CN103848799B - A kind of PTA of utilization residue prepares the method for pure mixed phthalic acid 2-glycidyl ester - Google Patents
A kind of PTA of utilization residue prepares the method for pure mixed phthalic acid 2-glycidyl ester Download PDFInfo
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- CN103848799B CN103848799B CN201410018692.2A CN201410018692A CN103848799B CN 103848799 B CN103848799 B CN 103848799B CN 201410018692 A CN201410018692 A CN 201410018692A CN 103848799 B CN103848799 B CN 103848799B
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- phthalic acid
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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 present invention is a kind of method that the PTA of utilization residue prepares pure mixed phthalic acid 2-glycidyl ester, belongs to organic synthesis field.Carry out according to following step: with PTA residue and epoxy chloropropane for starting raw material, add a certain amount of organic solvent, heating and catalyzer effect under, 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.To the present invention proposes with PTA secondary residual as raw material, accomplished the recycle of resource, the cost of raw material is reduced greatly, effectively protect environment simultaneously; Use solvent method to greatly reduce the consumption of epoxy chloropropane, avoid a difficult problem for epoxy chloropropane recovery, improve oxirane value and the productive rate of product, facilitate the widespread use of this based epoxy resin.
Description
Technical field
The present invention relates to a kind of preparation method of glycidyl ester, belong to organic synthesis field.
Background technology
Containing phenyl ring and the stronger Racemic glycidol ester bond of polarity in the molecular structure of phthalic acid 2-glycidyl ester, can be made into sizing agent and the insulating material of excellent property, be applicable to the matrix doing matrix material, also can react with acrylic compounds and make epoxy acrylic etc.Phthalic acid 2-glycidyl ester prior synthesizing method mainly respectively with pure terephthalic acid (PTA), m-phthalic acid and phthalic acid for prepared by raw material, make phthalic acid 2-glycidyl ester preparation cost high, constrain its widespread use; In addition, the synthesis of traditional phthalic acid 2-glycidyl ester is generally the technique adopting epoxy chloropropane greatly excessive, not only make the oxirane value of product low, but also bring a difficult problem for epoxy chloropropane recovery, cause the defect that quality product is low and product cost is high, significantly limit 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, this based epoxy resin widespread use can not only be promoted, and the effective and reasonable utilization of PTA residue waste can also be accomplished, 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 such as formula shown in I and formula II:
Formula I open loop and esterification
Formula II ring-closure reaction
A kind of PTA of utilization residue prepares the method for pure mixed phthalic acid 2-glycidyl ester, carry out according to following step: with PTA residue and epoxy chloropropane for starting raw material, add a certain amount of organic solvent, heating and catalyzer effect under, 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., preferred 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 having reclaimed phenylformic acid and cobalt-manganese catalyst, and be PTA secondary residual, its acid number is 617mgKOH/g, converts as carboxylic acid content is 11mmol/g.The feed ratio of open loop and esterification is: the carboxylic acid in PTA secondary residual and the mol ratio 1.0:1.5-1.0:2.5 of epoxy chloropropane, and catalyzer is the 0.5%-3% of PTA secondary residual quality, and reaction solvent consumption is 2-3 times of PTA secondary residual quality; In ring-closure reaction, the charging capacity of mineral alkali is 2-3 times of carboxylic acid mole number in PTA secondary residual.
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 are all commercially.
Novelty of the present invention is: first, to the present invention proposes with PTA secondary residual as raw material, has accomplished the recycle of resource, the cost of raw material is reduced greatly, effectively protects environment simultaneously; Secondly, use solvent method to greatly reduce the consumption of epoxy chloropropane, avoid a difficult problem for epoxy chloropropane recovery, improve oxirane value and the productive rate of product, facilitate 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
In 100ml four-hole boiling flask, add the PTA secondary residual 10.1g that acid number is 617mgKOH/g successively, catalyzer triphenylphosphine is 0.5% of the quality of PTA residue, i.e. 0.05g, and solvent acetic acid butyl ester is 2 times of PTA secondary residual, i.e. 20g.Stir, be heated to backflow, with the ratio of the mol ratio 1.0:1.5 of the carboxylic acid in PTA secondary residual 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, after continuing to stir cooling 1h, suction filtration removes 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, slowly the NaOH aqueous solution is dripped under whipped state, to in reaction filtrate, after stirring at room temperature reaction 3h, be washed to neutrality, layering, take off layer, revolve steaming, give light yellow oil 5.4g, oxirane value 5.3mol/100g.
Embodiment 2
In 100ml four-hole boiling flask, add the PTA secondary residual 10.1g that acid number is 617mgKOH/g successively, catalyzer triphenylphosphine is 1% of the quality of PTA residue, i.e. 0.1g, and solvent toluene is 2.5 times of PTA secondary residual, i.e. 25g.Stir, be heated to backflow, with the ratio of the mol ratio 1.0:2.0 of the carboxylic acid in PTA secondary residual and epoxy chloropropane, take epoxy chloropropane 20.2g, drop in reaction solution, after back flow reaction 3h, stop heating, add 0.5g activated carbon, after continuing to stir cooling 1h, suction filtration removes activated carbon, with the ratio of mol ratio 1:2.5, take NaOH solid 4.4g, the preparation 50%NaOH aqueous solution, slowly the NaOH aqueous solution is dripped under whipped state, to in reaction filtrate, after stirring at room temperature reaction 4h, be washed to neutrality, layering, take off layer, revolve steaming, give light yellow oil 4.2g, oxirane value 5.6mol/100g.
Embodiment 3
In 100ml four-hole boiling flask, add the PTA secondary residual 10.1g that acid number is 617mgKOH/g successively, catalyzer triphenylphosphine is 3% of the quality of PTA residue, i.e. 0.3g, 3 times of solvent acetic acid butyl ester PTA secondary residual, i.e. 30g.Stir, be heated to backflow, with the ratio of the mol ratio 1.0:2.5 of the carboxylic acid in PTA secondary residual 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, after continuing to stir cooling 1h, suction filtration removes activated carbon, filtrate is revolved and is steamed except desolventizing, weigh, add q. s. methylene chloride, with the ratio of mol ratio 1:3, take NaOH solid 5.2g, the preparation 50%NaOH aqueous solution, slowly the NaOH aqueous solution is dripped under whipped state, after stirring 5h, be washed to neutrality, layering, take off layer, revolve steaming, give light yellow oil 9.5g, oxirane value 8.1mol/100g.
Claims (3)
1. the method utilizing PTA residue to prepare pure mixed phthalic acid 2-glycidyl ester, it is characterized in that carrying out according to following step: with PTA residue and epoxy chloropropane for starting raw material, add a certain amount of organic solvent, heating and catalyzer effect under, 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 Tetrabutyl amonium bromide, cetyl trimethylammonium bromide, 4-methylimidazole, glyoxal ethyline, triphenylphosphine; Wherein said organic solvent is: butylacetate, toluene; 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 having reclaimed phenylformic acid and cobalt-manganese catalyst, and be PTA secondary residual, its acid number is 620mgKOH/g, converts as carboxylic acid content is 11mmol/g; The feed ratio of wherein said open loop and esterification is: the carboxylic acid in PTA secondary residual and the mol ratio 1.0:1.5-1.0:2.5 of epoxy chloropropane, catalyzer is the 0.1%-3% of PTA secondary residual quality, and reaction solvent consumption is 2-3 times of PTA secondary residual quality; In ring-closure reaction, the charging capacity of mineral alkali is 2-3 times of carboxylic acid mole number in PTA secondary residual; Wherein the temperature of occurred ring-opening reaction is: 110 DEG C-125 DEG C; Reaction times is: 0.5-3 hour; Wherein the ring-closure reaction time is: 3-5 hour.
2. a kind of PTA of utilization residue according to claim 1 prepares the method for pure mixed phthalic acid 2-glycidyl ester, it is characterized in that wherein said catalyzer is triphenylphosphine.
3. a kind of PTA of utilization residue according to claim 1 prepares the method for pure mixed phthalic acid 2-glycidyl ester, it is characterized in that wherein said organic solvent is: butylacetate.
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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 |
| CN1632024A (en) * | 2004-12-22 | 2005-06-29 | 华南理工大学 | Structural pressure-sensitive adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5546908B2 (en) * | 2010-03-09 | 2014-07-09 | 株式会社日本触媒 | Method for producing glycidyl acrylate |
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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 |
| CN1632024A (en) * | 2004-12-22 | 2005-06-29 | 华南理工大学 | Structural pressure-sensitive adhesive |
Non-Patent Citations (6)
| Title |
|---|
| "PTA"残渣混合酸合成对苯二甲酸二异辛酯的研究;樊友;《杭州化工》;20111231;第41卷(第4期);24-28 * |
| 对苯二甲酸二缩水甘油酯的合成;余磊 等;《广东化工》;20091231;第36卷(第6期);26-28、252 * |
| 对苯二甲酸二缩水甘油酯的合成;蔡亚 等;《应用化工》;20081231;第37卷(第12期);1465-1467 * |
| 对苯二甲酸残渣生产对苯二甲酸二甲酯;舒新华;《江苏化工》;19971231;第25卷(第6期);29-31 * |
| 邻苯二甲酸二缩水甘油酯合成的工艺条件研究;李安伍 等;《衡阳师范学院学报》;20080630;第29卷(第3期);87-91 * |
| 间苯二甲酸二缩水甘油酯的合成;石宁 等;《热固性树脂》;20000731;第15卷(第3期);5-9 * |
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