CN103508892A - Synthetic method for phthalate compound - Google Patents
Synthetic method for phthalate compound Download PDFInfo
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- CN103508892A CN103508892A CN201310470215.5A CN201310470215A CN103508892A CN 103508892 A CN103508892 A CN 103508892A CN 201310470215 A CN201310470215 A CN 201310470215A CN 103508892 A CN103508892 A CN 103508892A
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- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention discloses a method for using phthalic anhydride as a raw material to efficiently synthesize a phthalate compound. The synthetic method comprises the following steps: firstly taking reaction to phthalic anhydride and alcohol to generate monophthalate, then taking reaction to monophthalate and alcohol in the presence of a catalyst, carrying a following fabrication processing (3) to neutralize the reaction mixture obtained in the step (2) with an alkali metal hydroxide water solution, carrying out water washing to remove the salt generated in the reaction, then distilling and drying the solution to remove moisture, and at last using a column chromatography or rectification method to separate out the phthalate compound to obtain the pure product. The synthetic method is simple and efficient. In the method, the reaction condition requirements are low, and the high temperature reaction is not required or concentrated sulfuric acid. The requirement to the device is far lower than those of the prior art. No impurity generates; the follow-up fabrication treatment steps are simple; in addition, compared to the prior art, the synthetic method causes less environment pollution.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of phthalate compound synthetic method that Tetra hydro Phthalic anhydride is raw material of take.
Background technology
Phthalic ester (Phthalates), claims again phthalate, and abbreviation PAEs is the general designation of the ester that forms of phthalic acid, is generally that volatility is very low, stability is high and colourlessly has aromatic odour or a scentless thickness oily liquids.In water, solubleness is very little, is easily dissolved in most non-polar organic solvents.Phthalic ester is modal softening agent/tenderizer/plasticizer in plastics industry, extensively make an addition to the production of daily and industrial high molecular weight plastic product, to strengthen elasticity, transparency, wearing quality and work-ing life, phthalic ester also can be used to softening polyvinyl chloride (PVC).Its Application Areas contains tackiness agent and glue, electronics industry, agriculture adjuvant, material of construction, personal care product, medicine equipment, washing composition and tensio-active agent, packing business, toy for children, sculpture soil, wax, paint, ink, coating, medicine, food and textile industry etc.In global range, consume every year the fluidizer of approximately 6,000,000 tons, wherein the consumption in Europe is about 1,000,000 tons, accounts for the 10-60% of whole plastics weight.
In addition, research shows that part phthalic ester can disturbance endocrine, makes that mankind spermatozoon quantity reduces, motor capacity is low, paramophia, and serious also can cause necrospermia and carcinoma of testis, is " arch-criminal " who causes male genetic problem.Phthalic ester hydrolysis and photodissociation speed are all very slow, belong to difficult degradation pollutent.They have " three cause " effect, belong to environment incretion interferent, and Environmental Protection Agency (EPA) and China have been classified as priority pollutants.So, no matter from industrial application or examination criteria product development aspect, all need efficiently to synthesize the synthetic method of phthalic ester sterling.
At present, the method for synthetic phthalic ester is to adopt alkyd direct esterification conventionally.The method is carried out esterification under vitriol oil effect, esterifying liquid through neutralization, dehydration, fractionation and finished product.Owing to using the reaction conditions of concentrated acid and high temperature, impurity in products content is high, and thermostability is looked into; Reaction easily generates the foreign pigment of ethers and the polymerization of acids impurity, makes product painted, increases postprocessing working procedures; Cannot synthesize the diester that two ester groups are different hydrocarbons group; There is equipment corrosion large, the problem such as environmental pollution is serious simultaneously.
Summary of the invention
The invention provides and a kind ofly take Tetra hydro Phthalic anhydride as raw material, efficiently the method for synthetic phthalate compound.Such phthalate compound has following general formula:
Wherein, R1, R2 are independently selected from respectively alkyl or cycloalkyl, Ar group or the ArCH2 substituting group of C1-10;
Above-mentioned Ar is aromatic group;
Or
Wherein, R3, R4, R5, R6 are independently selected from respectively the alkyl of C1-5.
Described phthalic ester synthetic method, comprises the following steps:
(1) under alkali exists, in organic solvent or solvent-free, Tetra hydro Phthalic anhydride and alcohol reaction generate phthalic monoester, and the mol ratio of acid anhydrides and alcohol is 1:0.5-10, and temperature of reaction is 100 ℃ of-20 ℃ –, and the reaction times is 0.5-24 hour;
(2) phthalic monoester is under catalyzer exists, in organic solvent or solvent-free, reaction generates phthalic ester with alcohol, the mol ratio of phthalic monoester and catalyzer is 1:0.01-1.5, the mol ratio of phthalic monoester and alcohol is 1:0.5-10, temperature of reaction is 250 ℃ of 20 ℃ –, and the reaction times is 1-24 hour;
(3) reaction mixture of step (2) gained is neutralized with alkali metal hydroxide aqueous solution, through water-washing step, remove the salt that reaction generates again, by distillation, drying step, remove moisture afterwards, finally use the method separation of column chromatography or rectifying to obtain sterling.
Alcohol used is selected from: C
1-10direct-connected or side chain or cycloalkyl alcohol, C
1-10containing at least one in the alkyl alcohol of ether, arylmethyl alcohol, fragrant phenol.
Alkali used is selected from: at least one in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, triethylamine, diisopropyl ethyl amine, pyridine, 4-(N, N-dimethylamino)-pyridine.
Organic solvent used is selected from: hexanaphthene, benzene,toluene,xylene, acetonitrile, acetone, methylene dichloride, chloroform, tetracol phenixin, 1, at least one in 2-ethylene dichloride, ether, tetrahydrofuran (THF), methyl alcohol, ethanol, DMF or dimethyl sulfoxide (DMSO).
Catalyzer used is selected from: sulfur oxychloride, trifluoroacetic acid, methylsulfonic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, p-methyl benzenesulfonic acid, 3-nitrobenzene-sulfonic acid, 4-nitrobenzene-sulfonic acid, 2, at least one in 4-dinitrobenzene sulfonic acid, sulfuric acid, nitric acid, hydrochloric acid, titanium tetrachloride, tetraisopropoxy titanium, four titanium butoxide, titanium oxide, tin tetrachloride, silicon oxide, ferric oxide, iron(ic) chloride, iron nitrate, stannic oxide solid acid.
Synthetic method of the present invention is simply efficient, and reaction conditions requires low, does not need at high temperature to react, and does not need to use the vitriol oil, much lower compared to existing technology to equipment requirements; Do not produce impurity, subsequent processing steps is simple; Environmental pollution is also much lower compared to existing technology for method of the present invention in addition.
Embodiment
By following embodiment, contribute to further to understand the present invention, but do not limit the content of invention.
The synthetic method of embodiment 1 mono-ethyl phthalate
Pyridine (3mL) is joined in the mixture of Tetra hydro Phthalic anhydride (3.0g, 20.2mmol) and ethanol (1.2mL, 20.3mmol), under room temperature, stir 24h, after concentrating under reduced pressure, be dissolved in ether, with dilute hydrochloric acid, wash away pyridine.Anhydrous Na after saturated common salt water washing for organic phase
2sO
4dry.Filter removal of solvent under reduced pressure.Resistates obtains mono-ethyl phthalate (3.65g, 93.0%) with benzene recrystallization.
Embodiment 2 take tosic acid as catalyzer from mono-ethyl phthalate synthetic diethyl phthalate
In flask, add phthalic monoester (1.94g, 10.0mmol), ethanol (1.3mL, 23.5mmol) and hexanaphthene (10mL), after stirring and dissolving, add tosic acid (0.7g, 4mmol), connect water trap, the backflow of reflux condensing tube post-heating, cooling after reaction 8h, air distillation is except desolventizing and unreacted benzylalcohol.After crude product n-hexane dissolution, use 5%Na
2cO
3the aqueous solution is neutralized to neutrality, separated organic layer.Anhydrous Na after saturated common salt water washing for organic phase
2sO
4dry.Filter, removal of solvent under reduced pressure, underpressure distillation obtains diethyl phthalate (1.64g, 73.7%).
Embodiment 3 take four titanium butoxide as catalyzer from mono-ethyl phthalate synthetic diethyl phthalate
Through in the there-necked flask of Non-aqueous processing, add mono-ethyl phthalate (1.94g, 10.0mmol), ethanol (1.7mL, 30.0mmol), four titanium butoxide (60 μ L, 0.2mmol) and p-Xylol (20mL), be back to reaction and substantially finish (TLC follows the tracks of reaction).Return to room temperature, the diethyl phthalate of underpressure distillation after removal of solvent under reduced pressure (1.98g, 89.4%).
Embodiment 4 take stannic oxide solid acid as catalyzer from mono-ethyl phthalate synthetic diethyl phthalate
Through in the there-necked flask of Non-aqueous processing, add mono-ethyl phthalate (1.94g, 10.0mmol), ethanol (1.7mL, 30.0mmol), stannic oxide solid acid (170mg) and p-Xylol (20mL), be back to reaction and substantially finish (TLC follows the tracks of reaction).Return to room temperature, the diethyl phthalate of underpressure distillation after removal of solvent under reduced pressure (2.06g, 92.8%).
The synthetic method of embodiment 5 stannic oxide solid acids
Ammoniacal liquor acts on tin tetrachloride and forms colloid, after washing, filters, and at 200 ℃, dries 4h, obtains vitreous solid.Solid is soaked in to 30min in dilute sulphuric acid (1mol/L, solid-to-liquid ratio 1:10), filters.Filter cake dries 4h at 500 ℃ and obtains stannic oxide solid acid.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.So every, do not depart from the equivalence completing under principles of this disclosure or revise, all falling into the scope of protection of the invention.
Claims (5)
1. a synthetic method for phthalate compound, compound has following general formula:
Wherein, R
1, R
2independently be selected from respectively C
1-10alkyl or cycloalkyl, Ar group or ArCH
2substituting group;
Above-mentioned Ar is aromatic group;
Or
Wherein, R
3, R
4, R
5, R
6independently be selected from respectively C
1-5alkyl;
It is characterized in that, this comprises the following steps:
(1) under alkali exists, in organic solvent or solvent-free, Tetra hydro Phthalic anhydride and alcohol reaction generate phthalic monoester, and the mol ratio of acid anhydrides and alcohol is 1:0.5-10, and temperature of reaction is 100 ℃ of-20 ℃ –, and the reaction times is 0.5-24 hour;
(2) phthalic monoester is under catalyzer exists, in organic solvent or solvent-free, reaction generates phthalic ester with alcohol, the mol ratio of phthalic monoester and catalyzer is 1:0.01-1.5, the mol ratio of phthalic monoester and alcohol is 1:0.5-10, temperature of reaction is 250 ℃ of 20 ℃ –, and the reaction times is 1-24 hour;
(3) reaction mixture of step (2) gained is neutralized with alkali metal hydroxide aqueous solution, through water-washing step, remove the salt that reaction generates again, by distillation, drying step, remove moisture afterwards, finally use the method separation of column chromatography or rectifying to obtain sterling.
2. the method for claim 1, is characterized in that, alcohol used is selected from: C
1-10direct-connected or side chain or cycloalkyl alcohol, C
1-10containing at least one in the alkyl alcohol of ether, arylmethyl alcohol, fragrant phenol.
3. the method for claim 1, it is characterized in that, alkali used is selected from: at least one in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, triethylamine, diisopropyl ethyl amine, pyridine, 4-(N, N-dimethylamino)-pyridine.
4. the method for claim 1, it is characterized in that, organic solvent used is selected from: hexanaphthene, benzene,toluene,xylene, acetonitrile, acetone, methylene dichloride, chloroform, tetracol phenixin, 1, at least one in 2-ethylene dichloride, ether, tetrahydrofuran (THF), methyl alcohol, ethanol, DMF or dimethyl sulfoxide (DMSO).
5. the method for claim 1, it is characterized in that, catalyzer used is selected from: sulfur oxychloride, trifluoroacetic acid, methylsulfonic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, p-methyl benzenesulfonic acid, 3-nitrobenzene-sulfonic acid, 4-nitrobenzene-sulfonic acid, 2, at least one in 4-dinitrobenzene sulfonic acid, sulfuric acid, nitric acid, hydrochloric acid, titanium tetrachloride, tetraisopropoxy titanium, four titanium butoxide, titanium oxide, tin tetrachloride, silicon oxide, ferric oxide, iron(ic) chloride, iron nitrate, stannic oxide solid acid.
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|---|---|---|---|
| CN201310470215.5A CN103508892A (en) | 2013-10-10 | 2013-10-10 | Synthetic method for phthalate compound |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496818A (en) * | 2014-12-19 | 2015-04-08 | 河南奥思达新材料有限公司 | Method or producing DBP by utilizing composite Lewis acid catalysis method |
| CN104860821A (en) * | 2014-05-23 | 2015-08-26 | 山东瀚霖生物技术有限公司 | Diacid monomer acid monoester and preparation method therefor |
| CN104860817A (en) * | 2015-04-10 | 2015-08-26 | 上海化工研究院 | Stable isotope labeled benzyl butyl phthalate and synthesis method thereof |
| CN105348792A (en) * | 2015-12-11 | 2016-02-24 | 安徽律正科技信息服务有限公司 | Anti-aging plasticizer for wood plastic composite material |
| CN106831429A (en) * | 2017-02-06 | 2017-06-13 | 常州工程职业技术学院 | A kind of method that maleic anhydride waste residue prepares diethyl phthalate |
| CN109776317A (en) * | 2019-03-27 | 2019-05-21 | 山东润科化工股份有限公司 | A kind of synthetic method of bis- (2- ethylhexyl) esters of tetrabromophthalate |
| CN109796341A (en) * | 2019-01-25 | 2019-05-24 | 上海阿拉丁生化科技股份有限公司 | A kind of synthetic method of high-purity o phthalic acid n-pentyl isopentyl ester |
| CN110003001A (en) * | 2019-05-08 | 2019-07-12 | 葫芦岛市载大瀛嘉化工有限公司 | A kind of preparation method of diphenyl phthalate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733695A (en) * | 2005-09-05 | 2006-02-15 | 吉化集团公司 | Diisodecyl phthalate preparation method |
| CN1777475A (en) * | 2003-04-23 | 2006-05-24 | 株式会社日本能源 | Solid acid catalyst containing tin and method for preparation thereof |
| CN101654441A (en) * | 2008-08-19 | 2010-02-24 | 信谊药厂 | Anticoagulant compound, composition and application thereof |
| CN102224128A (en) * | 2008-11-24 | 2011-10-19 | 埃克森美孚化学专利公司 | Improved method for the manufacture of long chain phthalate dialkyl ester compositions |
| CN103159625A (en) * | 2011-12-08 | 2013-06-19 | 沈阳工业大学 | Method of producing trimethylolpropane oleate with single kettle |
-
2013
- 2013-10-10 CN CN201310470215.5A patent/CN103508892A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1777475A (en) * | 2003-04-23 | 2006-05-24 | 株式会社日本能源 | Solid acid catalyst containing tin and method for preparation thereof |
| CN1733695A (en) * | 2005-09-05 | 2006-02-15 | 吉化集团公司 | Diisodecyl phthalate preparation method |
| CN101654441A (en) * | 2008-08-19 | 2010-02-24 | 信谊药厂 | Anticoagulant compound, composition and application thereof |
| CN102224128A (en) * | 2008-11-24 | 2011-10-19 | 埃克森美孚化学专利公司 | Improved method for the manufacture of long chain phthalate dialkyl ester compositions |
| CN103159625A (en) * | 2011-12-08 | 2013-06-19 | 沈阳工业大学 | Method of producing trimethylolpropane oleate with single kettle |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860821A (en) * | 2014-05-23 | 2015-08-26 | 山东瀚霖生物技术有限公司 | Diacid monomer acid monoester and preparation method therefor |
| CN104496818A (en) * | 2014-12-19 | 2015-04-08 | 河南奥思达新材料有限公司 | Method or producing DBP by utilizing composite Lewis acid catalysis method |
| CN104860817A (en) * | 2015-04-10 | 2015-08-26 | 上海化工研究院 | Stable isotope labeled benzyl butyl phthalate and synthesis method thereof |
| CN105348792A (en) * | 2015-12-11 | 2016-02-24 | 安徽律正科技信息服务有限公司 | Anti-aging plasticizer for wood plastic composite material |
| CN106831429A (en) * | 2017-02-06 | 2017-06-13 | 常州工程职业技术学院 | A kind of method that maleic anhydride waste residue prepares diethyl phthalate |
| CN109796341A (en) * | 2019-01-25 | 2019-05-24 | 上海阿拉丁生化科技股份有限公司 | A kind of synthetic method of high-purity o phthalic acid n-pentyl isopentyl ester |
| CN109776317A (en) * | 2019-03-27 | 2019-05-21 | 山东润科化工股份有限公司 | A kind of synthetic method of bis- (2- ethylhexyl) esters of tetrabromophthalate |
| CN110003001A (en) * | 2019-05-08 | 2019-07-12 | 葫芦岛市载大瀛嘉化工有限公司 | A kind of preparation method of diphenyl phthalate |
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Application publication date: 20140115 |