CN101774909B - Method for preparing 4, 4'-diphenyl ether dicarboxylic acid - Google Patents
Method for preparing 4, 4'-diphenyl ether dicarboxylic acid Download PDFInfo
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- CN101774909B CN101774909B CN201010113376A CN201010113376A CN101774909B CN 101774909 B CN101774909 B CN 101774909B CN 201010113376 A CN201010113376 A CN 201010113376A CN 201010113376 A CN201010113376 A CN 201010113376A CN 101774909 B CN101774909 B CN 101774909B
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- dioctyl phthalate
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Abstract
The invention discloses a method for preparing 4, 4'-diphenyl ether dicarboxylic acid, which comprises the following steps: 1, adding 4, 4'-dimethyl ether, catalysts, organic acids as solvents and bromide as oxide additives into a reaction device; 2, adopting a bubbling method for introducing oxygen under the liquid level of the solvent in the reaction device, and heating the mixture to 110 to 160 DEG C for oxidation reaction for 1 to 10 h, or adopting an intermittent method for pressing the oxygen into the reaction device in two to five times, pressurizing to 1.0 to 4.0 MPa, and simultaneously raising the temperature to 110 to 160 DEG C for oxidation reaction for 1 to 10 h; and 3, carrying out cooling, suction filtration, washing and drying on materials after the reaction. The method of the invention has few steps, short time and easy post treatment, and is applicable to industrial large-scale production, wherein the high-pressure oxidation method also has the advantages of little catalyst consumption, high yield and the like.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic binary carboxylic acid, particularly relate to a kind of preparation 4, the method for 4'-phenyl ether dioctyl phthalate.
Background technology
4,4'-phenyl ether dioctyl phthalate is a kind of important high polymer monomer, is mainly used in the high performance polybenzoxazoles resin of preparation, polyarylate resin, high-performance fiber, insulating material and thermoplastic liquid crystal polymer.Synthesize 4 at present, the method for 4'-phenyl ether dioctyl phthalate mainly contains following several kinds:
Chinese patent document CN1019484B (application number is 89109210) discloses a kind of synthetic 4 by p-Nitrobenzenecarboxylic acid, the method for 4'-phenyl ether dioctyl phthalate.This method is raw material with the p-Nitrobenzenecarboxylic acid; Carry out cyanogenation with POCl3 and ammonia earlier and make p-nitrophenyl first cyanogen; Carry out condensation reaction with nitrite and carbonate again and make 4,4'-dicyano phenyl ether, hydrolysis makes 4 in basic soln at last; 4'-phenyl ether dioctyl phthalate, yield are 73.5%.The deficiency of this method is: whole process need three-step reaction, and length consuming time, cost is high, and midbody p-nitrophenyl formonitrile HCN is a kind of hypertoxic organism, and yield is not high yet.
European patent document EP1211235 discloses a kind of under the catalysis of trifluoromethayl sulfonic acid hafnium; By phenyl ether Fu/gram acylation reaction taking place makes 4; 4'-diacetyl diphenyl sulphone ether, and then carry out haloform reaction with NaClO and slough trichloromethyl and make 4,4'-phenyl ether dioctyl phthalate.The deficiency of this method is: Fu/gram acylation reaction need use expensive trifluoromethayl sulfonic acid hafnium as catalyzer, and also must add a large amount of LiClO in the reaction
4, therefore also be difficult to suitability for industrialized production.
Chinese patent document CN1004808B (application number is 86101171) discloses a kind of 4; The compound method of 4'-phenyl ether dioctyl phthalate, this method at first make 4 through condensation reaction, 4'-dimethyl-phenyl ether with para-bromo toluene and p-cresol and Pottasium Hydroxide; Then earlier in pyridine solvent with potassium permanganate to 4; 4'-dimethyl-phenyl ether carries out the oxidation first time, under alkaline condition, carries out the oxidation second time with potassium permanganate again, thus make purity greater than 99% 4; 4'-phenyl ether dioctyl phthalate, the yield of oxidizing reaction are 85%.The deficiency of this method is: need carry out the two-step oxidation reaction, and whole process length consuming time, complex operation, cost is higher, and yield is not high yet; And the pyridine solvent stink that adopts is big, toxicity is big, and environmental pollution is serious, is not suitable for suitability for industrialized production.
" 4,4'-phenyl ether dioctyl phthalate synthesising process research " literary composition of " Hebei chemical industry " 11 phases in 2007 has been introduced a kind of with 4, and 4'-dimethyl-phenyl ether is a raw material, synthesizes 4, the method for 4'-phenyl ether dioctyl phthalate through the reaction of air liquid-phase catalysis.The deficiency of this method is: 1. catalyst levels is high: cobalt salt and 4 in the catalyst levels of its top condition, and the mol ratio of 4'-dimethyl-phenyl ether is 0.081, manganese salt and 4, the mol ratio of 4'-dimethyl-phenyl ether is 0.082, so cost is higher.2. long reaction time: this method needs the above reaction times of 30h.3. aftertreatment is loaded down with trivial details: need to adopt acid-alkali treatment, and carry out activated carbon decolorizing.The highest yield of the document also only is 90.1%.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, provide a kind of reaction times short, yield is high, cost is low, be applicable to the preparation 4 that large-scale industrialization is produced, the method for 4'-phenyl ether dioctyl phthalate.
One of technical scheme that realizes the object of the invention is: a kind of preparation 4; The method of 4'-phenyl ether dioctyl phthalate; Have following steps: 1. in reaction unit, add 4,4'-dimethyl-phenyl ether, catalyzer, as the organic acid of solvent and as the bromide of oxidation additive; Said catalyzer is cobalt salt and manganese salt, cobalt salt and 4 wherein, and the mol ratio of 4'-dimethyl-phenyl ether is 0.01: 1～0.08: 1, manganese salt and 4, the mol ratio of 4'-dimethyl-phenyl ether is 0.01: 1～0.08: 1; Organic acid and 4, the weight ratio of 4'-dimethyl-phenyl ether is 3: 1～15: 1; Bromide and 4, the mol ratio of 4'-dimethyl-phenyl ether is 0.01: 1～1: 1; 2. the method that adopts bubbling feeds oxygen (excessive) below the solvent liquid level in the reaction unit, is heated to 110 ℃～160 ℃ and generate 4, the oxidizing reaction 1h～10h of 4'-phenyl ether dioctyl phthalate; 3. with step 2. the material after the oxidizing reaction be cooled to 15 ℃～30 ℃, suction filtration is used organic acid and the water washing filter cake 1. identical with step successively then, last vacuum-drying filter cake obtains 4,4'-phenyl ether dioctyl phthalate.
Negatively charged ion in the catalyzer of above-mentioned steps described in 1. in cobalt salt and the manganese salt is halide anion or acetate moiety, and the mol ratio of manganese salt and cobalt salt is 1: 0.5～1: 1.
The organic acid of above-mentioned steps described in 1. is a kind of in glacial acetic acid, propionic acid, butanic acid, the isopropylformic acid, organic acid and 4, and the weight ratio of 4'-dimethyl-phenyl ether is 5: 1～10: 1.
The bromide of above-mentioned steps described in 1. is a kind of in Potassium Bromide, Sodium Bromide, brometo de amonio, hydrogen bromide, the tetrabromoethane, bromide and 4, and the mol ratio of 4'-dimethyl-phenyl ether is 0.03: 1～0.3: 1.
The oxidation time of above-mentioned steps in 2. is 3h～5h.
Another technical scheme that realizes the object of the invention is: a kind of preparation 4; The method of 4'-phenyl ether dioctyl phthalate; Have following steps: 1. in high pressure reaction assembly, add 4,4'-dimethyl-phenyl ether, catalyzer, as the organic acid of solvent and as the bromide of oxidation additive; Said catalyzer is cobalt salt and manganese salt, cobalt salt and 4 wherein, and the mol ratio of 4'-dimethyl-phenyl ether is 0.005: 1～0.03: 1, manganese salt and 4, the mol ratio of 4'-dimethyl-phenyl ether is 0.005: 1～0.03: 1; Organic acid and 4, the weight ratio of 4'-dimethyl-phenyl ether is 3: 1～15: 1; Bromide and 4, the mol ratio of 4'-dimethyl-phenyl ether is 0.01: 1～1: 1; 2. adopt interrupter method that oxygen (excessive) is divided and be pressed in the high pressure reaction assembly for 2～5 times, be forced into 1.0Mpa～4.0MPa, be warming up to 110 ℃～160 ℃ and generate 4,4'-phenyl ether dioctyl phthalate oxidizing reaction 1h～10h simultaneously; 3. with step 2. the material after the oxidizing reaction be cooled to 15 ℃～30 ℃, suction filtration is used organic acid and the water washing filter cake 1. identical with step successively then, last vacuum-drying filter cake obtains 4,4'-phenyl ether dioctyl phthalate.
Negatively charged ion in the catalyzer of above-mentioned steps described in 1. in cobalt salt and the manganese salt is halide anion or acetate moiety, and the mol ratio of cobalt salt and manganese salt is 1: 0.5～1: 1.
The organic acid of above-mentioned steps described in 1. is a kind of in glacial acetic acid, propionic acid, butanic acid, the isopropylformic acid, organic acid and 4, and the weight ratio of 4'-dimethyl-phenyl ether is 5: 1～10: 1.
The bromide of above-mentioned steps described in 1. is a kind of in Potassium Bromide, Sodium Bromide, brometo de amonio, hydrogen bromide, the tetrabromoethane, bromide and 4, and the mol ratio of 4'-dimethyl-phenyl ether is 0.03: 1～0.3: 1.
The oxidation time of above-mentioned steps in 2. is 3h～5h.
Reaction formula is following:
In the above-mentioned reaction formula, I is 4,4'-dimethyl-phenyl ether, and II is 4,4'-phenyl ether dioctyl phthalate.
The positively effect that method of the present invention has: (1) atmospheric pressure oxidation method of the present invention has that step is few, time short (only needing about 4h), the simple advantage of aftertreatment, and yield can reach about 90%, is suitable for industrial and large-scale production.(2) high-pressure oxidation method of the present invention not only has the above-mentioned advantage of atmospheric pressure oxidation method; Also have catalyst levels few (cobalt salt and manganese salt and 4; The mol ratio of 4'-dimethyl-phenyl ether is all less than 0.03), the yield advantages of higher, cost reduces greatly, yield is up to more than 95%.
Embodiment
(embodiment 1)
Present embodiment is non-pressure process (reaction vessel and atmosphere during reaction) preparation 4, and 4'-phenyl ether dioctyl phthalate has following steps:
1. with the reactant 4 of 12g, the catalyzer four water cobaltous acetates of 4'-dimethyl-phenyl ether, 1g, the catalyzer manganous acetate of 0.75g, the oxidation additive Sodium Bromide of 0.6g join in the 100mL reaction flask, and then add the organic acid propionic acid as solvent of 50g.
2. adopt the method for bubbling that excess of oxygen is fed below the liquid level in the reaction unit fast, be heated to 120 ℃ and generate 4, the oxidizing reaction 4h of 4'-phenyl ether dioctyl phthalate is until there being a large amount of white solids to separate out.
3. the material after the oxidizing reaction is cooled to 20 ℃, suction filtration then earlier with propionic acid washing 2 times, is used water washing 3 times more then, and last vacuum-drying gets the white solid 4 of 14g, and 4'-phenyl ether dioctyl phthalate, yield are 89.5%, purity >=99%.
(embodiment 2～embodiment 5)
The preparation method of each embodiment and embodiment 1 are basic identical, and difference is seen table 1.
(embodiment 6)
Present embodiment is high-pressure process (reaction vessel is in air-tight state during reaction) preparation 4, and 4'-phenyl ether dioctyl phthalate has following steps:
1. with the reactant 4 of 6g; The catalyzer four water cobaltous acetates of 4'-dimethyl-phenyl ether, 0.17g, the catalyzer manganous acetate of 0.11g, the oxidation additive Sodium Bromide of 0.32g join in the autoclave of 100mL, and then add the organic acid glacial acetic acid as solvent of 30g.
2. in autoclave, feed excess of oxygen and be pressurized to 1.0MPa and generate 4; The oxidizing reaction of 4'-phenyl ether dioctyl phthalate is heated with stirring to 135 ℃ simultaneously, and the autoclave internal pressure descends rapidly immediately; When pressure is reduced to 0.5MPa; Again aerating oxygen and be forced into 1.0MPa so circulates 2～4 times, keeps 1h to the autoclave internal pressure and no longer descends.
3. the material after the oxidizing reaction is cooled to 20 ℃, has a large amount of white solids to separate out suction filtration in the reaction solution; Then earlier with glacial acetic acid washing 2 times, use water washing again 3 times, last vacuum-drying obtains 4 of 7.3g; 4'-phenyl ether dioctyl phthalate white solid, yield is 93.4%, purity >=99%.
(embodiment 7～embodiment 10)
The preparation method of each embodiment and embodiment 6 are basic identical, and difference is seen table 2.
Claims (5)
1. one kind prepares 4, and the method for 4'-phenyl ether dioctyl phthalate is characterized in that having following steps:
1. in high pressure reaction assembly, add 4,4'-dimethyl-phenyl ether, catalyzer, as the organic acid of solvent and as the bromide of oxidation additive; Said catalyzer is cobalt salt and manganese salt, cobalt salt and 4 wherein, and the mol ratio of 4'-dimethyl-phenyl ether is 0.005: 1～0.03: 1, manganese salt and 4, the mol ratio of 4'-dimethyl-phenyl ether is 0.005: 1～0.03: 1; Organic acid and 4, the weight ratio of 4'-dimethyl-phenyl ether is 3: 1～15: 1; Bromide and 4, the mol ratio of 4'-dimethyl-phenyl ether is 0.01: 1～1: 1;
2. adopt interrupter method that oxygen is divided and be pressed in the high pressure reaction assembly for 2～5 times, be forced into 1.0Mpa～4.0MPa, be warming up to 110 ℃～160 ℃ and generate 4,4'-phenyl ether dioctyl phthalate oxidizing reaction 1h～10h simultaneously;
3. with step 2. the material after the oxidizing reaction be cooled to 15 ℃～30 ℃, suction filtration is used organic acid and the water washing filter cake 1. identical with step successively then, last vacuum-drying filter cake obtains 4,4'-phenyl ether dioctyl phthalate.
2. preparation 4 according to claim 1,4'-phenyl ether dioctyl phthalate method is characterized in that: the negatively charged ion in the catalyzer of step described in 1. in cobalt salt and the manganese salt is halide anion or acetate moiety, and the mol ratio of cobalt salt and manganese salt is 1: 0.5～1: 1.
3. preparation 4 according to claim 1; 4'-phenyl ether dioctyl phthalate method; It is characterized in that: the organic acid of step described in 1. is a kind of in glacial acetic acid, propionic acid, butanic acid, the isopropylformic acid, organic acid and 4, and the weight ratio of 4'-dimethyl-phenyl ether is 5: 1～10: 1.
4. preparation 4 according to claim 1; 4'-phenyl ether dioctyl phthalate method; It is characterized in that: the bromide of step described in 1. is a kind of in Potassium Bromide, Sodium Bromide, brometo de amonio, hydrogen bromide, the tetrabromoethane; Bromide and 4, the mol ratio of 4'-dimethyl-phenyl ether is 0.03: 1～0.3: 1.
5. preparation 4 according to claim 1,4'-phenyl ether dioctyl phthalate method is characterized in that: the oxidation time of step in 2. is 3h～5h.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104311408B (en) * | 2014-09-12 | 2019-11-08 | 沈阳化工研究院有限公司 | The preparation method of 4,4 '-oxydibenzoic acids |
| CN106008174A (en) * | 2016-05-24 | 2016-10-12 | 青岛和新精细化工有限公司 | Preparation method of 4,4'-dialkoxy methyl diphenyl ether |
| CN108484381A (en) * | 2018-03-08 | 2018-09-04 | 上海应用技术大学 | A kind of method that Anderson types polyacid catalysis oxidation prepares 4,4`- oxydibenzoic acids |
| CN108276275A (en) * | 2018-03-08 | 2018-07-13 | 上海应用技术大学 | A kind of method that metal oxide oxidation catalyst oxidation prepares 4,4`- oxydibenzoic acids |
| CN112409142B (en) * | 2019-08-20 | 2022-04-19 | 帕潘纳(北京)科技有限公司 | Preparation method of 4-p-chlorophenoxyl acetophenone compounds |
| CN115650840B (en) * | 2022-12-29 | 2023-03-31 | 中节能万润股份有限公司 | Preparation method of 4,4' -diphenyl ether dicarboxylic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1019484B (en) * | 1989-12-08 | 1992-12-16 | 鞍山钢铁学院 | Synthesizing 4,4' diphenyl ether diformic acid from p-nitrophenyl formic acid |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1019484B (en) * | 1989-12-08 | 1992-12-16 | 鞍山钢铁学院 | Synthesizing 4,4' diphenyl ether diformic acid from p-nitrophenyl formic acid |
Non-Patent Citations (2)
| Title |
|---|
| 王玉环等.4 4"-二苯醚二甲酸合成工艺研究.《河北化工》.2007 |
| 王玉环等.4,4"-二苯醚二甲酸合成工艺研究.《河北化工》.2007,第30卷(第11期),41-42. * |
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Owner name: CHANGZHOU SUNLIGHT PHARMACEUTICAL CO., LTD. Free format text: FORMER NAME: CHANGZHOU SUNLIGHT MEDICAL RAW MATERIAL CO., LTD. |
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Address after: 213134 Jiangsu province Changzhou city Wujin district nine Street Benniu town Patentee after: Changzhou Sunlight Pharmaceutical Co., Ltd. Patentee after: Sichuan University Address before: 213134 Jiangsu province Changzhou city Wujin district nine Street Benniu town Patentee before: Changzhou Sunlight Medical Raw Material Co., Ltd. Patentee before: Sichuan University |