CN103483198B - A kind of preparation method of triethylene glycol dibenzoate - Google Patents
A kind of preparation method of triethylene glycol dibenzoate Download PDFInfo
- Publication number
- CN103483198B CN103483198B CN201210193726.2A CN201210193726A CN103483198B CN 103483198 B CN103483198 B CN 103483198B CN 201210193726 A CN201210193726 A CN 201210193726A CN 103483198 B CN103483198 B CN 103483198B
- Authority
- CN
- China
- Prior art keywords
- structural formula
- reaction
- triglycol
- potassium carbonate
- triethylene glycol
- 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.)
- Active
Links
- AHSGHEXYEABOKT-UHFFFAOYSA-N 2-[2-(2-benzoyloxyethoxy)ethoxy]ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOCCOC(=O)C1=CC=CC=C1 AHSGHEXYEABOKT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 76
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 37
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000004821 distillation Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 28
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 229940095102 methyl benzoate Drugs 0.000 description 9
- 230000004044 response Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000003870 refractory metal Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- -1 triethyleneglycol ester compounds Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides the preparation method that a kind of structural formula is the triethylene glycol dibenzoate of (I), under the method is included in the catalyzer existence containing Anhydrous potassium carbonate, be that triglycol and the benzoic ether PhCOOR of (II) reacts by structural formula, generate that to comprise structural formula be the triethylene glycol dibenzoate of (I) and the product of corresponding alcohol HOR; Wherein, R is methyl or ethyl.The inventive method is beneficial to environment protection; Product yield is high, and purity is good.
Description
Technical field
The present invention relates to the preparation method of plasticizer components triethyleneglycol ester compounds, be specifically related to the preparation method of triethylene glycol dibenzoate.
Background technology
Softening agent refers to the additives for plastics used in the plastics processing processes such as polyvinyl chloride, and it adds in polymeric system can make polymer glass temperature reduce, and plasticity increases, and makes it to be easy to processing.The output of softening agent accounts for 60% of additives for plastics total amount, is mainly used in polrvinyl chloride product, and consumption accounts for 80%.The kind of softening agent is many, and the overwhelming majority is ester class, and wherein the output of phthalate (comprising DOP, DBP, BBP, DINP, DIDP, DnOP etc.) accounts for 85%.But use phthalic ester plasticizer to be restricted in Europe and the U.S., under the background of Taiwan " fluidizer " event, the cry using non-phthalate environment-friendly plasticizer will be more and more higher.
CN101155772B discloses a kind of preparation method for plasticizer for polyvinyl chloride component triethylene glycol dibenzoate and triglycol dicarboxylic ester.For raw material, under catalyst action, esterification is there is, the triglycol dicarboxylic ester needed for generation, and by " entrainment agent ", the water byproduct of generation is discharged to outside, to improve the transformation efficiency of triglycol in the method with triglycol and carboxylic acid.The catalyzer that this patented method is mentioned has: the metal oxide such as metal-salt, heteropolyacid, natural/synthetic zeolite, the ion exchange resin etc. such as an acidic catalyst such as organo-metallic, tosic acid, calcium chloride such as tetra isopropyl titanate.According to the whole embodiment 1-3 of CN101155772B, under the katalysis of tetra isopropyl titanate, the phenylformic acid in reaction raw materials and triglycol generation esterification, generate triethylene glycol dibenzoate.But, need neutralization, washing step after the reaction of this patented method terminates, thus bring sewage handling problem, and thick product also to add sorbent material after decompression dehydration, filtration just can obtain required purified product.These are all unfavorable for scale operation.
Summary of the invention
The object of the invention is, in order to overcome shortcoming of the prior art, to provide a kind of preparation method of new triethylene glycol dibenzoate.
To achieve these goals, the invention provides the preparation method that a kind of structural formula is the triethylene glycol dibenzoate of (I), it is characterized in that, under described method is included in the catalyzer existence containing Anhydrous potassium carbonate, be that triglycol and the benzoic ether PhCOOR of (II) reacts by structural formula, generate that to comprise structural formula be the triethylene glycol dibenzoate of (I) and the product of corresponding alcohol HOR;
Wherein, R is methyl or ethyl.
The preparation method of triethylene glycol dibenzoate provided by the invention, substitutes phenylformic acid as acylating agent with benzoic ether PhCOOR; The carboxylic esterification catalysts such as the tetra isopropyl titanate affecting quality product are substituted with the catalyzer containing Anhydrous potassium carbonate, avoid and react the neutralization after terminating, washing step, solve the effluent problem brought in prior art plasticizer production process, be conducive to protection of the environment or safety in production, be suitable for large-scale commercial production; Product and reactant and catalyzer easily separated, yield is high, and purity is good, carrys out purified product without the need to adding sorbent material.The inventive method can be widely used in industrial production.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides the preparation method that a kind of structural formula is the triethylene glycol dibenzoate of (I), under described method is included in the catalyzer existence containing Anhydrous potassium carbonate, be that triglycol and the benzoic ether PhCOOR of (II) reacts by structural formula, generate that to comprise structural formula be the triethylene glycol dibenzoate of (I) and the product of corresponding alcohol HOR;
Wherein, R is methyl or ethyl.
According to the present invention, under the catalyzer containing Anhydrous potassium carbonate exists, be that triglycol and the benzoic ether PhCOOR of (II) reacts by structural formula, it is the triethylene glycol dibenzoate of (I) and the product of corresponding alcohol HOR that generation comprises structural formula; Wherein, R is methyl or ethyl, can realize object of the present invention, namely be beneficial to environment protection, product and reactant and catalyzer easily separated, yield is high, and purity is good.But under preferable case, described transesterification reaction is reacted under being included in distillation or rectifying condition, and reaction removes the alcohol HOR of generation simultaneously; Further preferred version is, is reacting 3-7 hour with the rear entrainer adding alcohol HOR in reaction solution, with the alcohol HOR generated except dereaction by the mode of component distillation or azeotropic distillation.This preferred version can further improve yield and the purity of the product that structural formula is (I).
In the present invention, what steadily continue to enable above-mentioned preferred version carries out forward, reaction brings into use upper end " skimmer " of prolong to be housed as water distilling apparatus, and described " skimmer " refers to that the Dean and Stark apparatus (DeanandStarkapparatuswithastopcockatthelowerend) of piston switch is arranged at bottom.
After reaction 3-7 hour, the feed postition of entrainer is preferably and point joins for 5-7 time in reaction solution, and the adjacent timed interval added for twice is 1.1-2.5 hour, and relative to the triglycol of 1 mole during reaction beginning, each add-on of entrainer is 60-120mL.
Another mode applying entrainer is, water distilling apparatus or rectifier unit are brought into use in reaction, under distillation or rectifying condition after transesterification reaction 3-7 hour, entrainer Continuous Flow under distillation or rectifying condition is added in reaction solution, the triglycol of 1 mole when starting relative to reaction, flow acceleration is 20-180mL/ hour, and it is 5-7 hour that stream adds the time.
What those skilled in the art should understand that is, gradation adds fashionable, when adding entrainer, can not lower the temperature, also the temperature of reaction solution can be cooled under the boiling point of entrainer, then add entrainer, under the boiling point being preferably cooled to entrainer in laboratory, time needed for general cooling is no more than half an hour, preferred 0.1-0.5 hour; The Continuous Flow added-time, carry out between the boiling point of the azeotrope that the alcohol that temperature of reaction should control to generate at the boiling point of entrainer and entrainer and reaction is formed, flow acceleration can regulate according to the kind of speed of response, entrainer and consumption, and the mode that entrainer Continuous Flow under distillation or rectifying condition is added to reaction solution is applicable to scale operation.
In the present invention, entrainer is preferably the aromatic hydrocarbon solvent that boiling point is 80-145 DEG C, is more preferably one or more in dimethylbenzene, toluene and benzene; More preferably toluene.
The boiling point of benzoic ether PhCOOR is higher than the boiling point of alcohol HOR, and structural formula is that the triglycol of (II) and the transesterification reaction of benzoic ether PhCOOR also can distilled or react under rectifying condition, to remove the alcohol HOR of generation in reaction simultaneously.
In the present invention, the amount of reactant is preferably, at least 2 times of the mole number of benzoic ether PhCOOR to be structural formula the be mole number of the triglycol of (II); Be more preferably, structural formula is the triglycol of (II) and the mol ratio of benzoic ether PhCOOR is 1:2-10; More preferably, structural formula is the triglycol of (II) and the mol ratio of benzoic ether PhCOOR is 1:4-5.It will be understood by those skilled in the art that the mole dosage along with benzoic ether increases, speed of response is accelerated, and yield improves, but also affects product separation.
The kind of the present invention to the catalyzer containing Anhydrous potassium carbonate is not particularly limited, as long as just can realize goal of the invention containing Anhydrous potassium carbonate in catalyzer, as Anhydrous potassium carbonate can use with the form loading to carrier.Preferably, described catalyzer is the loaded catalyst (namely catalytic active component is Anhydrous potassium carbonate) that Anhydrous potassium carbonate itself or Anhydrous potassium carbonate load are formed on inorganic refractory metal oxide carrier.When described catalyzer be Anhydrous potassium carbonate load at the loaded catalyst that inorganic refractory metal oxide carrier is formed time, with the gross weight of this catalyzer for benchmark, the content of described Anhydrous potassium carbonate is 5-95%, and the content of preferred Anhydrous potassium carbonate is 10-30%.In the present invention, described inorganic refractory metal oxide carrier can be aluminum oxide, molecular sieve or zirconium white.No matter use the catalyzer of which kind of form, be all preferably, structural formula is that in the triglycol of (II) and catalyzer, the mol ratio of contained Anhydrous potassium carbonate is 1:0.001-0.5; Be more preferably, structural formula is that in the triglycol of (II) and catalyzer, the mol ratio of contained Anhydrous potassium carbonate is 1:0.01-0.2.It will be understood by those skilled in the art that the consumption along with catalyzer increases, speed of response is accelerated, but also affects product separation.
In the present invention, the temperature of reaction is preferably 65-160 DEG C, more preferably 65-120 DEG C.In laboratory operation, the temperature of reaction solution is along with the boiling point bp65 DEG C removing the lower boiling by-product alcohol HOR(such as methyl alcohol that dereaction generates in reaction process) and increase.In laboratory, adopt conventional glass flask as reactor, with water-bath or oil bath as the thermal source of heating, when the temperature controlling water-bath or oil bath is 100-160 DEG C, when being preferably 150-160 DEG C, temperature of reaction can be made to control 65-120 DEG C of scope.In the industrial production, the temperature of water-bath or oil bath can be provided by the various known method in this area, and such as 100 DEG C provide by water vapor bath or oil bath heating, and the temperature range of 100-160 DEG C provides by pressured steam bath or oil bath heating.In the present invention, the type of heating of reaction adopts conventional heating mode, such as, can adopt the type of heating etc. of temperature-gradient method.
What those skilled in the art should understand that is, in order to obtain the triethylene glycol dibenzoate that the higher structural formula of purity is (I), the inventive method preferably also comprises after termination of the reaction, is that the triethylene glycol dibenzoate of (I) is separated from the rear gained mixture of reaction by structural formula.It is the method that the triethylene glycol dibenzoate of (I) is separated from the rear gained mixture of reaction by structural formula, comprising alcohol HOR, the catalyzer containing Anhydrous potassium carbonate, unreacted benzoic ether PhCOOR and the structural formula in reaction gained mixture is the triglycol of (II), and a small amount of intermediate product 2-(2-(2-benzoyloxyethyloxy) oxyethyl group) ethanol and impurity, remove from reaction gained mixture.For the method removed without particular requirement, the thinkable various method of those skilled in the art can be adopted, in the present invention, preferably first by the method for distillation or rectifying, the alcohol HOR of reaction generation is removed from reaction gained mixture, again by filtering, catalyzer containing Anhydrous potassium carbonate removes by the method for centrifugation or extraction from reaction gained mixture, finally by the method for underpressure distillation or rectification under vacuum, by the triglycol that unreacted benzoic ether PhCOOR and structural formula are (II), and a small amount of intermediate product 2-(2-(2-benzoyloxyethyloxy) oxyethyl group) ethanol and impurity, remove from reaction gained mixture.
In the present invention, R is preferably methyl.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention." skimmer " described in embodiment refers to that the Dean and Stark apparatus (DeanandStarkapparatuswithastopcockatthelowerend) of piston switch is arranged at bottom.
Embodiment 1
This embodiment is for illustration of the preparation method of triethylene glycol dibenzoate provided by the invention.
30g(0.2mol is added in the 250mL round-bottomed flask of band condenser, skimmer, agitator) triglycol (gas-chromatography content 99.2%, wherein containing 0.8% glycol ether), 108.9g(0.8mol) methyl benzoate, 5.5g(0.04mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 2.1 hours, add 12mL at every turn, react 2 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 6 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, again by filtrate under 667Pa at 68 DEG C underpressure distillation remove unreacted methyl benzoate and other impurity, obtain triethylene glycol dibenzoate 69.5g, yield 97%, analyze through gas chromatography-mass spectrography (GC-MS), containing 2.2% diethylene glycol dibenzoate in purity 97.4%(product gas phase chromatogram).The results are shown in Table 1.
MS（EI，m/z）：179（M-179）
+，150，149（M-209）
+，131，122，114，105，77，51。
IR（cm
-1）:3063,2951,2874,1720,1602,1584,1491,1452,1315,1275,1177,1111，1071,1028,712。
1HNMR（CDCl
3/TMS,300MHZ）（δppm）:3.726（s,4H,2CH
2OCH
2CH
2OCOC
6H
5）,3.824-3.856（m,4H,2CH
2OCH
2CH
2OCOC
6H
5）,4.450-4.482（m,4H,2CH
2OCH
2CH
2OCOC
6H
5）,7.394-7.447（m,4H,2C
6H
5）,7.517-7.571（m,2H,2C
6H
5）,8.040-8.067（m,4H,2C
6H
5）。
Embodiment 2
This embodiment is for illustration of the preparation method of triethylene glycol dibenzoate provided by the invention.
22.53g(0.15mol is added in the 150mL single port flask of band condenser, skimmer, agitator) triglycol (gas-chromatography content 99.2%, wherein containing 0.8% glycol ether), 81.69g(0.6mol) methyl benzoate, 2.07g(0.015mol) Anhydrous potassium carbonate, the oil bath of contact single port flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, dimethylbenzene is added in single port flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 2.1 hours, add 12mL at every turn, after adding dimethylbenzene, the oil bath of contact single port flask is heated to 170 DEG C at every turn, react 2 hours and dimethylbenzene and azeotrope distilled out single port flask simultaneously, question response liquid cooling but adds dimethylbenzene next time after about 6 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in single port flask after reaction terminates, again by filtrate under 520Pa at 66 DEG C underpressure distillation remove unreacted methyl benzoate and other impurity, obtain triethylene glycol dibenzoate 53g, yield 99%, analyze through gas chromatography-mass spectrography (GC-MS), containing 2.1% diethylene glycol dibenzoate in purity 96.6%(product gas phase chromatogram).The results are shown in Table 1.
Embodiment 3
This embodiment loads to Anhydrous potassium carbonate the method that alumina catalyst support makes catalyzer prepare triethylene glycol dibenzoate for illustration of provided by the invention.
(1) Anhydrous potassium carbonate loads to the preparation of the catalyzer of aluminum oxide
By stand-by for neutral alumina roasting 4 hours at 550 DEG C.By Anhydrous potassium carbonate 105 DEG C of air dry oven inner dryings 3 hours, the Anhydrous potassium carbonate getting 6g drying is dissolved in 40mL deionized water, adds 24g neutral alumina after fully dissolving, after fully stirring static 24 hours.Mixture is put into furnace pot evaporating water, then put into air dry oven at 105 DEG C dry 24 hours.By the roasting 5 hours at 600 DEG C in retort furnace of gained solid, obtain the catalyst fines 28.89g that Anhydrous potassium carbonate loads to aluminum oxide.
(2) preparation of triethylene glycol dibenzoate
22.53g(0.15mol is added in the 150mL round-bottomed flask of band condenser, skimmer, agitator) triglycol (gas-chromatography content 99.2%, wherein containing 0.8% glycol ether), 81.69g(0.6mol) methyl benzoate, the obtained Anhydrous potassium carbonate load of the present embodiment step (1) on neutral alumina catalyst fines 4.15g(be about 0.006mol containing Anhydrous potassium carbonate), the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 1.5 hours, add 12mL at every turn, react 1 hour after adding toluene at every turn and benzene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 30 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, again by filtrate under 260Pa at 63 DEG C underpressure distillation remove unreacted methyl benzoate and other impurity, obtain triethylene glycol dibenzoate 50.86g, yield 95%, analyze through gas chromatography-mass spectrography (GC-MS), containing 2.2% diethylene glycol dibenzoate in purity 81%(product gas phase chromatogram).The results are shown in Table 1.
Embodiment 4
This embodiment is for illustration of the preparation method of triethylene glycol dibenzoate provided by the invention.
30g(0.2mol is added in the 250mL round-bottomed flask of band condenser, skimmer, agitator) triglycol (gas-chromatography content 99.2%, wherein containing 0.8% glycol ether), , 68.1g(0.5mol) methyl benzoate, 5.5g(0.04mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 145 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 3 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 2.1 hours, add 12mL at every turn, react 2 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 6 minutes again.After reaction terminates, flask is cooled.Cross and filter Anhydrous potassium carbonate, again by the filtrate decompression distillation most of unreacted methyl benzoate of removing and other impurity, obtain triethylene glycol dibenzoate 61.9g, yield 86%, analyze through gas chromatography-mass spectrography (GC-MS), containing 1.8% diethylene glycol dibenzoate in purity 95.3%(product gas phase chromatogram).The results are shown in Table 1.
MS（EI，m/z）：179（M-179）
+，150，149（M-209）
+，131，122，114，105，77，51。
Embodiment 5
This embodiment is for illustration of the preparation method of triethylene glycol dibenzoate provided by the invention.
22.53g(0.15mol is added in the 250mL round-bottomed flask of band condenser, skimmer, agitator) triglycol (gas-chromatography content 99.2%, wherein containing 0.8% glycol ether), 90.11g(0.6mol) ethyl benzoate, 5.5g(0.03mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 5 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 1.5 hours, add 12mL at every turn, react 1.4 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 6 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, again by filtrate under 230Pa at 68 DEG C underpressure distillation remove unreacted ethyl benzoate and other impurity, obtain triethylene glycol dibenzoate 52.9g, yield 98%, analyze through gas chromatography-mass spectrography (GC-MS), containing 2.3% diethylene glycol dibenzoate in purity 96.1%(product gas phase chromatogram).The results are shown in Table 1.
Table 1
* note: by the percentage calculation of actual output and theoretical yield
As can be seen from Table 1, the triethylene glycol dibenzoate yield adopting the inventive method obtained is higher, and purity is higher, is conducive to environment protection.
Embodiment 1 and embodiment 4 are compared and can find out, increases the molar feed ratio of methyl benzoate and triglycol, and extend the reaction times before adding toluene, be conducive to the preparation of triethylene glycol dibenzoate.
To sum up, the preparation method of triethylene glycol dibenzoate provided by the invention is conducive to environment protection, is suitable for large-scale commercial production; Product and reactant and catalyzer easily separated, yield is high, and purity is good.The inventive method safety, environmental protection, can be widely used in industrial production.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a structural formula is the preparation method of the triethylene glycol dibenzoate of (I), it is characterized in that, described method comprises in the presence of a catalyst, be that triglycol and the benzoic ether PhCOOR of (II) reacts by structural formula, generate that to comprise structural formula be the triethylene glycol dibenzoate of (I) and the product of corresponding alcohol HOR; Described catalyzer is Anhydrous potassium carbonate; In reaction solution, the entrainer of alcohol HOR is added after 3-7 hour in reaction, and further by the alcohol HOR that distillation generates except dereaction;
Wherein, described entrainer divides and joins for 5-7 time in reaction solution, and the adjacent timed interval added for twice is 1.1-2.5 hour, the triglycol of 1 mole when starting relative to reaction, and each add-on of entrainer is 60-120mL;
Wherein, R is methyl or ethyl.
2. method according to claim 1, wherein, described distillation is rectifying, and described distillation condition is rectifying condition.
3. method according to claim 1 and 2, wherein, described entrainer be selected from dimethylbenzene, toluene and benzene one or more.
4. method according to claim 1 and 2, wherein, described structural formula is the triglycol of (II) and the mol ratio of described benzoic ether PhCOOR is 1:2-10.
5. method according to claim 4, wherein, described structural formula is the triglycol of (II) and the mol ratio of described benzoic ether PhCOOR is 1:4-5.
6. method according to claim 1 and 2, wherein, the form that described catalyzer loads to aluminum oxide with Anhydrous potassium carbonate uses.
7. method according to claim 6, wherein, described structural formula is the triglycol of (II) and the mol ratio of described Anhydrous potassium carbonate is 1:0.001-0.5.
8. method according to claim 7, wherein, described structural formula is the triglycol of (II) and the mol ratio of described Anhydrous potassium carbonate is 1:0.01-0.2.
9. method according to claim 1 and 2, wherein, the temperature of described reaction is 65-160 DEG C.
10. method according to claim 1 and 2, wherein, described method also comprises after termination of the reaction, is that the triethylene glycol dibenzoate of (I) is separated from the rear gained mixture of reaction by structural formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210193726.2A CN103483198B (en) | 2012-06-12 | 2012-06-12 | A kind of preparation method of triethylene glycol dibenzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210193726.2A CN103483198B (en) | 2012-06-12 | 2012-06-12 | A kind of preparation method of triethylene glycol dibenzoate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103483198A CN103483198A (en) | 2014-01-01 |
| CN103483198B true CN103483198B (en) | 2015-11-25 |
Family
ID=49823855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210193726.2A Active CN103483198B (en) | 2012-06-12 | 2012-06-12 | A kind of preparation method of triethylene glycol dibenzoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103483198B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4112240A (en) * | 1973-09-15 | 1978-09-05 | Dynamit Nobel Aktiengesellschaft | Process for the manufacture of light colored dipropyleneglycol dibenzoate |
| CN1199042A (en) * | 1997-05-10 | 1998-11-18 | 许绍东 | Process for preparation of emtrol benzoate plasticizer |
| CN101155772A (en) * | 2005-04-12 | 2008-04-02 | Lg化学株式会社 | Triethylene glycol ester-based plasticizer composition for polyvinyl chloride resin and preparation method thereof |
-
2012
- 2012-06-12 CN CN201210193726.2A patent/CN103483198B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4112240A (en) * | 1973-09-15 | 1978-09-05 | Dynamit Nobel Aktiengesellschaft | Process for the manufacture of light colored dipropyleneglycol dibenzoate |
| CN1199042A (en) * | 1997-05-10 | 1998-11-18 | 许绍东 | Process for preparation of emtrol benzoate plasticizer |
| CN101155772A (en) * | 2005-04-12 | 2008-04-02 | Lg化学株式会社 | Triethylene glycol ester-based plasticizer composition for polyvinyl chloride resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103483198A (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103819337B (en) | A kind of trifunctional pentaerythritol acrylate preparation method | |
| CN102229529B (en) | Preparation method of (methyl) crylic acid phenylethanol ester compounds | |
| CN102329233B (en) | Method for catalytically synthesizing diisooctyl terephthalate under action of ionic liquid | |
| CN103360243B (en) | Preparation method of 1,3-diacyloxy dimethylmethane compound | |
| CN103664620B (en) | The preparation method of a kind of bis--terephthalate | |
| CN104513161A (en) | Preparation method of pentaerythritol tetraacrylate mixture | |
| CN104045555B (en) | A kind of preparation method of triglycol dicarboxylic ester | |
| CN103483198B (en) | A kind of preparation method of triethylene glycol dibenzoate | |
| JP6006801B2 (en) | Method for producing hydroxyalkyl acrylate | |
| KR102017925B1 (en) | Method for the production of 2-octyl acrylate by means of transesterification | |
| CN101092357B (en) | Potassium hydrogen sulfate catalyzes the method for synthesizing dibasic carboxylic acid ester | |
| JP5516090B2 (en) | Method for producing hydroxyalkyl (meth) acrylic acid ester | |
| JPH10139700A (en) | Production of 1,1-bis (chloromethyl)-1 hydroxymethylpropane and 1-mono(chloromethyl)-1,1-bis (hydroxymethyl) propane | |
| CN103588640B (en) | A kind of preparation method of glycol ether dicarboxylic ester | |
| CN102795976A (en) | Method for preparing diethoxymethane by using active carbon supported solid acid catalyst | |
| CN103483197B (en) | Preparation method of diethylene glycol dibenzoate | |
| CN104230705A (en) | Preparation method for pentaerythritol tetracarboxylate | |
| WO2014035240A1 (en) | Ester formation | |
| JPWO2013180210A1 (en) | Hydroxyalkyl (meth) acrylate and method for producing the same | |
| CN116332763A (en) | Method for co-producing propylene glycol by catalyzing and synthesizing dimethyl carbonate by using supported ionic liquid | |
| JP6899420B2 (en) | o-Phenylphenoxyalkyl acrylate and its production method | |
| CN105481691A (en) | Methacrylic acid dicyclopentenyl oxygen-ethyl ester synthetic method | |
| CN101863782A (en) | Synthetic method of ultraviolet photoinitiator p-dimethylaminobenzoic acid ester compound | |
| CN111153794A (en) | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst | |
| JP2018135285A (en) | Method for producing 2-methyl-2-hydroxy-1-propyl (meth)acrylate and/or 3-methyl-3-hydroxy-1-butyl(meth)acrylate and composition comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |