributional difference at two peaks illustrates that 2,5- dihydric para-phthalic acid and epichlorohydrin reaction generate the mistake of dimer
Journey is relatively single, and relative complex by the process that dimerization precursor reactant generates the tetramer, not single to generate the simple tetramer.Color
Spectrogram result proves that the epoxychloropropane that present embodiment uses and 2,5-Dihydroxyterephthalic acid are reacted, and successfully makes
The standby self curable epoxy resin being mainly made of dimer and the tetramer.
Fig. 3 is infrared spectrogram, comparison reacting precursor system (a), reaction after system (b) and washing, extract and remove solvent
Self curable epoxy resin infrared line afterwards is it can be found that addition has occurred in carboxyl and epoxy group in dihydroxy phthalic acid
Reaction, carboxylic group has been fully converted to ester group, and the phenolic hydroxyl group in dihydric para-phthalic acid it is most of not with ring
Oxygen solvent carries out addition reaction, and phenolic hydroxy group is preferably retained in the epoxy.Therefore, the epoxy resin of preparation includes
There are phenolic hydroxyl group and epoxy group, the functional group basis with self-curing.
Fig. 4 is differential scanning calorimeter test result.The glycidyl ester type self curable epoxy resin of this patent preparation exists
It does not add and occurs solidification peak under conditions of other reagents such as curing agent between 160 DEG C~200 DEG C, there is self-curing characteristic.
In addition, experiments verify that using 2,5-Dihydroxyterephthalic acid and epoxychloropropane molar ratio for 1:17.5 or so
When, temperature change is smaller in system in reaction process, and reaction speed is very fast, is conducive to efficient stable and produces.
The glycidyl ester type self curable epoxy resin of present embodiment preparation can be stable at room temperature in sealing container
Storage 9 months or more.
1 self curable epoxy resin molecular weight distribution of table
| Peak serial number | Mn | Mw | Mp | PDI |
| 1 | 1240 | 1466 | 947 | 1.18 |
| 2 | 492 | 514 | 532 | 1.04 |
Embodiment 2
A kind of preparation method of glycidyl ester type self curable epoxy resin, includes the following steps:
(1) it is added 3,6- dihydroxy phthalic acid and tetramethylammonium hydroxide pentahydrate into epoxy bromopropane, two
Hydroxyl phthalic acid and epoxy solvent molar ratio are 1:35, and tetramethylammonium hydroxide pentahydrate accounts for dihydroxy phthalic acid quality
10%, 80 DEG C at a temperature of be stirred to react 1h and obtain product, the product naturally cools to room temperature.
(2) product and water after cooling in step (1) are sufficiently washed to stratification after shaking according to the mass ratio of 2:1,
Taking lower layer is product, and repeated washing repeatedly, obtains the mixing of epoxy solvent Yu glycidyl ester type self curable epoxy resin
Object.
(3) mixture that step (2) obtains is placed in 90 DEG C, devolatilization under vacuum environment, is contracted after removing epoxy solvent
Water glycerol ester type self curable epoxy resin product.
The experiment proved that epoxy resin manufactured in the present embodiment is formed with dimer and the tetramer, have in the epoxy resin
There is the functional group basis of self-curing, in 160 DEG C~200 DEG C self-curings under conditions of not adding other reagents such as curing agent.
Under the reaction condition, temperature change is smaller in system in reaction process, and reaction speed is very fast, and it is raw to be conducive to efficient stable
It produces.
The glycidyl ester type self curable epoxy resin of present embodiment preparation can be stable at room temperature in sealing container
Storage 9 months or more.
Embodiment 3
A kind of preparation method of glycidyl ester type self curable epoxy resin, includes the following steps:
(1) 2,6- dihydric para-phthalic acid and five water of tetramethylammonium hydroxide are added into epoxy solvent epoxychloropropane
Object is closed, dihydroxy phthalic acid and epoxy solvent molar ratio are 17.5:35, and ammonium hydroxide pentahydrate accounts for dihydroxy benzenes two
The 15% of formic acid quality, 100 DEG C at a temperature of be stirred to react 3h and obtain product, the product naturally cools to room temperature.
(2) product and water after cooling in step (1) are sufficiently washed to stratification after shaking according to the mass ratio of 3:1,
Taking lower layer is product, and repeated washing repeatedly, obtains the mixture of epoxy solvent Yu glycidyl ester type self curable epoxy resin.
(3) mixture that step (2) obtains is placed in 100 DEG C, devolatilization under vacuum environment, is contracted after removing epoxy solvent
Water glycerol ester type self curable epoxy resin product.
The experiment proved that epoxy resin manufactured in the present embodiment is formed with dimer and the tetramer, have in the epoxy resin
There is the functional group basis of self-curing, in 160 DEG C~200 DEG C self-curings under conditions of not adding other reagents such as curing agent.
Under the reaction condition, temperature change is smaller in system in reaction process, and reaction speed is very fast, and it is raw to be conducive to efficient stable
It produces.
The glycidyl ester type self curable epoxy resin of present embodiment preparation can be stable at room temperature in sealing container
Storage 9 months or more.
Claims (4)
1. a kind of preparation method of glycidyl ester type self curable epoxy resin, which comprises the steps of:
(1) dihydroxy phthalic acid and tetramethylammonium hydroxide pentahydrate, dihydroxy phthalic acid are added into epoxy solvent
It is 1:17.5~35 with epoxy solvent molar ratio, tetramethylammonium hydroxide pentahydrate accounts for the 10% of dihydroxy phthalic acid quality
~15%, 80~100 DEG C at a temperature of be stirred to react 1~3h and obtain product, the product naturally cools to room temperature.
(2) product and water after cooling in step (1) are sufficiently washed to stratification after shaking according to the mass ratio of 2~3:1, taken
Lower layer is product, without black floating material in repeated washing to sample, obtains epoxy solvent and glycidyl ester type cured epoxy
The mixture of resin.
(3) mixture that step (2) obtains is placed in 70~140 DEG C, devolatilization under vacuum environment, is contracted after removing epoxy solvent
Water glycerol ester type self curable epoxy resin product.
2. the preparation method of glycidyl ester type self curable epoxy resin according to claim 1, which is characterized in that step
(1) structural formula of the dihydroxy phthalic acid described in are as follows:
3. the preparation method of glycidyl ester type self curable epoxy resin according to claim 1, which is characterized in that step
(1) structural formula of the epoxy solvent used in are as follows:
Wherein R is alkyl or phenyl, and X is chlorine atom, bromine atom or iodine atom.
4. the preparation method of glycidyl ester type self curable epoxy resin according to claim 1, which is characterized in that described
Dihydroxy phthalic acid and epoxy solvent molar ratio are 1:17.5 in step (1), and tetramethylammonium hydroxide pentahydrate accounts for dihydroxy
The 12% of base phthalic acid quality.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113174228A (en) * | 2021-03-24 | 2021-07-27 | 深圳市新亚电子制程股份有限公司 | UV moisture dual-curing organic silicon coating adhesive and preparation method and application thereof |
| CN117467339A (en) * | 2023-12-27 | 2024-01-30 | 北京超智控信科技有限公司 | Self-closing wire self-curing insulating coating material for electrified railway |
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| CN117467339A (en) * | 2023-12-27 | 2024-01-30 | 北京超智控信科技有限公司 | Self-closing wire self-curing insulating coating material for electrified railway |
| CN117467339B (en) * | 2023-12-27 | 2024-03-08 | 北京超智控信科技有限公司 | Self-closing wire self-curing insulating coating material for electrified railway |
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