CN1473815A - Synthesis method of propylene glycol methyl ether propionate - Google Patents
Synthesis method of propylene glycol methyl ether propionate Download PDFInfo
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- CN1473815A CN1473815A CNA031322646A CN03132264A CN1473815A CN 1473815 A CN1473815 A CN 1473815A CN A031322646 A CNA031322646 A CN A031322646A CN 03132264 A CN03132264 A CN 03132264A CN 1473815 A CN1473815 A CN 1473815A
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- propylene glycol
- monomethyl ether
- glycol monomethyl
- sulfuric acid
- ether acetate
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Abstract
The synthesis of propylene glycol methyl ether propionate includes the reaction of materials propylene glycol methyl ether and propionic acid in the molar ratio of 0.7-1.4 at 100-160 deg.c in the presence of azeotrope dewatering agent and catalyst, with the azeotrope dewatering agent being benzene, toluene, xylene or cyclohexane in the amount of 5-20 wt% of reactant material. The present invention features that the catalyst sulfuric solid superstrong acid in the amount of 0.2-5 wt% of reactant material. The catalyst is easy to prepare, stable, easy to be separated from the product and reusable and has no corrosion to apparatus. Clean production is realized.
Description
One, technical field:
The present invention relates to a kind of propylene glycol monomethyl ether acetate synthetic method, specifically is to be raw material with propylene glycol monomethyl ether and propionic acid, and under catalyzer and azeotropy dehydrant effect, direct esterification generates the synthetic method of propylene glycol monomethyl ether acetate.
Two, technical background:
Propylene glycol monomethyl ether acetate (PMP) is a kind of nontoxic, density is little, smell is light, solvency power is strong high boiling solvent.Have good solvability and relative high inclined to one side oiliness,, also can be used as synthetic resins, binding agent, printing ink, weaving and leather coloring solvent, substitute trichloroethane electronic cleaning agent and used for cosmetic solvent except that as the environmentally friendly paint thinner.The synthetic method of propylene glycol monomethyl ether acetate mainly is propylene glycol monomethyl ether and propionic acid direct esterification under the effect of catalyzer and azeotropy dehydrant both at home and abroad at present.Catalyzer is generally used an acidic catalyst, usually with mineral acid or organic acid.Mineral acid mainly contains phosphoric acid, hydrochloric acid, the vitriol oil, chlorsulfonic acid etc.; Be many generally with the vitriol oil.Organic acid mainly contains oxalic acid, tosic acid, methylsulfonic acid etc.; Generally use tosic acid.Dewatering agent mainly contains benzene,toluene,xylene, hexanaphthene etc.The branch water effect of benzene is best, but because toxicity is bigger, generally selects toluene for use.Chinese patent application prospectus CN1092060A, open day is on September 14th, 1994, catalyzer is with sulfuric acid, tosic acid, methylsulfonic acid an acidic catalyst in the synthetic method of the propylene glycol monomethyl ether acetate that discloses in the disclosure specification sheets; Wherein to have shortcoming be that selectivity is bad to sulfuric acid catalyst, causes a series of side reactions, and by product has ether, unsaturated compound, sulfuric ester, carbonyl compound etc., and reclaiming and recycle to excess raw material makes troubles; Need after the reaction reaction product is neutralized, generate vitriol, vitriol crystal grain is thin, separates trouble, and easily stifled again rectifying tower, brings more inconvenience for the industrialization continuous production; Sulfuric acid is serious to equipment corrosion again, thereby equipment requirements is higher.Though the Catalyzed by p-Toluenesulfonic Acid agent has overcome the bad shortcoming of sulfuric acid catalyst selectivity, also exist and the difficult etching problem that reaches equipment of reactants separate.
Three, technology contents:
For overcoming above-mentioned shortcoming, the catalyzer that the object of the present invention is to provide its use of a kind of propylene glycol monomethyl ether acetate synthetic method not etching apparatus, easily separate with product, can cleaner production.
Technology contents of the present invention is: a kind of propylene glycol monomethyl ether acetate synthetic method, comprise that with propylene glycol monomethyl ether and propionic acid be raw material, temperature of reaction is at 100～160 ℃, and in the presence of azeotropy dehydrant, catalyzer, temperature of reaction is carried out direct esterification synthesizing propylene glycol monomethyl ether propionic ester for 100～160 ℃; The mole proportioning of propylene glycol monomethyl ether and propionic acid is 0.7～1.4; Azeotropy dehydrant is benzene,toluene,xylene, hexanaphthene, and the azeotropy dehydrant consumption is 5～20% of a reaction mass total mass, it is characterized by: catalyzer is sulfuric acid solid super-strong acid SO
4 2-/ TiO
2NM
xO
y, M=Zr, Si, Al, n=0～1, sulfuric acid solid super-strong acid consumption is 0.2～5% of a reaction mass total mass.
In a preferred method of the invention, suitable temperature of reaction is at 120～160 ℃, and optimal reaction temperature is 130～150 ℃; The suitable mole proportioning of propylene glycol monomethyl ether and propionic acid is 0.8～1.2, the mole proportioning of propylene glycol monomethyl ether and propionic acid the best is 1.1～1.2, also be excessive 10～20% (mol ratios) of propylene glycol monomethyl ether, the mole proportioning of propylene glycol monomethyl ether and propionic acid is excessive or too small, except to react influential, rectifying load to product brings burden, and energy consumption increases; The preferred toluene of azeotropy dehydrant, suitable consumption are 6～15% of reaction mass total mass, and optimum amount is 8～10% of a reaction mass total mass; Catalyzer is with sulfuric acid solid super-strong acid SO
4 2-/ TiO
2Catalytic effect the best, the suitable consumption of catalyzer is 0.6～3% of a reaction mass total mass, optimum amount is 1～2% of a reaction mass total mass.
Sulfuric acid solid super-strong acid SO wherein
4 2-/ TiO
2The preparation method, comprise the steps:
(1), with TiCl
4In aromatic solvents such as hexanaphthene, toluene, dimethylbenzene, be made into the solution that concentration is 10%～30% (mass percent);
(2), slowly dropping ammonia is to alkalescence in the process that stirs with the solution for preparing, pH value is controlled at 8～10, makes the carrier parent;
(3), with still aging at least 24 hours of carrier parent, more after filtering with deionised water to there not being Cl
-, drying gets amorphous carrier then;
(4), with concentration be the H of 0.25～1.0mol/l
2SO
4Or (NH
4)
2SO
4Amorphous carrier was soaked 12 hours at least, then with dry again after the deionised water;
(5), 400～600 ℃ of roastings at least 3 hours.
Sulfuric acid solid super-strong acid SO
4 2-/ TiO
2M
xO
y, the preparation of M=Zr, Si, Al needs only the Na with 10～30% (mass percents)
2SiO
3, Zr (NO
3)
4Or AlCl
3The aqueous solution is added drop-wise to TiCl
410%～30% (mass percent) solution of hexanaphthene, toluene or dimethylbenzene in, the same SO of other step
4 2-/ TiO
2Preparation process.
Sulfuric acid solid super-strong acid preparation method's preferred method is in the present invention: TiCl
4Wiring solution-forming in aromatic solvent is arranged is solvent, TiCl with toluene
4Concentration 15% (mass percent) is best; Sedimentary pH value is best with pH=9; Soaking suitable soaking concentration at sulfuric acid is 0.5～1.0mol/l, and best soaking concentration is 0.75mol/l; Suitable maturing temperature is 400～500 ℃, and optimum calcination temperature is 400～450 ℃.
The catalyst activity that this method makes is better, the sealing excellent storage stability, and depositing did not influence reactive behavior in 2 months.
Can be recycled after reaction product and the catalyst separating three times, use the H of 0.75mol/l then
2SO
4Washing, immersion still can recycle after 400～450 ℃ of roastings in air, and activity of such catalysts is constant substantially.
The present invention with the advantage that propylene glycol/monomethyl ether acetate synthetic method of making catalyzer with sulfuric acid, tosic acid, methylsulfonic acid is compared institute's tool is: catalyst sulfuric acid solid super-strong acid used in the synthetic method is easy to prepare, good stability, easily separate with product, can use repeatedly, etching apparatus not can cleaner production.
Four, description of drawings:
Fig. 1 is the technical process of propylene glycol monomethyl ether acetate production process.
Five, inventive embodiments:
Further describe the present invention below in conjunction with drawings and Examples:
The propylene glycol monomethyl ether acetate esterification adopts reaction rectification technique.Propylene glycol monomethyl ether, propionic acid and azeotropy dehydrant, super acidic catalyst added in the reactor that has rectifying tower, condenser and water trap react, constantly will react the moisture that generates at cat head goes out, and azeotropy dehydrant returns and heats up in a steamer to tower, and after drainage water reached theoretical value, reaction finished.With the reaction product sedimentation, tell that catalyst recirculation is used or regeneration after recycle.Product is delivered to rectifying tower I, and dewatering agent, unreacting material are steamed, and returns to recycle, and the thick product of tower still is delivered to rectifying tower II, steams the product propylene glycol monomethyl ether acetate.The atmospheric distillation that reaction product is at first carried out, it controls still temperature less than 165 ℃, top temperature≤150 ℃, reflux ratio 1～8 steams foreshot and recycles.Remove the rectifying that the thick product behind the foreshot carries out, its control still temperature is collected reflux ratio 3～1 less than 175 ℃, 157～165 ℃ of cuts of top temperature, and product content is greater than 99.5%.
Propylene glycol monomethyl ether acetate esterification main raw material propylene glycol monomethyl ether is a technical grade in following examples, and the happy chemical industry company limited that reaches produces by Jiangyin, carries out catalyzed reaction by propylene oxide and methyl alcohol, makes by rectifying, and product purity is greater than 99.0%.Propionic acid is a chemical pure, and Shanghai Ling Feng chemical reagent company limited produces, and content is greater than 99.0%.
Will be further understood that the present invention from following illustrative embodiment.In all embodiments, except that other explanation, all concentration are mass percent concentration.
Example 1:
With 40.4gTiCl
4(analytical pure, Shanghai Ling Feng chemical reagent is limited) is dissolved in the toluene (analytical pure), is made into 15% solution, and under agitation, slowly dropping ammonia (analytical pure, the Wuxi City apricot reaches the chemical plant) drips off in the 1h, and control PH=9 obtains unformed Ti (OH)
4Precipitation leaves standstill slaking 24h, and suction filtration is washed with deionized water and to be dripped to there not being Cl
-(use AgNO
3Solution check washing water do not have white precipitate), behind 110 ℃ of dry 14h, use 0.75mol/LH
2SO
4Solution soaking 12h filters, dry 2h under 110 ℃, and 450 ℃ of following roasting 3h get sulfuric acid solid super-strong acid SO
4 2-/ TiO
2, sealing is preserved standby.
Example 2:
With 40.4gTiCl
4Be dissolved in the toluene, be made into 15% solution, the water glass of 13.2g (analytical pure, Shanghai anticipate for a long time chemical reagent limited) is made into 15% solution.Earlier under agitation slowly sodium silicate solution is added drop-wise to TiCl
4Toluene solution, dropping ammonia slowly drips off in the 1h again, to PH=9, obtains amorphous precipitated thing, leaves standstill slaking 24h, and suction filtration is washed with deionized water and to be dripped to there not being Cl
-, behind 110 ℃ of dry 14h, use 1.0mol/LH
2SO
4Solution soaking 12h filters, 110 ℃ of following dry 2h, and 430 ℃ of following roasting 3h get sulfuric acid solid super-strong acid SO
4 2-/ TiO
2-SiO
2, sealing is preserved.
Example 3:
Having water trap, returning in the 500ml there-necked flask heat up in a steamer condenser φ 20 * 1000 packing towers and add propylene glycol monomethyl ether 200g respectively, propionic acid 150g, the sulfuric acid solid super-strong acid SO that example 1 newly makes
4 2-/ TiO
22.1g, toluene 28g, 130～150 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 5.5h gets thick product 323g, the reaction product gas chromatographic analysis, propylene glycol monomethyl ether acetate content is 64.5% in the reaction system, and propylene glycol monomethyl ether acetate one way esterification yield is 70.4%.
Example 4:
Having water trap, returning in the 500ml there-necked flask heat up in a steamer condenser φ 20 * 1000 packing towers and add propylene glycol monomethyl ether 200g respectively, propionic acid 150g, the sulfuric acid solid super-strong acid SO that example 2 newly makes
4 2-/ TiO
2SiO
22.1g, toluene 28g, 135～146 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, reaction 5.0h gets thick product 331g, propylene glycol monomethyl ether acetate content is 57.2% in the gas chromatographic analysis reaction system, and propylene glycol monomethyl ether acetate one way esterification yield is 64.0%.
Example 5:
Having water trap, returning in the 500ml there-necked flask heat up in a steamer condenser φ 20 * 1000 packing towers and add propylene glycol monomethyl ether 200g respectively, propionic acid 150g, the sulfuric acid solid super-strong acid SO that example 1 newly makes
4 2-/ TiO
25.0g, toluene 28g, 135～155 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 5.5h gets thick product 324g, the reaction product gas chromatographic analysis, propylene glycol monomethyl ether acetate content is 74.6% in the reaction system, and propylene glycol monomethyl ether acetate one way esterification yield is 81.8%.
Example 6:
Having water trap, returning in the 500ml there-necked flask heat up in a steamer condenser φ 20 * 1000 packing towers and add propylene glycol monomethyl ether 200g respectively, propionic acid 150g, the sulfuric acid solid super-strong acid SO that example 1 newly makes
4 2-/ TiO
25.0g, benzene 52g, 115～125 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 5.5h gets thick product 376.5g, the reaction product gas chromatographic analysis, propylene glycol monomethyl ether acetate content is 59.0% in the reaction system, and propylene glycol monomethyl ether acetate one way esterification yield is 75.0%.
Example 7:
Having water trap, returning in the 500ml there-necked flask heat up in a steamer condenser φ 20 * 1000 packing towers and add propylene glycol monomethyl ether 200g respectively, propionic acid 150g, the sulfuric acid solid super-strong acid SO that example 1 newly makes
4 2-/ TiO
25.6g, toluene 28g, 130～155 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 5.5h gets thick product 331.3g, the reaction product gas chromatographic analysis, propylene glycol monomethyl ether acetate content is 76.9% in the reaction system, and propylene glycol monomethyl ether acetate one way esterification yield is 83.5%.
Example 8:
Having water trap, returning in the 1000ml there-necked flask heat up in a steamer condenser φ 20 * 1000 packing towers and add propylene glycol monomethyl ether 400g respectively, propionic acid 300g, the sulfuric acid solid super-strong acid SO that example 1 newly makes
4 2-/ TiO
210g, toluene 60g, 130～150 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, reaction 5.5h gets thick product 668.5g, propylene glycol monomethyl ether acetate content is 80.4% in the gas chromatographic analysis reaction system, and propylene glycol monomethyl ether acetate one way esterification yield is 90.8%.
Example 9:
Add propylene glycol monomethyl ether 400g respectively in the 1000ml there-necked flask of φ 20 * 1000 packing towers that have water trap, propionic acid 300g stores the sulfuric acid solid super-strong acid SO that 2 months examples 1 make
4 2-/ TiO
210g, toluene 60g, 130～150 ℃ of control reaction temperature keep reactant to be in boiling state all the time, and reaction 6.5h gets thick product 655g, and product is 81.6% with gas chromatographic analysis propylene glycol monomethyl ether acetate content, its table composed as follows:
Propylene glycol monomethyl ether acetate one way esterification yield is 91.9%.
| Form | Water | Propionic acid | Propylene glycol monomethyl ether | Toluene | Propylene glycol monomethyl ether acetate |
| Content (%) | ????0.4 | ????1.0 | ????7.2 | ????9.7 | ?????81.6 |
Example 10:
In the 500ml there-necked flask of φ 20 * 1000 packing towers that have water trap, add propylene glycol monomethyl ether 200g respectively, propionic acid 150g, reclaim and regenerated sulfuric acid solid super-strong acid SO example 9 reaction backs
4 2-/ TiO
25.0g, toluene 35g, 130～150 ℃ of control reaction temperature keep reactant to be in boiling state all the time, and reaction 4.5h gets thick product 341g, gas chromatographic analysis reaction system table composed as follows:
Propylene glycol monomethyl ether acetate one way esterification yield is 77.5%.
| Form | Water | Propionic acid | Propylene glycol monomethyl ether | Toluene | Propylene glycol monomethyl ether acetate |
| Content (%) | ??1.1 | ??6.0 | ????15.3 | ????10.2 | ??????67.3 |
Claims (10)
1, a kind of propylene glycol monomethyl ether acetate synthetic method comprises that with propylene glycol monomethyl ether and propionic acid be raw material, and in the presence of azeotropy dehydrant, catalyzer, temperature of reaction is carried out direct esterification synthesizing propylene glycol monomethyl ether propionic ester for 100～160 ℃; The mole proportioning of propylene glycol monomethyl ether and propionic acid is 0.7～1.4; Azeotropy dehydrant is benzene,toluene,xylene, hexanaphthene, and the dewatering agent consumption is 5～20% of a reaction mass total mass, it is characterized in that catalyzer is sulfuric acid solid super-strong acid SO
4 2-/ TiO
2NM
xO
y, M=Zr, Si, Al, n=0～1, sulfuric acid solid super-strong acid consumption is 0.2～5% of a reaction mass total mass.
2, a kind of propylene glycol monomethyl ether acetate synthetic method according to claim 1, wherein temperature of reaction is at 120～160 ℃, the mole proportioning of propylene glycol monomethyl ether and propionic acid is 0.8～1.2, and azeotropy dehydrant is a toluene, and the dewatering agent consumption is 6～15% of a reaction mass total mass.
3, a kind of propylene glycol monomethyl ether acetate synthetic method according to claim 2, wherein temperature of reaction is at 130～150 ℃, and the mole proportioning of propylene glycol monomethyl ether and propionic acid is 1.1～1.2, and the dewatering agent consumption is 8～10% of a reaction mass total amount.
4, a kind of propylene glycol monomethyl ether acetate synthetic method according to claim 1 is characterized in that sulfuric acid solid super acid catalyst consumption is 0.6～2% of a reaction mass total mass.
5, a kind of propylene glycol monomethyl ether acetate synthetic method according to claim 4 is characterized in that sulfuric acid solid super acid catalyst consumption is 1～2% of a reaction mass total mass.
6,, it is characterized in that catalyzer is sulfuric acid solid super-strong acid SO according to claim 1,4 or 5 described a kind of propylene glycol monomethyl ether acetate synthetic methods
4 2-/ TiO
2
7, a kind of propylene glycol monomethyl ether acetate synthetic method according to claim 1 is characterized in that the preparation method of sulfuric acid solid super acid catalyst, and this method comprises the steps:
(1), with TiCl
4In aromatic solvents such as hexanaphthene, toluene, dimethylbenzene, be made into mass percent concentration and be 10%～30% solution or be 10%～30% TiCl at mass percent concentration
4Be added dropwise to the Na of mass percent concentration 10～30% in hexanaphthene, toluene or the xylene solution
2SiO
3, Zr (NO
3)
4Or AlCl
3The aqueous solution;
(2), slowly dropping ammonia is to alkalescence in the process that stirs with the solution for preparing, pH value is controlled at 8～10, makes the carrier parent;
(3), with still aging at least 24 hours of carrier parent, more after filtering with deionised water to there not being Cl
-, drying gets amorphous carrier then;
(4), with concentration be the H of 0.25～1.0mol/l
2SO
4Or (NH
4)
2SO
4Amorphous carrier was soaked 12 hours at least, then with dry again after the deionised water;
(5), 400～600 ℃ of roastings at least 3 hours.
8, a kind of propylene glycol monomethyl ether acetate synthetic method according to claim 7 is characterized in that the preparation method of sulfuric acid solid super acid catalyst, wherein TiCl
4In toluene, be made into the solution that concentration is 15% (mass percent); Sedimentary pH value is pH=9; Soak in sulfuric acid, soaking concentration is 0.5～1.0mol/l; Maturing temperature is 400～500 ℃.
9, a kind of propylene glycol monomethyl ether acetate synthetic method according to claim 8 is characterized in that the preparation method of sulfuric acid solid super acid catalyst, and wherein the soaking concentration that soaks at sulfuric acid is 0.75mol/l; Maturing temperature is 400～450 ℃.
10, a kind of propylene glycol monomethyl ether acetate synthetic method according to claim 1 is characterized in that the renovation process of sulfuric acid solid super acid catalyst, is sulfuric acid solid super acid catalyst that need regeneration the is used H with 0.75mol/l
2SO
4Washing, soak, in air in 450～450 ℃ of roastings.
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|---|---|---|---|
| CN 03132264 CN1243712C (en) | 2003-08-07 | 2003-08-07 | Synthesis method of propylene glycol methyl ether propionate |
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|---|---|---|---|
| CN 03132264 CN1243712C (en) | 2003-08-07 | 2003-08-07 | Synthesis method of propylene glycol methyl ether propionate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327956C (en) * | 2005-01-31 | 2007-07-25 | 南京工业大学 | Preparation method of solid super acidic catalyst for preparing tetraisooctyl pyromellitate by reaction of pyromellitic acid and isooctyl alcohol |
| CN102010329A (en) * | 2010-11-30 | 2011-04-13 | 江苏怡达化工有限公司 | Synthesis method for aliphatic diacid alkoxy ethyl ester or propyl ester |
| CN104549372A (en) * | 2015-01-24 | 2015-04-29 | 福州大学 | Solid super acid for catalytically synthesizing PMA (2-acetoxy-1-methoxypropane), and catalytic rectification technique and apparatus thereof |
| CN113929572A (en) * | 2021-11-11 | 2022-01-14 | 润泰新材料股份有限公司 | Method for synthesizing triethylene glycol dipropyl ester and application thereof |
-
2003
- 2003-08-07 CN CN 03132264 patent/CN1243712C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327956C (en) * | 2005-01-31 | 2007-07-25 | 南京工业大学 | Preparation method of solid super acidic catalyst for preparing tetraisooctyl pyromellitate by reaction of pyromellitic acid and isooctyl alcohol |
| CN102010329A (en) * | 2010-11-30 | 2011-04-13 | 江苏怡达化工有限公司 | Synthesis method for aliphatic diacid alkoxy ethyl ester or propyl ester |
| CN104549372A (en) * | 2015-01-24 | 2015-04-29 | 福州大学 | Solid super acid for catalytically synthesizing PMA (2-acetoxy-1-methoxypropane), and catalytic rectification technique and apparatus thereof |
| CN104549372B (en) * | 2015-01-24 | 2017-01-25 | 福州大学 | Solid super acid for catalytically synthesizing PMA (2-acetoxy-1-methoxypropane), and catalytic rectification technique and apparatus thereof |
| CN113929572A (en) * | 2021-11-11 | 2022-01-14 | 润泰新材料股份有限公司 | Method for synthesizing triethylene glycol dipropyl ester and application thereof |
| CN113929572B (en) * | 2021-11-11 | 2024-03-15 | 润泰新材料股份有限公司 | Method for synthesizing triethylene glycol dipropyl ester and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1243712C (en) | 2006-03-01 |
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Address after: Nanjing City, Jiangsu province 210037 Longpan road Xinzhuang No. 9 Patentee after: NANJING FORESTRY University Patentee after: JIANGSU YIDA CHEMICAL Co.,Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan road Xinzhuang No. 9 Patentee before: Nanjing Forestry University Patentee before: Jiangsu Yida Chemical Co.,Ltd. Address after: Nanjing City, Jiangsu province 210037 Longpan road Xinzhuang No. 9 Patentee after: NANJING FORESTRY University Patentee after: Jiangsu Yida Chemical Co.,Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan road Xinzhuang No. 9 Patentee before: Nanjing Forestry University Patentee before: Jiangyin Yida Chemical Co.,Ltd. |
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Granted publication date: 20060301 |
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| CX01 | Expiry of patent term |