CN103467288A - Production method of 1, 2-propylene glycol diacetate - Google Patents
Production method of 1, 2-propylene glycol diacetate Download PDFInfo
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- CN103467288A CN103467288A CN2013104157553A CN201310415755A CN103467288A CN 103467288 A CN103467288 A CN 103467288A CN 2013104157553 A CN2013104157553 A CN 2013104157553A CN 201310415755 A CN201310415755 A CN 201310415755A CN 103467288 A CN103467288 A CN 103467288A
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- propylene glycol
- production method
- catalyst
- exchange resin
- diacetate esters
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Abstract
The invention provides a production method of 1, 2-propylene glycol diacetate, and relates to a chemical synthesis technology. The production method comprises the following steps of carrying out esterification reaction by using propylene glycol monomethyl ether and acetic acid as raw materials in the existence of a catalyst, and rectifying a produced 1, 2-propylene glycol diacetate crude product so as to obtain the high-quality 1, 2-propylene glycol diacetate product, wherein the catalyst is a styrene-divinyl benzenesulfonic acid type acid cation exchange resin which is modified by metal ions and has compound enhancement type macropores, and the cation exchange resin is prepared by sulfonating on a benzene ring after polymerizing styrene and a divinyl benzene monomer, and an ion is any one of Zn<2+>, Fe<3+>, Al<3+>, Na<+>, Fe<2+> or K<+>. The production method has the advantages that the adopted catalyst has high activity and long service life, the selectivity and the yield of the product are high, few byproducts are generated, and after the catalyst is inactivated, the catalyst is filtered, recovered, subjected to acid treatment and dried so as to be recycled.
Description
Technical field
The present invention relates to the chemical industry synthetic technology, particularly the production technical field of 1,2-PD diacetate esters.
Background technology
1,2-PD diacetate esters (PGDA) is a kind of important industrial solvent, and this solvent molecule structure uniqueness, have again polar group with existing non-polar group in a part, so it all has dissolving power preferably to polarity and apolar substance.It has that solubility property high (can dissolving cellulos and polymer substance), thermal stability are good, viscosity changes the characteristics such as little, that toxic is little and corrodibility is little.As the solvent that is widely used as the industry such as printing ink, paint, plastics, spices, medicine, as the solvent of conduct delaying property solvent and resol baked paint in baking finish for car.
" the Green Chemistry approach of Synthesize 1,2-Propylene Glycol Diacetate from Acetic Anhydride Inserted by Propylene Oxide " reported a kind of method with diacetyl oxide and propylene oxide synthesizing propylene glycol monomethyl ether diacetate esters in autoclave.Defect responds needs high pressure (0.4-0.6Mpa); Temperature of reaction higher (130-135 ℃); Low by reactor rhythmic reaction efficiency, yield poorly, be unfavorable for scale operation; Drip feeding mode speed slow, complex technical process.The reactant diacetyl oxide is control type medicine.
Summary of the invention
The present invention seeks to propose a kind of production method that can overcome the 1,2-PD diacetate esters of existing production technology defect that method is brought.
Under the condition that the present invention exists at catalyzer, take propylene glycol monomethyl ether and acetic acid as raw material, carry out esterification, the 1,2-PD diacetate esters crude product of production is obtained 1,2-PD diacetate esters elaboration after rectifying; It is characterized in that: described catalyzer is the metal ion-modified styrene-divinylbenzene sulfonic acid type acidic cation-exchange resin with composite enhanced macropore, described ion exchange resin with vinylbenzene and Vinylstyrene monomer polymerization and on phenyl ring sulfonation make, in monomer, the mole number of Vinylstyrene accounts for 36%～40%, add weight to account for the nm-class silicon carbonite whisker palpus of monomer total amount 3%-4%, adopt ion exchange method to carry out modification to ion exchange resin, described ion is Zn
2+, Fe
3+, Al
3+, Na
+, Fe
2+or K
+in any one.
The catalyzer that the present invention adopts is high, and the life-span is long, and product selectivity and yield are high, and by product is few.After inactivation, after filtration, recovery, acid treatment, oven dry, can reuse.
The present invention can be continuously produced 1,2-propylene-glycol diacetate (PGDA), operating method is simple, the raw material air speed is high, has significantly improved the production efficiency of 1,2-PD diacetate esters, reduce its production cost, and can reduce solid pollutant and discharge of wastewater, reaction product is neutralized without a large amount of alkali, the catalyzer long service life.There is splendid scale words industrial application value.
The temperature condition of esterification of the present invention is 115～125 ℃.For esterification, when temperature is hanged down, speed of response is low, and the yield of product is low; When temperature is high, in the easy inactivation of catalyzer, caking, product, heavy constituent content uprises.
The molar ratio of described propylene glycol monomethyl ether and acetic acid is 1:1.5～2.When feed ratio hangs down, can save material, speed of response is very fast, but the yield of reactant is low; Feed ratio is when high, and energy consumption increases.
When guaranteeing that material arrives fixed-bed reactor, temperature can reach required temperature of reaction the soonest, after the present invention first is preheated to 100 ℃ by propylene glycol monomethyl ether and acetic acid with catalyst mix.
Embodiment
One, Kaolinite Preparation of Catalyst:
1, please introduce in detail the preparation method of catalyzer:
By 732
#ion exchange resin soaks 8-12h with 4%NaOH after being washed till the outflow clear water with deionized water, then with deionized water, is washed till neutrality, then uses 5% salt acid soak 8-12h, makes H
+the type resin.Get the ZnCl that massfraction is 0.1%～10%
2, FeCl
3, AlCl
3, NaCl, FeCl
2or a kind of solution in KCl, carry out ion-exchange with ion exchange resin at a certain temperature, finally with deionized water, be washed till without Cl
-exist, be dried to constant weight in vacuum drying oven, both obtained modified ion-exchange resin catalyst.
2, the feature of catalyzer:
There is the characteristics such as metal ion, enhancement type, macropore.
Two, produce 1,2-PD diacetate esters (PGDA):
In fixed-bed reactor, mol ratio with 1:1.5～2 is mixed propylene glycol monomethyl ether and acetic acid, and is preheated to 100 ℃, then with the flow of 40L/h, passes into continuously the catalyzer of preparation, reaction system is warming up to 115～125 ℃ and carries out esterification, the air speed of reaction is 4h
-1, question response is put into dehydration tower by product after finishing and is dewatered.
Dehydration is under the existence of entrainer benzene, forms azeotropes in 64～67 ℃, and through the condensation layering, the organic phase on upper strata is returned to dehydration tower, the processing of anhydrating of the water of lower floor.Simultaneously, dehydration tower tower reactor material enters de-light.
When de-light, the tower top light constituent refluxes to return in fixed-bed reactor and proceeds esterification.De-light tower reactor material enters rectifying tower rectifying, and going out purity in tower top rectifying is the product more than 99.5%---1,2-PD diacetate esters (PGDA).
The summary sheet of the raw material that following table is the esterification reaction temperature different propylene glycol monomethyl ethers that are 120 ℃ and acetic acid feed ratio, the 1,2-PD diacetate esters (before rectifying) that esterification generates:
| Ratio | Acetic acid | Propylene glycol monomethyl ether | 1-Methoxy-2-propyl acetate | The 1,2-PD diacetate esters |
| 1:1.5 | 8.10% | 21.30% | 29.70% | 38.40% |
| 1:1.8 | 12.10% | 18.30% | 19.70% | 45.40% |
| 1:2 | 15.80% | 15.10% | 17.80% | 38.30% |
Following table is, with the molar ratio of 1:1.8, propylene glycol monomethyl ether and acetic acid mixed, before the PGDA(rectifying of carrying out obtaining after esterification under different temperature condition) summary sheet:
| Temperature (℃) | Acetic acid | Propylene glycol monomethyl ether | 1-Methoxy-2-propyl acetate | The 1,2-PD diacetate esters |
| 115 | 13.10% | 23.70% | 15.90% | 41.30% |
| 120 | 12.10% | 18.30% | 19.70% | 45.40% |
| 125 | 7.90% | 16.10% | 21.80% | 44.20% |
Claims (4)
1. the production method of a 1,2-PD diacetate esters, under the condition existed at catalyzer, take propylene glycol monomethyl ether and acetic acid as raw material, carry out esterification, 1 of production, 2-propylene-glycol diacetate crude product is obtained 1,2-PD diacetate esters elaboration after rectifying; It is characterized in that described catalyzer is the metal ion-modified styrene-divinylbenzene sulfonic acid type acidic cation-exchange resin with composite enhanced macropore, described ion exchange resin with vinylbenzene and Vinylstyrene monomer polymerization and on phenyl ring sulfonation make, in monomer, the mole number of Vinylstyrene accounts for 36%～40%, add weight to account for the nm-class silicon carbonite whisker palpus of monomer total amount 3%-4%, adopt ion exchange method to carry out modification to ion exchange resin, described ion is Zn
2+, Fe
3+, Al
3+, Na
+, Fe
2+or K
+in any one.
2. the production method of 1,2-PD diacetate esters according to claim 1, the temperature condition that it is characterized in that described esterification is 115～125 ℃.
3. according to the production method of the described 1,2-PD diacetate esters of claim 1 or 2, the molar ratio that it is characterized in that described propylene glycol monomethyl ether and acetic acid is 1:1.5～2.
4. the production method of 1,2-PD diacetate esters according to claim 1, after it is characterized in that first propylene glycol monomethyl ether and acetic acid are preheated to 100 ℃ again with catalyst mix.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104157553A CN103467288A (en) | 2013-09-13 | 2013-09-13 | Production method of 1, 2-propylene glycol diacetate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104157553A CN103467288A (en) | 2013-09-13 | 2013-09-13 | Production method of 1, 2-propylene glycol diacetate |
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| CN103467288A true CN103467288A (en) | 2013-12-25 |
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|---|---|---|---|
| CN2013104157553A Pending CN103467288A (en) | 2013-09-13 | 2013-09-13 | Production method of 1, 2-propylene glycol diacetate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417530A (en) * | 2016-05-23 | 2017-12-01 | 微宏动力系统（湖州）有限公司 | A kind of nonaqueous electrolytic solution double carboxy acid ester's compound, the nonaqueous electrolytic solution and secondary cell for including it |
| CN109206315A (en) * | 2018-08-31 | 2019-01-15 | 江苏华伦化工有限公司 | The method of separating propylene glycol acetate from propylene glycol methyl ether acetate heavy constituent |
| CN111944083A (en) * | 2019-05-14 | 2020-11-17 | 山东辰信新能源有限公司 | Preparation method of modified macroporous acidic cation exchange resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436163A (en) * | 2000-06-09 | 2003-08-13 | 国际人造丝公司 | Process for production of t-butyl acetate from MTBE |
| US20130109882A1 (en) * | 2011-10-27 | 2013-05-02 | Cpc Corporation, Taiwan | Method of Synthesizing Polyol Acetate by Using Catalyst of Ionic Liquid Heteropoly Acid |
-
2013
- 2013-09-13 CN CN2013104157553A patent/CN103467288A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436163A (en) * | 2000-06-09 | 2003-08-13 | 国际人造丝公司 | Process for production of t-butyl acetate from MTBE |
| US20130109882A1 (en) * | 2011-10-27 | 2013-05-02 | Cpc Corporation, Taiwan | Method of Synthesizing Polyol Acetate by Using Catalyst of Ionic Liquid Heteropoly Acid |
Non-Patent Citations (1)
| Title |
|---|
| 张凤 等: "ZnCl2改性离子交换树脂的制备及其催化乙醇和乙酸酯化反应性能", 《催化学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417530A (en) * | 2016-05-23 | 2017-12-01 | 微宏动力系统（湖州）有限公司 | A kind of nonaqueous electrolytic solution double carboxy acid ester's compound, the nonaqueous electrolytic solution and secondary cell for including it |
| CN109206315A (en) * | 2018-08-31 | 2019-01-15 | 江苏华伦化工有限公司 | The method of separating propylene glycol acetate from propylene glycol methyl ether acetate heavy constituent |
| CN111944083A (en) * | 2019-05-14 | 2020-11-17 | 山东辰信新能源有限公司 | Preparation method of modified macroporous acidic cation exchange resin |
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Application publication date: 20131225 |