CN103864724A - Method for synthesizing phthalic acid diglycidyl ester with high epoxy value - Google Patents
Method for synthesizing phthalic acid diglycidyl ester with high epoxy value Download PDFInfo
- Publication number
- CN103864724A CN103864724A CN201410080116.0A CN201410080116A CN103864724A CN 103864724 A CN103864724 A CN 103864724A CN 201410080116 A CN201410080116 A CN 201410080116A CN 103864724 A CN103864724 A CN 103864724A
- Authority
- CN
- China
- Prior art keywords
- phthalic acid
- glycidyl ester
- reaction
- epoxy value
- high epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a method for synthesizing a phthalic acid diglycidyl ester with a high epoxy value and belongs to the field of organic synthesis. The method comprises the following step: carrying out epoxy ring-opening and esterification reactions on phthalic acid serving as a starting material and epichlorohydrin in the presence of a catalyst in a heating manner, thereby obtaining the phthalic acid diglycidyl ester with the high epoxy value. According to the preparation process of the phthalic acid diglycidyl ester, the time of the ring-opening reaction in the first step is determined by measuring the acid value of reaction liquid, so that the generation of the excessive epichlorohydrin polymerization is effectively controlled. Thus, the epoxy value of the phthalic acid diglycidyl ester taken as a final product is greatly improved. Therefore, the difficulty in recycling and reusing the epichlorohydrin is solved; and even more important, the quality of the phthalic acid diglycidyl ester is improved to a great extent. Consequently, the wide application of the epoxy resin is promoted. As a result, the high economic and social benefits are obtained.
Description
Technical field
The present invention relates to a kind of method that improves phthalic acid glycidyl ester oxirane value, belong to organic synthesis field.
Background technology
In the molecular structure of phthalic acid 2-glycidyl ester, contain the Racemic glycidol ester bond that phenyl ring and polarity are stronger, can be made into sizing agent and the insulating material of excellent property, be applicable to do the matrix of matrix material, also can react and make epoxy acrylic etc. with acrylic compounds.Phthalic acid 2-glycidyl ester tradition preparation method is mainly respectively take pure terephthalic acid (PTA), m-phthalic acid and phthalic acid as raw material, adopt the greatly excessive technique of epoxy chloropropane, the excessive of epoxy chloropropane makes to react wayward, be easy to cause the generation of number of polymers, this has reduced the oxirane value of product to a great extent, cause the low and high defect of product cost of quality product, limited greatly its production efficiency and application.Therefore, the novel preparation method of the phthalic acid 2-glycidyl ester of research and development high epoxy value, the consumption of reduction epoxy chloropropane, has not only greatly improved the quality of product, and has promoted this based epoxy resin widespread use, has higher economic and social benefit.
Summary of the invention
The preparation of phthalic acid two sour water glyceryl ester can be divided into ring-opening reaction and ring-closure reaction, and reactions steps and principle are suc as formula shown in I and formula II:
The open loop of formula I and esterification
The ring-closure reaction of formula II
A kind of method of synthetic high epoxy value phthalic acid 2-glycidyl ester, carry out according to following step: take phthalic acid as starting raw material, with epichlorohydrin reaction, under the effect of heating and catalyzer, open loop and esterification that epoxy occurs, obtain high epoxy value phthalic acid 2-glycidyl ester.
Wherein, described phthalic acid is: terephthalic acid, phthalic acid, m-phthalic acid.
Wherein, described catalyzer is: quaternary ammonium salt (as Tetrabutyl amonium bromide, cetyl trimethylammonium bromide etc.), imidazoles (as 4-methylimidazole, glyoxal ethyline etc.), triphenylphosphine etc. are preferably wherein triphenylphosphine.
Wherein, described alkali is: sodium hydroxide or potassium hydroxide.
Wherein, the feed ratio of open loop and esterification is: the mol ratio 1.0:4.0-1.0:8.0 of phthalic acid and epoxy chloropropane, and catalyzer is the 0.5%-3% of phthalic acid quality; In ring-closure reaction, the charging capacity of mineral alkali is 2-3 times of carboxylic acid mole number in phthalic acid, and optimum value is 2.5 times.
Wherein, the reaction that the first step occurs is ring-opening reaction, and temperature is: 110 ℃-125 ℃; Reaction times is: 0.5-3 hour.
Wherein, the reaction that second step occurs is ring-closure reaction, and the time is: 3-5 hour.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Novelty of the present invention is: by the mensuration to reaction solution acid number, determine the first step ring-opening reaction time in phthalic acid 2-glycidyl ester preparation technology, effectively control the generation of excessive epoxy chloropropane polyreaction, thereby greatly improve the oxirane value of final product phthalic acid 2-glycidyl ester, not only avoid a difficult problem for epoxy chloropropane recovery, the more important thing is the quality that has improved to a great extent product, thereby promote this based epoxy resin widespread use, there is higher economic and social benefit.
Embodiment
Describe the present invention with specific examples.Protection scope of the present invention is not limited in specific examples mode, but is limited by claim.
Example 1
In 100ml four-hole boiling flask, add successively terephthalic acid 12.5g, catalyzer triphenylphosphine is terephthalic acid 0.5%, i.e. 0.06g, with the ratio of the mol ratio 1.0:4.0 of terephthalic acid and epoxy chloropropane, takes epoxy chloropropane 50.0g.Stir, be progressively warming up to backflow.In reaction process, follow the tracks of the acid number of reaction solution, in the time that acid number is less than 1mgKOH/g, stop heating.Be cooled to, after 50 ℃, add 0.5g activated carbon, continue to stir after cooling 1h, suction filtration is removed activated carbon, with the ratio of mol ratio 1.0:2.0, takes NaOH solid 6.3g, the preparation 50%NaOH aqueous solution slowly drips the NaOH aqueous solution, to reacting in filtrate under whipped state, after stirring at room temperature reaction 4h, be washed to neutrality, layering, take off layer, revolve steaming, obtain white solid 20.3g, oxirane value 7.4 mol/100g.
Example 2
In 100ml four-hole boiling flask, add successively m-phthalic acid 12.1g, catalyzer triphenylphosphine is terephthalic acid 0.5%, i.e. 0.06g, with the ratio of the mol ratio 1.0:6.0 of terephthalic acid and epoxy chloropropane, takes epoxy chloropropane 72.6g.Stir, be progressively warming up to backflow.In reaction process, follow the tracks of the acid number of reaction solution, in the time that acid number is less than 1gKOH/g, stop heating.Be cooled to, after 50 ℃, add 0.5g activated carbon, continue to stir after cooling 1h, suction filtration is removed activated carbon, with the ratio of mol ratio 1:2.5, takes NaOH solid 6.5g, the preparation 50%NaOH aqueous solution slowly drips the NaOH aqueous solution, to reacting in filtrate under whipped state, after stirring at room temperature reaction 4h, be washed to neutrality, layering, take off layer, revolve steaming, obtain white solid 22.4g, oxirane value 8.4 mol/100g.
Example 3
In 100ml four-hole boiling flask, add successively phthalic acid 12.3g, agent triphenylphosphine is terephthalic acid 0.5%, i.e. 0.06g, with the ratio of the mol ratio 1.0:8.0 of terephthalic acid and epoxy chloropropane, takes epoxy chloropropane 98.4g.Stir, be progressively warming up to backflow, in reaction process, follow the tracks of the acid number of reaction solution, in the time that acid number is less than 1gKOH/g, stop heating.Be cooled to, after 50 ℃, add 0.5g activated carbon, continue to stir after cooling 1h, suction filtration is removed activated carbon, with the ratio of mol ratio 1:3.0, takes NaOH solid 7.2 g, the preparation 50%NaOH aqueous solution slowly drips the NaOH aqueous solution, to reacting in filtrate under whipped state, after stirring at room temperature reaction 4h, be washed to neutrality, layering, take off layer, revolve steaming, obtain white solid 28.3g, oxirane value 7.6 mol/100g.
Claims (7)
1. the method for a synthetic high epoxy value phthalic acid 2-glycidyl ester, it is characterized in that carrying out according to following step: take phthalic acid as starting raw material, with epichlorohydrin reaction, under the effect of heating and catalyzer, first open loop and the esterification of epoxy occur, and then under inorganic strong alkali effect, cyclization obtains high epoxy value phthalic acid 2-glycidyl ester.
2. the method for a kind of synthetic high epoxy value phthalic acid 2-glycidyl ester according to claim 1, is characterized in that described phthalic acid is: terephthalic acid, phthalic acid, m-phthalic acid.
3. the method for a kind of synthetic high epoxy value phthalic acid 2-glycidyl ester according to claim 1, it is characterized in that described catalyzer is: quaternary ammonium salt (as Tetrabutyl amonium bromide, cetyl trimethylammonium bromide etc.), imidazoles (as 4-methylimidazole, glyoxal ethyline etc.), triphenylphosphine etc. are preferably wherein triphenylphosphine.
4. the method for a kind of synthetic high epoxy value phthalic acid 2-glycidyl ester according to claim 1, is characterized in that described alkali is: sodium hydroxide or potassium hydroxide.
5. the method for a kind of synthetic high epoxy value phthalic acid 2-glycidyl ester according to claim 1, the feed ratio that it is characterized in that open loop and esterification is: the mol ratio 1.0:4.0-1.0:8.0 of phthalic acid and epoxy chloropropane, and catalyzer is the 0.5%-3% of phthalic acid quality; In ring-closure reaction, the charging capacity of mineral alkali is 2-3 times of carboxylic acid mole number in phthalic acid, and optimum value is 2.5 times.
6. the method for a kind of synthetic high epoxy value phthalic acid 2-glycidyl ester according to claim 1, is characterized in that the reaction that the first step occurs is ring-opening reaction, and temperature is: 110 ℃-125 ℃; Reaction times is: 0.5-3 hour.
7. the method for a kind of synthetic high epoxy value phthalic acid 2-glycidyl ester according to claim 1, it is characterized in that the reaction that the first step is occurred is ring-opening reaction and esterification, by following the tracks of reaction solution acid number index, understand the consumer process of phthalic acid raw material, control the generation of polyethers by product, reach the object that improves phthalic acid 2-glycidyl ester oxirane value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410080116.0A CN103864724A (en) | 2014-03-06 | 2014-03-06 | Method for synthesizing phthalic acid diglycidyl ester with high epoxy value |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410080116.0A CN103864724A (en) | 2014-03-06 | 2014-03-06 | Method for synthesizing phthalic acid diglycidyl ester with high epoxy value |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103864724A true CN103864724A (en) | 2014-06-18 |
Family
ID=50903794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410080116.0A Pending CN103864724A (en) | 2014-03-06 | 2014-03-06 | Method for synthesizing phthalic acid diglycidyl ester with high epoxy value |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103864724A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484531A (en) * | 2018-04-25 | 2018-09-04 | 江苏正丹化学工业股份有限公司 | A kind of synthesis technology of terephthalic acid diglycidyl ester |
| CN108484532A (en) * | 2018-04-25 | 2018-09-04 | 江苏正丹化学工业股份有限公司 | A kind of synthesis technology of trimellitic acid three-glycidyl ester |
| CN109111412A (en) * | 2018-10-18 | 2019-01-01 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of terephthalic acid diglycidyl ester |
| CN109232479A (en) * | 2018-10-18 | 2019-01-18 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of trimellitic acid three-glycidyl ester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0822189A2 (en) * | 1996-07-19 | 1998-02-04 | Nissan Chemical Industries Ltd. | Method for producing purified epoxy compound |
| JP2011184373A (en) * | 2010-03-09 | 2011-09-22 | Nippon Shokubai Co Ltd | Method for producing glycidyl acrylate |
-
2014
- 2014-03-06 CN CN201410080116.0A patent/CN103864724A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0822189A2 (en) * | 1996-07-19 | 1998-02-04 | Nissan Chemical Industries Ltd. | Method for producing purified epoxy compound |
| JP2011184373A (en) * | 2010-03-09 | 2011-09-22 | Nippon Shokubai Co Ltd | Method for producing glycidyl acrylate |
Non-Patent Citations (1)
| Title |
|---|
| 蔡亚 等.: "对苯二甲酸二缩水甘油酯的合成", 《应用化工》, vol. 37, no. 12, 31 December 2008 (2008-12-31) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484531A (en) * | 2018-04-25 | 2018-09-04 | 江苏正丹化学工业股份有限公司 | A kind of synthesis technology of terephthalic acid diglycidyl ester |
| CN108484532A (en) * | 2018-04-25 | 2018-09-04 | 江苏正丹化学工业股份有限公司 | A kind of synthesis technology of trimellitic acid three-glycidyl ester |
| CN108484532B (en) * | 2018-04-25 | 2020-04-28 | 江苏正丹化学工业股份有限公司 | Synthesis process of trimellitic acid triglycidyl ester |
| CN108484531B (en) * | 2018-04-25 | 2020-06-30 | 江苏正丹化学工业股份有限公司 | Synthesis process of diglycidyl terephthalate |
| CN109111412A (en) * | 2018-10-18 | 2019-01-01 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of terephthalic acid diglycidyl ester |
| CN109232479A (en) * | 2018-10-18 | 2019-01-18 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of trimellitic acid three-glycidyl ester |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103864724A (en) | Method for synthesizing phthalic acid diglycidyl ester with high epoxy value | |
| CN102876462B (en) | Method for preparing high-quality epoxidized soybean oil | |
| CN102633626B (en) | A kind of 2,4,6-Three methyl Benzene Acetyl Chloride 98Min. synthesis technique | |
| CN102367238A (en) | Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide | |
| CN106831421A (en) | The preparation method of di-tert-butyl dicarbonate | |
| CN103739484A (en) | Preparation method of 1,4-naphthalenedicarboxylic acid | |
| KR101952060B1 (en) | Method for preparing furan-2,5-dicarboxylic acid (FDCA) from solid salt | |
| CN102838562A (en) | Method for synthesizing rubber vulcanization accelerator NS (N-tertiary butyl-2-benzothiazole sulfenamide) through two-step method by taking hydrogen peroxide as oxidant | |
| CN103706404A (en) | Magnetic composite microsphere for catalyzing CO2 and epoxy compound cycloaddition reaction as well as preparation method and application thereof | |
| CN103319439A (en) | Method for preparing epoxy fatty acid cyclohexyl ester | |
| CN103848799B (en) | A kind of PTA of utilization residue prepares the method for pure mixed phthalic acid 2-glycidyl ester | |
| CN103524450A (en) | Synthetic method for accelerator DZ by using methanol as solvent | |
| CN106588657A (en) | Method for synthesizing dimethyl carbonate | |
| CN103724203A (en) | Preparation method of o-methyl hydroxyphenylacetate | |
| CN103351363B (en) | Preparation method of chloropropylene oxide by utilizing dichloropropanol | |
| CN110452089A (en) | The synthetic method of p-chloromethyl styrene | |
| CN107641197B (en) | It is a kind of using carbon dioxide and 7-oxa-bicyclo[4.1.0 as the copolyreaction catalyst of monomer | |
| CN107793378A (en) | A kind of novel method for synthesizing of glycerin triglycidyl ether | |
| CN104447278A (en) | Method for preparing dicarboxylic acid zinc | |
| CN105348319A (en) | Titanium butanediol and preparation method thereof | |
| CN105131016A (en) | Preparation method of cefuroxime axetil | |
| CN101875681B (en) | Synthetic method of 16alpha-hydroxy prednisonlone | |
| CN205740838U (en) | A kind of system producing PPS coproduction SPS | |
| CN104447290A (en) | Method for preparing 2,4-dichlorophenoxyacetic acid | |
| CN104513197A (en) | 2-aminonicotinic acid synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140618 |