CN103483198A - Preparation method of triethylene glycol dibenzoate - Google Patents
Preparation method of triethylene glycol dibenzoate Download PDFInfo
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- CN103483198A CN103483198A CN201210193726.2A CN201210193726A CN103483198A CN 103483198 A CN103483198 A CN 103483198A CN 201210193726 A CN201210193726 A CN 201210193726A CN 103483198 A CN103483198 A CN 103483198A
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- AHSGHEXYEABOKT-UHFFFAOYSA-N O=C(c1ccccc1)OCCOCCOCCOC(c1ccccc1)=O Chemical compound O=C(c1ccccc1)OCCOCCOCCOC(c1ccccc1)=O AHSGHEXYEABOKT-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention provides a preparation method of triethylene glycol dibenzoate represented by the structural formula (I). The method includes the steps: in the presence of a catalyst containing anhydrous potassium carbonate, a reaction of triethylene glycol represented by the structural formula (II) and benzoic acid ester PhCOOR is carried out, and a product including triethylene glycol dibenzoate represented by the structural formula (I) and a corresponding alcohol HOR is generated, wherein R is methyl or ethyl. The method of the invention is conducive to environmental protection; and the product has high yield and good purity.
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 the 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 the ester class, and wherein the output of phthalate (comprising DOP, DBP, BBP, DINP, DIDP, DnOP etc.) accounts for 85%.Yet, in Europe and the U.S., use phthalic ester plasticizer to be restricted, under the background of Taiwan " fluidizer " event, it will be more and more higher using the cry of non-phthalate environment-friendly plasticizer.
CN101155772B discloses a kind of preparation method for plasticizer for polyvinyl chloride component triethylene glycol dibenzoate and triglycol dicarboxylic ester.It is raw material that the method be take triglycol and carboxylic acid, under catalyst action, esterification occurs, and generates required triglycol dicarboxylic ester, and by " entrainment agent ", the water byproduct of generation is discharged to outside, to improve the transformation efficiency of triglycol.The catalyzer that this patented method is mentioned has: the metal oxides such as the metal-salts such as an acidic catalysts such as the organo-metallic such as tetra isopropyl titanate, tosic acid, calcium chloride, heteropolyacid, natural/synthetic zeolite, ion exchange resin etc.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 this patented method reaction finishes, thereby brought sewage handling problem, and thick product also to add sorbent material, filtration just can obtain required purified product after decompression dehydration.These all are unfavorable for scale operation.
Summary of the invention
The objective of the invention is in order to overcome shortcoming of the prior art, a kind of preparation method of new triethylene glycol dibenzoate is provided.
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, described method is included under the catalyzer existence containing Anhydrous potassium carbonate, structural formula is reacted with benzoic ether PhCOOR for the triglycol of (II), and generation comprises triethylene glycol dibenzoate that structural formula is (I) and the product of corresponding pure HOR;
Wherein, R is methyl or ethyl.
The preparation method of triethylene glycol dibenzoate provided by the invention, substitute phenylformic acid as acylating agent with benzoic ether PhCOOR; Substitute the carboxylic esterification catalysts such as tetra isopropyl titanate that affect quality product with the catalyzer containing Anhydrous potassium carbonate, neutralization, washing step after reaction finishes have been avoided, solved 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 are easily separated, and yield is high, and purity is good, without adding sorbent material to carry out purified product.The inventive method can be widely used in industrial production.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation 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), described method is included under the catalyzer existence containing Anhydrous potassium carbonate, structural formula is reacted with benzoic ether PhCOOR for the triglycol of (II), and generation comprises triethylene glycol dibenzoate that structural formula is (I) and the product of corresponding pure HOR;
Wherein, R is methyl or ethyl.
According to the present invention, under existing containing the catalyzer of Anhydrous potassium carbonate, the triglycol that is (II) by structural formula is reacted with benzoic ether PhCOOR, and generation comprises triethylene glycol dibenzoate that structural formula is (I) and the product of corresponding pure HOR; Wherein, R is methyl or ethyl, can realize purpose of the present invention, is beneficial to environment protection, and product and reactant and catalyzer are easily separated, and yield is high, and purity is good.But under preferable case, described transesterification reaction is included under distillation or rectifying condition is reacted, and the pure HOR of generation is removed in reaction simultaneously; Further preferred version is, reaction 3-7 hour with the rear entrainer to adding pure HOR in reaction solution, the pure HOR generated except dereaction in the mode by 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, for carrying out forward that above-mentioned preferred version can steadily be continued, reaction brings into use " skimmer " that upper end is equipped with prolong as water distilling apparatus, and described " skimmer " refers to that the Dean and Stark apparatus (Dean and Stark apparatus with a stopcock at the lower end) of piston switch is arranged at bottom.
After reaction 3-7 hour, the mode that adds of entrainer is preferably and minute 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 reacting beginning, and the each add-on of entrainer is 60-120mL.
Another mode that applies 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 is during under distillation or rectifying condition, Continuous Flow is added to reaction solution, the triglycol of 1 mole while starting with respect 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, preferably be cooled in laboratory under the boiling point of entrainer, the required time of general cooling is no more than half an hour, preferably 0.1-0.5 hour; The Continuous Flow added-time, temperature of reaction should be controlled between the boiling point of entrainer and entrainer and the boiling point that reacts the azeotrope that the alcohol that generates forms carries out, flow acceleration can be regulated according to kind and the consumption of speed of response, entrainer, 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 ℃, more preferably one or more in dimethylbenzene, toluene and benzene; Toluene more preferably.
The boiling point of benzoic ether PhCOOR is higher than the boiling point of pure HOR, and the triglycol that structural formula is (II) also can be reacted with the transesterification reaction of benzoic ether PhCOOR under distillation or rectifying condition, to remove the pure HOR of generation in reaction simultaneously.
In the present invention, the amount of reactant is preferably, at least 2 times of the mole number that the mole number of benzoic ether PhCOOR is the structural formula triglycol that is (II); More preferably, the triglycol that structural formula is (II) and the mol ratio of benzoic ether PhCOOR are 1:2-10; More preferably, the triglycol that structural formula is (II) and the mol ratio of benzoic ether PhCOOR are 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 present invention is not particularly limited the kind of the catalyzer containing Anhydrous potassium carbonate, as long as contain Anhydrous potassium carbonate in catalyzer, just can realize goal of the invention, as Anhydrous potassium carbonate can be used with the form that loads to carrier.Preferably, described catalyzer is that Anhydrous potassium carbonate itself or Anhydrous potassium carbonate load on the loaded catalyst (being that catalytic active component is Anhydrous potassium carbonate) formed on inorganic heating resisting metal oxide carrier.When described catalyzer is Anhydrous potassium carbonate while loading on the loaded catalyst that inorganic heating resisting metal oxide carrier forms, the gross weight of this catalyzer of take is benchmark, and the content of described Anhydrous potassium carbonate is 5-95%, and preferably the content of Anhydrous potassium carbonate is 10-30%.In the present invention, described inorganic heating resisting metal oxide carrier can be aluminum oxide, molecular sieve or zirconium white.No matter use the catalyzer of which kind of form, all be preferably, in the triglycol that structural formula is (II) and catalyzer, the mol ratio of contained Anhydrous potassium carbonate is 1:0.001-0.5; More preferably, in the triglycol that structural formula is (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 ℃, more preferably 65-120 ℃.In laboratory operation, the temperature of reaction solution is along with the lower boiling by-product alcohol HOR(generated except dereaction in the reaction process boiling point bp65 ℃ of methyl alcohol for example) and increase.In laboratory, adopt conventional glass flask as reactor, the thermal source with water-bath or oil bath as heating, when the temperature of controlling water-bath or oil bath is 100-160 ℃, while being preferably 150-160 ℃, can make temperature of reaction be controlled at 65-120 ℃ of scope.In industrial production, the temperature of water-bath or oil bath can provide by the various known methods in this area, for example can bathe or oil bath heats to provide by water vapor for 100 ℃, and the temperature range of 100-160 ℃ can be bathed or oil bath heats to provide by pressured steam.In the present invention, the type of heating of reaction adopts the conventional heating mode to get final product, such as the type of heating that can adopt temperature-gradient method etc.
What those skilled in the art should understand that is, for the triethylene glycol dibenzoate that to obtain structural formula that purity is higher be (I), after the inventive method preferably also is included in reaction terminating, the triethylene glycol dibenzoate that is (I) by structural formula is separated in the gained mixture from reacting.The method that the triethylene glycol dibenzoate that is (I) by structural formula is separated in the gained mixture from reacting, comprise the pure HOR in reaction gained mixture, contain the triglycol that catalyzer, unreacted benzoic ether PhCOOR and the structural formula of Anhydrous potassium carbonate are (II), and a small amount of intermediate product 2-(2-(2-benzoxy base oxethyl) oxyethyl group) ethanol and impurity are removed from reaction gained mixture.For the method for removing without particular requirement, can adopt the thinkable the whole bag of tricks of those skilled in the art, in the present invention, preferably first by the method for distillation or rectifying, will react the pure HOR generated removes from reaction gained mixture, again by filtering, the method of centrifugation or extraction will be removed containing the catalyzer of Anhydrous potassium carbonate from reaction gained mixture, finally by the method for underpressure distillation or rectification under vacuum, the triglycol that is (II) by unreacted benzoic ether PhCOOR and structural formula, and a small amount of intermediate product 2-(2-(2-benzoxy base oxethyl) oxyethyl group) ethanol and impurity, from reaction gained mixture, remove.
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.Embodiment described " skimmer " refers to that the Dean and Stark apparatus (Dean and Stark apparatus with a stopcock at the lower end) of piston switch is arranged at bottom.
Embodiment 1
This embodiment is for illustrating the preparation method of triethylene glycol dibenzoate provided by the invention.
Add 30g(0.2mol in the 250mL round-bottomed flask with 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 ℃, under 0.1MPa, react, by distillating method, the alcohol of generation is steamed to skimmer and removes simultaneously in reaction, react after 6 hours, add toluene 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, after adding toluene, reaction also distills out round-bottomed flask by toluene and azeotrope in 2 hours simultaneously at every turn, the question response liquid cooling but approximately adds toluene next time after 6 minutes again.Reaction is removed Anhydrous potassium carbonate by the mixture cold filtration in round-bottomed flask after finishing, again filtrate is removed to unreacted methyl benzoate and other impurity 68 ℃ of lower underpressure distillation under 667Pa, obtain triethylene glycol dibenzoate 69.5g, yield 97%, analyze through gas chromatography-mass spectrography (GC-MS), contain 2.2% diethylene glycol dibenzoate in purity 97.4%(product gas-chromatography).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。
1H?NMR（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 illustrating the preparation method of triethylene glycol dibenzoate provided by the invention.
Add 22.53g(0.15mol in the 150mL single port flask with 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 ℃, under 0.1MPa, react, by distillating method, the alcohol of generation is steamed to skimmer and removes simultaneously in reaction, react after 6 hours, add dimethylbenzene in the 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, add after dimethylbenzene the oil bath that will contact the single port flask to be heated to 170 ℃ at every turn, react 2 hours and dimethylbenzene and azeotrope distilled out to the single port flask simultaneously, the question response liquid cooling but approximately adds dimethylbenzene next time after 6 minutes again.Reaction is removed Anhydrous potassium carbonate by the mixture cold filtration in the single port flask after finishing, again filtrate is removed to unreacted methyl benzoate and other impurity 66 ℃ of lower underpressure distillation under 520Pa, obtain triethylene glycol dibenzoate 53g, yield 99%, analyze through gas chromatography-mass spectrography (GC-MS), contain 2.1% diethylene glycol dibenzoate in purity 96.6%(product gas-chromatography).The results are shown in Table 1.
Embodiment 3
This embodiment provided by the inventionly loads to alumina catalyst support with Anhydrous potassium carbonate and makes the method for catalyzer and prepare triethylene glycol dibenzoate for illustrating.
(1) Anhydrous potassium carbonate loads to the preparation of the catalyzer of aluminum oxide
Neutral alumina is stand-by 550 ℃ of lower roastings 4 hours.By Anhydrous potassium carbonate, 105 ℃ of air dry oven inner dryings 3 hours, the Anhydrous potassium carbonate of getting the 6g drying was dissolved in the 40mL deionized water, after fully dissolving, added the 24g neutral alumina, the last fully stirring static 24 hours.Mixture is put into to the furnace pot evaporating water, then put into air dry oven under 105 ℃ dry 24 hours.By the 600 ℃ of lower roastings 5 hours 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
Add 22.53g(0.15mol in the 150mL round-bottomed flask with condenser, skimmer, agitator) triglycol (gas-chromatography content 99.2%, wherein containing 0.8% glycol ether), 81.69g(0.6mol) methyl benzoate, the Anhydrous potassium carbonate that the present embodiment step (1) makes load on neutral alumina catalyst fines 4.15g(containing the about 0.006mol of Anhydrous potassium carbonate), the oil bath of contact round-bottomed flask is heated to 155 ℃, under 0.1MPa, react, by distillating method, the alcohol of generation is steamed to skimmer and removes simultaneously in reaction, react after 6 hours, add toluene 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, after adding toluene, reaction also distills out round-bottomed flask by benzene and azeotrope in 1 hour simultaneously at every turn, the question response liquid cooling but approximately adds toluene next time after 30 minutes again.Reaction is removed Anhydrous potassium carbonate by the mixture cold filtration in round-bottomed flask after finishing, again filtrate is removed to unreacted methyl benzoate and other impurity 63 ℃ of lower underpressure distillation under 260Pa, obtain triethylene glycol dibenzoate 50.86g, yield 95%, analyze through gas chromatography-mass spectrography (GC-MS), contain 2.2% diethylene glycol dibenzoate in purity 81%(product gas-chromatography).The results are shown in Table 1.
Embodiment 4
This embodiment is for illustrating the preparation method of triethylene glycol dibenzoate provided by the invention.
Add 30g(0.2mol in the 250mL round-bottomed flask with 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 ℃, under 0.1MPa, react, by distillating method, the alcohol of generation is steamed to skimmer and removes simultaneously in reaction, react after 3 hours, add toluene 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, after adding toluene, reaction also distills out round-bottomed flask by toluene and azeotrope in 2 hours simultaneously at every turn, the question response liquid cooling but approximately adds toluene next time after 6 minutes again.Reaction is cooling by flask after finishing.Remove by filter Anhydrous potassium carbonate, again the filtrate decompression distillation is removed to most of unreacted methyl benzoate and other impurity, obtain triethylene glycol dibenzoate 61.9g, yield 86%, analyze through gas chromatography-mass spectrography (GC-MS), contain 1.8% diethylene glycol dibenzoate in purity 95.3%(product gas-chromatography).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 illustrating the preparation method of triethylene glycol dibenzoate provided by the invention.
Add 22.53g(0.15mol in the 250mL round-bottomed flask with 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 ℃, under 0.1MPa, react, by distillating method, the alcohol of generation is steamed to skimmer and removes simultaneously in reaction, react after 5 hours, add toluene 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, after adding toluene, reaction also distills out round-bottomed flask by toluene and azeotrope in 1.4 hours simultaneously at every turn, the question response liquid cooling but approximately adds toluene next time after 6 minutes again.Reaction is removed Anhydrous potassium carbonate by the mixture cold filtration in round-bottomed flask after finishing, again filtrate is removed to unreacted ethyl benzoate and other impurity 68 ℃ of lower underpressure distillation under 230Pa, obtain triethylene glycol dibenzoate 52.9g, yield 98%, analyze through gas chromatography-mass spectrography (GC-MS), contain 2.3% diethylene glycol dibenzoate in purity 96.1%(product gas-chromatography).The results are shown in Table 1.
Table 1
* annotate: by the percentage calculation of actual output and theoretical yield
As can be seen from Table 1, the triethylene glycol dibenzoate yield that adopts the inventive method to make is higher, and purity is higher, is conducive to environment protection.
Embodiment 1 and embodiment 4 are compared and can find out, increase the molar feed ratio of methyl benzoate and triglycol, and extend and add the toluene reaction times before, 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 are easily separated, and 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, in technical conceive scope 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 characterictic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, 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 (13)
1. the preparation method of the triethylene glycol dibenzoate that a structural formula is (I), it is characterized in that, described method is included under the catalyzer existence containing Anhydrous potassium carbonate, structural formula is reacted with benzoic ether PhCOOR for the triglycol of (II), and generation comprises triethylene glycol dibenzoate that structural formula is (I) and the product of corresponding pure HOR;
Wherein, R is methyl or ethyl.
2. method according to claim 1, wherein, described reaction is carried out under distillation or rectifying condition, with the pure HOR generated except dereaction in reaction process.
3. method according to claim 2 wherein, adds the entrainer of pure HOR in reaction after 3-7 hour, and further by distillation or rectifying, removes the pure HOR that dereaction generates in reaction solution.
4. method according to claim 3, 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 while starting with respect to reaction, the each add-on of entrainer is 60-120mL.
5. according to the described method of claim 3 or 4, wherein, described entrainer is selected from one or more in dimethylbenzene, toluene and benzene.
6. according to the described method of any one in claim 1-4, wherein, the triglycol that described structural formula is (II) and the mol ratio of described benzoic ether PhCOOR are 1:2-10.
7. method according to claim 6, wherein, the triglycol that described structural formula is (II) and the mol ratio of described benzoic ether PhCOOR are 1:4-5.
8. according to the described method of any one in claim 1-4, wherein, described catalyzer is Anhydrous potassium carbonate.
9. according to the described method of any one in claim 1-4, wherein, described catalyzer is that Anhydrous potassium carbonate loads to the loaded catalyst formed on aluminum oxide.
10. method according to claim 8 or claim 9, wherein, the triglycol that described structural formula is (II) and the mol ratio of described Anhydrous potassium carbonate are 1:0.001-0.5.
11. method according to claim 10, wherein, the triglycol that described structural formula is (II) and the mol ratio of described Anhydrous potassium carbonate are 1:0.01-0.2.
12., according to the described method of any one in claim 1-4, wherein, the temperature of described reaction is 65-160 ℃.
13., according to the described method of any one in claim 1-4, wherein, after described method also is included in reaction terminating, the triethylene glycol dibenzoate that is (I) by structural formula is separated in the gained mixture from reacting.
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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 | Triethyleneglycol ester based plasticizer composition for polyvinyl chloride resin and method of preparing the same |
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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 | Triethyleneglycol ester based plasticizer composition for polyvinyl chloride resin and method of preparing the same |
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