CN103848799A - Method of preparing mixed diglycidyl phthalate by using PTA (Purified Terephthalic Acid) residue - Google Patents
Method of preparing mixed diglycidyl phthalate by using PTA (Purified Terephthalic Acid) residue Download PDFInfo
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- CN103848799A CN103848799A CN201410018692.2A CN201410018692A CN103848799A CN 103848799 A CN103848799 A CN 103848799A CN 201410018692 A CN201410018692 A CN 201410018692A CN 103848799 A CN103848799 A CN 103848799A
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- pta
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- phthalic acid
- glycidyl ester
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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
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- 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
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Abstract
The invention relates to a method of preparing mixed diglycidyl phthalate by using a PTA (Purified Terephthalic Acid) residue, and belongs to the field of organic synthesis. The method comprises the following steps: by taking the PTA residue and epoxy chloropropane as initial raw materials, adding a certain amount of an organic solvent; under the effects of heating and a catalyst, firstly, carrying out ring-opening reaction of epoxy and esterification reaction; then, under the effect of inorganic base, carrying out ring-closure reaction to generate final product mixed diglycidyl phthalate. According to the method provided by the invention, by taking PTA secondary residue as the raw material, resources are recycled, so that the cost of the raw material is greatly lowered, and meanwhile, the environment is effectively protected. The use level of epoxy chloropropane is greatly reduced by using a solvent method, the problem of recovering and using epoxy chloropropane is avoided, the epoxide number and yield of the product are improved, and the epoxy resin is promoted to be widely applied.
Description
Technical field
The present invention relates to a kind of preparation method of glycidyl ester, 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 prior synthesizing method is mainly the preparation taking pure terephthalic acid (PTA), m-phthalic acid and phthalic acid as raw material respectively, makes phthalic acid 2-glycidyl ester preparation cost high, has restricted its widespread use; In addition, the synthetic of traditional phthalic acid 2-glycidyl ester is generally to adopt the greatly excessive technique of epoxy chloropropane, not only make the oxirane value of product low, but also bring the difficult problem of epoxy chloropropane recovery, cause the low and high defect of product cost of quality product, limited greatly its production efficiency and application.Therefore, utilize the phthalic acid 2-glycidyl ester new synthetic process route that terephthalic acid (PTA) residue research and development cost is low, oxirane value is high, can not only promote this based epoxy resin widespread use, and can also accomplish the effective and reasonable utilization of PTA residue waste to there is higher economic and social benefit.
Summary of the invention
The present invention, for overcoming above-mentioned deficiency, provides a kind of PTA of utilization residue to prepare the method for pure mixed phthalic acid 2-glycidyl ester.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 PTA of utilization residue is prepared the method for pure mixed phthalic acid 2-glycidyl ester, carry out according to following step: taking PTA residue and epoxy chloropropane as starting raw material, add a certain amount of organic solvent, under the effect of heating and catalyzer, first there is open loop and the esterification of epoxy, and then under the effect of mineral alkali, there is ring-closure reaction, generate final product pure mixed phthalic acid two sour water glyceryl ester.
Wherein said 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 said organic solvent is: butylacetate, toluene etc., preferably butylacetate.
Wherein said mineral alkali is: sodium hydroxide or potassium hydroxide.
Wherein PTA residue is the main mixture containing terephthalic acid, m-phthalic acid and tar ingredients that has reclaimed phenylformic acid and cobalt-manganese catalyst, is bis-residues of PTA, and its acid number is 617mgKOH/g, convert for carboxylic acid content be 11mmol/g.The feed ratio of open loop and esterification is: the carboxylic acid in bis-residues of PTA and the mol ratio 1.0:1.5-1.0:2.5 of epoxy chloropropane, and catalyzer is the 0.5%-3% of bis-residue quality of PTA, reaction solvent consumption is 2-3 times of bis-residue quality of PTA; In ring-closure reaction, the charging capacity of mineral alkali is 2-3 times of carboxylic acid mole number in bis-residues of PTA.
The reaction that wherein the first step occurs is open loop and esterification, and temperature is: 110 DEG C-125 DEG C; Reaction times is: 0.5-3 hour.
The reaction that wherein 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: first, the present invention proposes taking bis-residues of PTA as raw material, accomplished the recycle of resource, the cost of raw material is reduced greatly, effectively protected environment simultaneously; Secondly, use solvent method greatly reduces the consumption of epoxy chloropropane, has avoided a difficult problem for epoxy chloropropane recovery, has improved oxirane value and the productive rate of product, has promoted the widespread use of this based epoxy resin.
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.
Embodiment 1
Be bis-residue 10.1g of PTA of 617 mgKOH/g toward adding successively acid number in 100ml four-hole boiling flask, catalyzer triphenylphosphine be PTA residue quality 0.5%, i.e. 0.05g, solvent acetic acid butyl ester is 2 times of bis-residues of PTA, i.e. 20g.Stir, be heated to reflux, with the ratio of the mol ratio 1.0:1.5 of the carboxylic acid in bis-residues of PTA and epoxy chloropropane, take epoxy chloropropane 15.5g, drop in reaction solution, after back flow reaction 0.5h, stop heating, add 0.5g activated carbon, continue to stir after cooling 1h, suction filtration is removed activated carbon, filtrate is revolved and is steamed except desolventizing, weigh, add appropriate methylene chloride, with the ratio of mol ratio 1:2.0, take NaOH solid 4.1g, the preparation 50%NaOH aqueous solution, under whipped state, slowly drip the NaOH aqueous solution, to reacting in filtrate, after stirring at room temperature reaction 3h, be washed to neutrality, layering, take off layer, revolve steaming, obtain light yellow oil 5.4g, oxirane value 5.3 mol/100g.
Embodiment 2
Be bis-residue 10.1g of PTA of 617 mgKOH/g toward adding successively acid number in 100ml four-hole boiling flask, catalyzer triphenylphosphine be PTA residue quality 1%, i.e. 0.1g, solvent toluene is 2.5 times of bis-residues of PTA, i.e. 25g.Stir, be heated to reflux, with the ratio of the mol ratio 1.0:2.0 of the carboxylic acid in bis-residues of PTA and epoxy chloropropane, take epoxy chloropropane 20.2g, drop in reaction solution, after back flow reaction 3h, stop heating, 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, take NaOH solid 4.4g, the preparation 50%NaOH aqueous solution, under whipped state, slowly drip the NaOH aqueous solution, to reacting in filtrate, after stirring at room temperature reaction 4h, be washed to neutrality, layering, take off layer, revolve steaming, obtain light yellow oil 4.2g, oxirane value 5.6 mol/100g.
Embodiment 3
Be bis-residue 10.1g of PTA of 617 mgKOH/g toward adding successively acid number in 100ml four-hole boiling flask, catalyzer triphenylphosphine be PTA residue quality 3%, i.e. 0.3g, 3 times of bis-residues of solvent acetic acid butyl ester PTA, i.e. 30g.Stir, be heated to reflux, with the ratio of the mol ratio 1.0:2.5 of the carboxylic acid in bis-residues of PTA and epoxy chloropropane, take epoxy chloropropane 25.8g, drop in reaction solution, after back flow reaction 0.5h, stop heating, add 0.5g activated carbon, continue to stir after cooling 1h, suction filtration is removed activated carbon, filtrate is revolved and is steamed except desolventizing, weigh, add appropriate methylene dichloride, with the ratio of mol ratio 1:3, take NaOH solid 5.2g, the preparation 50%NaOH aqueous solution, under whipped state, slowly drip the NaOH aqueous solution, stir after 5h, be washed to neutrality, layering, take off layer, revolve steaming, obtain light yellow oil 9.5g, oxirane value 8.1 mol/100g.
Claims (8)
1. a method of utilizing PTA residue to prepare pure mixed phthalic acid 2-glycidyl ester, it is characterized in that carrying out according to following step: taking PTA residue and epoxy chloropropane as starting raw material, add a certain amount of organic solvent, under the effect of heating and catalyzer, first there is open loop and the esterification of epoxy, and then under the effect of mineral alkali, there is ring-closure reaction, generate final product pure mixed phthalic acid two sour water glyceryl ester.
2. a kind of PTA of utilization residue according to claim 1 is prepared the method for pure mixed phthalic acid 2-glycidyl ester, it is characterized in that wherein said 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.
3. a kind of PTA of utilization residue according to claim 1 is prepared the method for pure mixed phthalic acid 2-glycidyl ester, it is characterized in that wherein said organic solvent is: butylacetate, toluene etc., preferably butylacetate.
4. a kind of PTA of utilization residue according to claim 1 is prepared the method for pure mixed phthalic acid 2-glycidyl ester, it is characterized in that wherein said mineral alkali is: sodium hydroxide or potassium hydroxide.
5. a kind of PTA of utilization residue according to claim 1 is prepared the method for pure mixed phthalic acid 2-glycidyl ester, it is characterized in that wherein PTA residue is the main mixture containing terephthalic acid, m-phthalic acid and tar ingredients that has reclaimed phenylformic acid and cobalt-manganese catalyst, for bis-residues of PTA, its acid number is about 620mgKOH/g, converts and is about 11mmol/g for carboxylic acid content.
6. the feed ratio of open loop and esterification is: the carboxylic acid in bis-residues of PTA and the mol ratio 1.0:1.5-1.0:2.5 of epoxy chloropropane, and catalyzer is the 0.1%-3% of bis-residue quality of PTA, reaction solvent consumption is 2-3 times of bis-residue quality of PTA; In ring-closure reaction, the charging capacity of mineral alkali is 2-3 times of carboxylic acid mole number in bis-residues of PTA.
7. a kind of PTA of utilization residue according to claim 1 is prepared the method for pure mixed phthalic acid 2-glycidyl ester, it is characterized in that the temperature that ring-opening reaction wherein occurs is: 110 DEG C-125 DEG C; Reaction times is: 0.5-3 hour.
8. a kind of PTA of utilization residue according to claim 1 is prepared the method for pure mixed phthalic acid 2-glycidyl ester, it is characterized in that the wherein ring-closure reaction time is: 3-5 hour.
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Cited By (1)
| 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 |
Citations (3)
| 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 |
| CN1632024A (en) * | 2004-12-22 | 2005-06-29 | 华南理工大学 | Structural pressure-sensitive adhesive |
| JP2011184373A (en) * | 2010-03-09 | 2011-09-22 | Nippon Shokubai Co Ltd | Method for producing glycidyl acrylate |
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2014
- 2014-01-16 CN CN201410018692.2A patent/CN103848799B/en active Active
Patent Citations (3)
| 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 |
| CN1632024A (en) * | 2004-12-22 | 2005-06-29 | 华南理工大学 | Structural pressure-sensitive adhesive |
| JP2011184373A (en) * | 2010-03-09 | 2011-09-22 | Nippon Shokubai Co Ltd | Method for producing glycidyl acrylate |
Non-Patent Citations (6)
| Title |
|---|
| 余磊 等: "对苯二甲酸二缩水甘油酯的合成", 《广东化工》, vol. 36, no. 6, 31 December 2009 (2009-12-31) * |
| 李安伍 等: "邻苯二甲酸二缩水甘油酯合成的工艺条件研究", 《衡阳师范学院学报》, vol. 29, no. 3, 30 June 2008 (2008-06-30), pages 87 - 91 * |
| 樊友: ""PTA"残渣混合酸合成对苯二甲酸二异辛酯的研究", 《杭州化工》, vol. 41, no. 4, 31 December 2011 (2011-12-31), pages 24 - 28 * |
| 石宁 等: "间苯二甲酸二缩水甘油酯的合成", 《热固性树脂》, vol. 15, no. 3, 31 July 2000 (2000-07-31), pages 5 - 9 * |
| 舒新华: "对苯二甲酸残渣生产对苯二甲酸二甲酯", 《江苏化工》, vol. 25, no. 6, 31 December 1997 (1997-12-31), pages 29 - 31 * |
| 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), pages 1465 - 1467 * |
Cited By (2)
| 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 |
| 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 |
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Effective date of registration: 20210310 Address after: Room 407-2-6, building C, Tian'an Digital City, 588 Changwu South Road, Wujin high tech Industrial Development Zone, Changzhou City, Jiangsu Province 213000 Patentee after: CHANGZHOU XIAOGUO INFORMATION SERVICES Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |