CN102093212A - Synthesis method of aliphatic alkoxy oxethyl dibasic acid ethyl ester - Google Patents
Synthesis method of aliphatic alkoxy oxethyl dibasic acid ethyl ester Download PDFInfo
- Publication number
- CN102093212A CN102093212A CN2010105658796A CN201010565879A CN102093212A CN 102093212 A CN102093212 A CN 102093212A CN 2010105658796 A CN2010105658796 A CN 2010105658796A CN 201010565879 A CN201010565879 A CN 201010565879A CN 102093212 A CN102093212 A CN 102093212A
- Authority
- CN
- China
- Prior art keywords
- ethyl ester
- dibasic acid
- aliphatic dibasic
- alkoxyl group
- ethoxy ethyl
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a synthesis method of aliphatic alkoxy oxethyl dibasic acid ethyl ester, which is realized in a way that: aliphatic dibasic acid and monoalkyl ether of diethylene glycol, which are used as raw materials, are directly esterified to synthesize the aliphatic alkoxy oxethyl dibasic acid ethyl ester under the actions of a solid acid catalyst HZSM-5 or SO4<2->/TiO2 and an azeotropic dehydrating agent phenylmethane; the solid acid catalyst HZSM-5 or SO4<2->/TiO2 accounts for 0.1-10% of the total mass of the reactant alcohol acid; the mol ratio of the monoalkyl ether of diethylene glycol to the aliphatic dibasic acid is (2.0-3.0):1; and the azeotropic dehydrating agent phenylmethane accounts for 5-30 wt% of the reactants. By using the novel solid superstrong acid catalyst to synthesize the aliphatic alkoxy oxethyl dibasic acid ethyl ester, the method has the advantages of no equipment corrosion, no environmental pollution and economical reaction. The aliphatic alkoxy oxethyl dibasic acid ethyl ester product can be used as a plasticizer which has the advantages of excellent performance, low toxicity and cold resistance.
Description
Technical field
The present invention relates to the synthetic of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester, is to be raw material with aliphatic dibasic acid and Diethylene Glycol monoalky lether, under solid acid catalyst and azeotropy dehydrant effect, carries out direct esterification reaction and production process; Aliphatic dibasic acid comprises pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid etc., and the Diethylene Glycol monoalky lether comprises diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether etc.Belong to field of chemical technology.
Background technology
Aliphatic dibasic acid alkoxyl group ethoxy ethyl ester general structure:
C
mH
2m+1O(CH
2CH
2O)
2OC(CH
2)
nCO(OCH
2CH
2)
2OC
mH
2m+1
In the formula: n=3 ~ 8, m=1 ~ 4.
Aliphatic dibasic acid alkoxyl group ethoxy ethyl ester comprises following products: aliphatic dibasic acid alkoxyl group ethoxy ethyl ester comprises following products: pentanedioic acid two (methoxy ethoxy) ethyl ester, hexanodioic acid two (methoxy ethoxy) ethyl ester, nonane diacid two (methoxy ethoxy) ethyl ester, sebacic acid two (methoxy ethoxy) ethyl ester; Pentanedioic acid two (ethoxy ethoxy) ethyl ester, hexanodioic acid two (ethoxy ethoxy) ethyl ester, nonane diacid two (ethoxy ethoxy) ethyl ester, sebacic acid two (ethoxy ethoxy) ethyl ester; Pentanedioic acid two (propoxy-oxyethyl group) ethyl ester, hexanodioic acid two (propoxy-oxyethyl group) ethyl ester, nonane diacid two (propoxy-oxyethyl group) ethyl ester, sebacic acid two (propoxy-oxyethyl group) ethyl ester; Pentanedioic acid two (butoxy oxyethyl group) ethyl ester, hexanodioic acid two (butoxy oxyethyl group) ethyl ester, nonane diacid two (butoxy oxyethyl group) ethyl ester, sebacic acid two (butoxy ethoxy oxyethyl group second) ester.
Diprotic acid alkoxyl group ethoxy ethyl ester contains ehter bond and ester group functional group, is a kind of nontoxic low temperature resistant softening agent, can give goods good low-temperature pliability, also has certain light stability and water tolerance.The cold-resistant plasticizer that is used for paracril, chloroprene rubber, urethanes, acrylic elastomer isopolarity rubber also can be used as the softening agent of PVC, Vinylite, celluosic resin.The typical products characteristic is as follows:
Pentanedioic acid diethylene glycol monobutyl ether esterification formal name used at school is pentanedioic acid two (butoxy oxyethyl group) ethyl ester, relative density 1.02(25 ℃), viscosity 22mPas(25 ℃), fusing point＜-60 ℃, 144 ℃ of flash-points (opening agar diffusion method), specific refractory power 1.444(25 ℃), can be used as the softening agent of resins such as polyvinyl chloride, nitrocellulose and cellulose acetate butyrate.
Hexanodioic acid diethylene glycol monobutyl ether esterification formal name used at school is hexanodioic acid two (butoxy oxyethyl group) ethyl ester, be light amber liquid, relative density 1.010 ~ 1.015(25 ℃), 350 ℃ of boiling points (533Pa), zero pour-25 ℃, viscosity 15 ~ 25mPas(25 ℃), can be used as the softening agent of Vinylite, celluosic resin, paracril, urethanes, acrylic elastomer, thiorubber, volatility is low, and winter hardiness and good heat resistance give goods good low-temperature pliability.
Sebacic acid diethylene glycol monobutyl ether esterification formal name used at school is sebacic acid two (butoxy oxyethyl group) ethyl ester, be oily liquids, relative density 0.990(25 ℃), viscosity 27mPas(25 ℃), zero pour-6 ℃, this product is a cold-resistant plasticizer, can be used for resins such as polyvinyl chloride, vinyl chloride acetate copolymer, polyvinyl butyral acetal, polyvinyl acetate, polymethylmethacrylate, nitrocellulose, cellulose acetate butyrate.
The synthetic direct esterification method that mainly contains of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester.Directly carrying out esterification by aliphatic dibasic acid and Diethylene Glycol monoalky lether under the acid catalyst effect makes, generally use acid as the direct esterification catalyst for reaction at present, acid catalyst commonly used has protonic acids such as sulfuric acid, phosphoric acid, tosic acid, chlorsulfonic acid, thionamic acid.Thereby the effect of acid is to make hydroxyl protonization improve the reactive behavior of hydroxyl.
English Patent GB143069 report adopts tank reactor, makes catalyzer with the vitriol oil, and the distillation water-eliminating method prepares diester; Chinese patent CN200310108748.5 has reported a kind of diester softening agent and manufacture method thereof, diprotic acid and alcohol ether are under the sulfuric acid catalyst effect, under vacuum 84-97kPa, dewater, reaction product is with 10% sodium carbonate solution neutralization, washing, activated carbon decolorizing, makes target product after reclaiming excessive alcohol ether.
Sulfuric acid catalyst is easy to get, inexpensive, the catalytic activity height, but have following shortcoming: selectivity is bad, can with alcohol a series of side reaction take place because of its oxidation, dehydration, generate aldehyde, ether, sulfuric acid monoester, sulfuric acid dibasic acid esters, unsaturates and carboxylic compound, the product color is dark, the product purification complexity; Need neutralize, wash processing to reaction product, environment is had pollution; Serious to equipment corrosion; Store and use dangerous.The oxidisability of tosic acid a little less than, can prevent the heat-tinting of reaction product, also less to the corrodibility of equipment, but tosic acid still exists and problems such as product separation difficulty.
In order to overcome the deficiency of liquid protonic acid catalyzed synthesis of fatty family diester, people have carried out development research to solid acid catalyst: heteropolyacid or immobilized heteropoly acid catalysis synthesis of dibasic acid ester, the immobilized heteropolyacid of bibliographical information has: SiW
12/ SiO
2, H
3PW
12O
40There are the high problem of price in/C, heteropolyacid.Chinese patent CN200710064315.2 discloses a kind of preparation method of diester, adopt continuous process, adopt strongly acidic ion-exchange resin catalyst, but this catalyzer easily swelling, temperature tolerance are poor in acid, catalyzer is in case the surface just can't coke burning regeneration because of the carbon deposit inactivation.Chinese patent CN200910237017.8 discloses SO
4 2-/ TiO
2-SiO
2Solid super acid catalyst prepares the method for diester; Document has also been reported SO
4 2-/ Fe
2O
3, SO
4 2-/ ZrO
2– TiO
2, SO
4 2-/ TiO
2-MoO
3, SO
4 2-/ TiO
2-Al
2O
3, SO
4 2-/ Si-Zr-CLR(silicon zirconium crosslink clay), SO
4 2-/ TiO
2-Al
2O
3-SnO
2, SO
4 2-/ TiO
2-Sm
3+Deng the solid super-strong acid synthesis of dibasic acid ester.
Summary of the invention
The objective of the invention is to develop a kind of solid acid catalysis system, provide that a kind of economical in reaction, catalyzer separate with product easily, the method for the synthetic fat family diprotic acid alkoxyl group ethoxy ethyl ester of, cleanliness without any pollution little to equipment corrosion.
The object of the present invention is achieved like this: a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method, described method is to be raw material with aliphatic dibasic acid and Diethylene Glycol monoalky lether, under the effect of solid acid catalyst and methylbenzene azeotropic dewatering agent, direct esterification synthetic fat family diprotic acid alkoxyl group ethoxy ethyl ester, reaction expression is as follows:
HOOC(CH
2)
nCOOH+2C
mH
2m+1O(CH
2CH
2O)
2H===
C
mH
2m+1O(CH
2CH
2O)
2OC(CH
2)
nCO(OCH
2CH
2)
?2OC
mH
2m+1＋2H
2O
In the formula: n=3 ~ 8, m=1 ~ 4
The catalyzer that the present invention uses is HZSM-5 or SO
4 2-/ TiO
2Solid acid, this solid acid catalyst is little to equipment corrosion, can separate with product after filtration after the reaction, realizes recycling, and environmentally safe can cleaner production.The mass percent consumption of catalyzer is 0.1～10% of a reactant alkyd total mass, suitable catalyst quality per-cent consumption is 0.3～5% of a reactant alkyd total mass, and optimum catalyst quality per-cent consumption is 0.5～2% of a reactant alkyd total mass.Catalyst levels is excessive, can cause side reaction to increase; Catalyst levels is too small, causes speed of response to slow down inevitably.
The preparation method of HZSM-5 is as follows: ZSM-5 is a kind of crystalline aluminosilicate, has a series of tetrahedron skeleton structures, the Na on it
+Can with H
+Exchange; Based on ZSM-5, by with NH
4Cl or the exchange of HCl solion, washing, drying, roasting just can obtain HZSM-5.
Solid super-strong acid SO
4 2-/ TiO
2The preparation method as follows: TiCl
4With the ammoniacal liquor reaction, throw out ageing, filtration, washing are to there not being Cl
-, dry carrier TiO
2With concentration is the H of 0.25 ~ 1.0mol/L
2SO
4With TiO
2Carrier soaks, and washing, dry, 400 ~ 600 ℃ of roasting 2 ~ 5h make solid super-strong acid SO
4 2-/ TiO
2Catalyzer, airtight preservation is standby.
The reaction feed ratio that the present invention prepares aliphatic dibasic acid alkoxyl group ethoxy ethyl ester is: the Diethylene Glycol monoalky lether: the charge ratio of aliphatic dibasic acid is 2.0～3.0: 1(mol), suitable charge ratio is 2.2～2.8: 1(mol), optimum charge ratio is 2.3～2.7: 1(mol).The mole proportioning of Diethylene Glycol monoalky lether and aliphatic dibasic acid is excessive, and it is big that esterification yield can not increase the energy consumption that removes excessive Diethylene Glycol monoalky lether simultaneously; The mole proportioning of Diethylene Glycol monoalky lether and aliphatic dibasic acid is too small, and the aliphatic dibasic acid transformation efficiency is low, and aliphatic dibasic acid removes difficulty, causes quality product low.
The temperature of reaction that the present invention prepares aliphatic dibasic acid alkoxyl group ethoxy ethyl ester is 140 ~ 200 ℃, and suitable temperature of reaction is 150 ~ 190 ℃, and optimum temperature of reaction is 160 ~ 180 ℃.Temperature is low excessively, and speed of response is slow excessively, and temperature is too high, and esterification can at high temperature produce impurity and influence the quality and the color and luster of product.The reaction system remains at boiling state, and the water of telling to reaction only reaches stoichiometric number.
Azeotropy dehydrant mass percent consumption is that 5～30%(is benchmark with the reaction mass), suitable mass percent consumption is that 8～20%(is benchmark with the reaction mass), best in quality per-cent consumption is that 8～15%(is benchmark with the reaction mass).The dewatering agent consumption is lower than 5%, can not fully form azeotrope with reacting the water that forms, and causes dehydrating effect not good; The dewatering agent consumption is greater than 30%, and dehydrating effect can not increase, and reaction system also can lower temperature of reaction because of the component change and cause esterification yield to reduce, and the increasing of aftertreatment energy consumption, there is no need.
Esterification main raw material Diethylene Glycol list first (second, third, fourth) ether is technical grade, and the happy chemical industry company limited that reaches produces, and carries out catalyzed reaction by oxyethane and first (second, third, fourth) alcohol, makes by rectifying, and product purity is greater than 99.0%.
The present invention has developed the HZSM-5 and the SO42-/TiO2 solid acid catalyst of acid strong, Heat stability is good.
HZSM-5 is the micro-pore zeolite molecular sieve that has exchanged H+, belongs to the MFI structure, has 3 D pore canal, comprises a cover ten-ring straight hole road and the orthogonal with it sinusoidal ten-ring of cover duct, the aperture ovalize, and SiO2 and Al2O3 mass ratio are 25: 1 ~ 130: 1.1), the reaction product aftertreatment is simple, can save neutralization, water-washing step, simplified flow process has following characteristics as esterifying catalyst:; 2), by-product olefinic polymerization coking in the esterification, stopping up the duct is the major cause of catalyst deactivation, catalyst deactivation is after reusable after the high-temperature calcination, activation; 3), nontoxic, do not contain heavy metal ion.
Solid super acid catalyst SO42-/TiO2 is to be carrier with metal oxide TiO2, is loaded article with SO42-, and is easy to prepare, and SO42-forms stronger L acid or B acid site in the absorption of TiO2 surface coordination, the reactive behavior height, and selectivity is good; This catalyst tolerates warm nature is good, and is little to equipment corrosion, can separate with product after filtration after the reaction, can recycle, and environmentally safe can cleaner production.But have water to generate in the reaction system, the SO2-of part absorption can lose, active can the reduction.
To have water to generate in the direct esterification reaction process, to carry out in order reacting fully, by-product water need be removed; Available azeotropy dehydrant is removed by azeotropic dehydration, and after azeotrope was cooled, azeotropy dehydrant can separate from water and recycle.According to the chemical thermodynamics theory, dewatering agent can form azeotrope and take water out of reaction system with by-product water, breaks the esterification thermodynamic(al)equilibrium, and reaction is carried out to the direction that helps generating ester, has improved the esterification rate.Esterification often takes place with side reaction, adds dewatering agent and has reduced the esterification system temperature, can suppress side reaction and take place, and improves raw material availability.
The dewatering agent consumption has bigger influence to reaction, and the dewatering agent consumption does not have at least and is with the water effect preferably, and chemical equilibrium becomes controlled step in the reaction dehydration; Consumption crosses that to cause reaction temperature to be spent at most low, and chemical kinetics becomes controlled step in the reaction system; The dewatering agent consumption is many simultaneously, and energy consumption is many when removing dewatering agent.Thereby having an optimum amount, consumption is all relevant, especially closely related with catalyst system therefor with reactant species, alkyd proportioning and catalyst type etc.Azeotropy dehydrant commonly used at present mainly contains benzene, toluene, hexanaphthene etc.The branch water effect of benzene is best, but its toxicity is big, and is harmful to people's health; Hexanaphthene and water azeotropic point are low, cause temperature of reaction low, long reaction time, and reaction conversion ratio is low.They are unfavorable azeotropy dehydrants.Generally select for use toluene to make azeotropy dehydrant.
Be equipped with aliphatic dibasic acid alkoxyl group ethoxy ethyl ester for aliphatic dibasic acid and Diethylene Glycol monoalky lether direct esterification legal system, its core is to select suitable catalyzer and azeotropy dehydrant for use, determine rational reaction conditions, to improve activity, selectivity and the esterification yield of esterification.
Advantage of the present invention is: adopt novel solid super-strong acid catalyzer synthetic fat family diprotic acid alkoxyl group ethoxy ethyl ester, this technology does not have corrosion to equipment, environmentally safe, and economical in reaction is a kind of production method of new and effective, environmental protection.
Embodiment
In an embodiment, the acid number of system calculates the esterification transformation efficiency before and after the measured reaction.
Example 1:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monobutyl ether 302.6g respectively, hexanodioic acid 146.14g, HZSM-5(H38) 3g, toluene 60g, 171 ~ 180 ℃ of control reaction temperature keep reactant to be in boiling state, back flow reaction 6h all the time, divide water outlet 33.1 g, hexanodioic acid two (butoxy oxyethyl group) ethyl ester esterification yield is 98.6%.
Example 2:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monobutyl ether 276.8g respectively, sebacic acid 123.2g, HZSM-5(H38) 6g, toluene 50g, 170 ~ 180 ℃ of control reaction temperature keep reactant to be in boiling state, back flow reaction 1.5h all the time, divide water outlet 15.8 g, sebacic acid two (butoxy oxyethyl group) ethyl ester esterification yield is 73.5%.
Example 3:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monomethyl ether 256.8g respectively, nonane diacid 143.5g, HZSM-5(H25) 3g, toluene 60g, 150 ~ 170 ℃ of control reaction temperature keep reactant to be in boiling state, back flow reaction 5.5h all the time, divide water outlet 36.4g, nonane diacid two (methoxy ethoxy) ethyl ester esterification yield is 89.4%.
Example 4:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monomethyl ether 287.2g respectively, pentanedioic acid 112.8g, HZSM-5(H38) 2g, toluene 60g, 150 ~ 162 ℃ of control reaction temperature keep reactant to be in boiling state, back flow reaction 4h all the time, divide water outlet 37.4 g, pentanedioic acid two (methoxy ethoxy) ethyl ester esterification yield is 69.7%.
Example 5:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monoethyl ether 288g respectively, hexanodioic acid 112g, HZSM-5(H70) 10g, toluene 60g, control reaction temperature 131-150 ℃, keep reactant to be in boiling state, back flow reaction 1.5h all the time, divide water outlet 35.0 g, hexanodioic acid two (ethoxy ethoxy) ethyl ester esterification yield is 89.4%.
Example 6:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monoethyl ether 260g respectively, sebacic acid 140g, HZSM-5(H130) 20g, toluene 80g, control reaction temperature 140-170 ℃, keep reactant to be in boiling state, back flow reaction 6h all the time, divide water outlet 24.5g, sebacic acid two (ethoxy ethoxy) ethyl ester esterification yield is 70.3%.
Example 7:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monobutyl ether 293.9g respectively, hexanodioic acid 106.1g, the solid super-strong acid SO that newly makes
4 2-/ TiO
23g, toluene 60g, 171 ~ 180 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 4.5h divides water outlet 28.0 g, decompression removes excessive diethylene glycol monobutyl ether, refining product 400.4g, and hexanodioic acid two (butoxy oxyethyl group) ethyl ester esterification yield is 98.1%.
Example 8:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monobutyl ether 266.8g respectively, sebacic acid 133.2g, the solid super-strong acid SO that newly makes
4 2-/ TiO
23g, toluene 60g, 170 ~ 180 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 4.5h divides water outlet 24.8 g, decompression removes excessive diethylene glycol monobutyl ether, refining product 426.2g, and sebacic acid two (butoxy oxyethyl group) ethyl ester esterification yield is 96.8%.
Example 9:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monomethyl ether 245.8g respectively, nonane diacid 154.2g, the solid super-strong acid SO that newly makes
4 2-/ TiO
23g, toluene 70g, 160 ~ 176 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 4.5h divides water outlet 31.3 g, decompression removes excessive diethylene glycol monomethyl ether, refining product 419.1g, and nonane diacid two (methoxy ethoxy) ethyl ester esterification yield is 96.5%.
Example 10:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monomethyl ether 277.7g respectively, pentanedioic acid 122.3g, the solid super-strong acid SO that newly makes
4 2-/ TiO
23g, toluene 60g, 160 ~ 172 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 4.5h divides water outlet 35.3 g, decompression removes excessive diethylene glycol monomethyl ether, refining product 416.7g, and pentanedioic acid two (methoxy ethoxy) ethyl ester esterification yield is 97.5%.
Example 11:
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monoethyl ether 278.5g respectively, hexanodioic acid 121.5g, the solid super-strong acid SO that newly makes
4 2-/ TiO
23g, toluene 50g, 161 ~ 180 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 4.5h divides water outlet 31.0 g, decompression removes excessive diethylene glycol monoethyl ether, refining product 417.7g, and hexanodioic acid two (ethoxy ethoxy) ethyl ester esterification yield is 97.1%.
Example 12
In the 1000ml there-necked flask that has water trap, reflux exchanger Φ 20 * 300 packing towers, add diethylene glycol monoethyl ether 249.4g respectively, sebacic acid 150.6g, the solid super-strong acid SO that newly makes
4 2-/ TiO
23g, toluene 60g, 164 ~ 180 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, back flow reaction 4.5h divides water outlet 26.7g, decompression removes excessive diethylene glycol monoethyl ether, refining product 425.8g, and sebacic acid two (ethoxy ethoxy) ethyl ester esterification yield is 94.5%.
Claims (9)
1. aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method is characterized in that described method is is raw material with aliphatic dibasic acid and Diethylene Glycol monoalky lether, at HZSM-5 or SO
4 2-/ TiO
2Under the effect of solid acid catalyst and methylbenzene azeotropic dewatering agent, direct esterification synthetic fat family diprotic acid alkoxyl group ethoxy ethyl ester;
Described HZSM-5 is for the micro-pore zeolite molecular sieve of low silicon to middle silicon, by Na among the ZSM-5
+With H
+Exchange makes silica alumina ratio (SiO by washing, drying, roasting
2/ Al
2O
3) be 25 ~ 130: 1; SO
4 2-/ TiO
2Be solid super-strong acid, by H
2SO
4Be immersed in TiO
2On the carrier, make by washing, drying, roasting;
Described HZSM-5 or SO
4 2-/ TiO
2The mass percent consumption of solid acid catalyst is 0.1～10% of a reactant alkyd total mass;
The reaction molar ratio of described preparation aliphatic dibasic acid alkoxyl group ethoxy ethyl ester is: Diethylene Glycol monoalky lether: aliphatic dibasic acid=2.0～3.0: 1;
The temperature of reaction of described preparation aliphatic dibasic acid alkoxyl group ethoxy ethyl ester is 140 ~ 200 ℃;
Described methylbenzene azeotropic dewatering agent mass percent consumption is 5～30%, is benchmark with the reaction mass.
2. a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method according to claim 1 is characterized in that described HZSM-5 of stating or SO
4 2-/ TiO
2The mass percent consumption of solid acid catalyst is 0.3～5% of a reactant alkyd total mass.
3. a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method according to claim 2 is characterized in that described HZSM-5 or SO
4 2-/ TiO
2The mass percent consumption of solid acid catalyst is 0.5～2% of a reactant alkyd total mass.
4. according to claim 1 ~ 3 each described a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method wherein, it is characterized in that the reaction molar ratio of described preparation aliphatic dibasic acid alkoxyl group ethoxy ethyl ester is: Diethylene Glycol monoalky lether: aliphatic dibasic acid=2.2～2.8: 1.
5. a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method according to claim 4 is characterized in that the reaction molar ratio of described preparation aliphatic dibasic acid alkoxyl group ethoxy ethyl ester is: Diethylene Glycol monoalky lether: aliphatic dibasic acid=2.3～2.7: 1.
6. according to claim 1 ~ 3 each described a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method wherein, it is characterized in that the temperature of reaction of described preparation aliphatic dibasic acid alkoxyl group ethoxy ethyl ester is 150 ~ 190 ℃.
7. a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method according to claim 6 is characterized in that the temperature of reaction of described preparation aliphatic dibasic acid alkoxyl group ethoxy ethyl ester is 160 ~ 180 ℃.
8. according to claim 1 ~ 3 each described a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method wherein, it is characterized in that described methylbenzene azeotropic dewatering agent mass percent consumption is 8～20%, is benchmark with the reaction mass.
9. a kind of aliphatic dibasic acid alkoxyl group ethoxy ethyl ester synthetic method according to claim 8 is characterized in that described methylbenzene azeotropic dewatering agent mass percent consumption is 8～15%, is benchmark with the reaction mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105658796A CN102093212A (en) | 2010-11-30 | 2010-11-30 | Synthesis method of aliphatic alkoxy oxethyl dibasic acid ethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105658796A CN102093212A (en) | 2010-11-30 | 2010-11-30 | Synthesis method of aliphatic alkoxy oxethyl dibasic acid ethyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102093212A true CN102093212A (en) | 2011-06-15 |
Family
ID=44126503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105658796A Pending CN102093212A (en) | 2010-11-30 | 2010-11-30 | Synthesis method of aliphatic alkoxy oxethyl dibasic acid ethyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102093212A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351692A (en) * | 2011-10-10 | 2012-02-15 | 山东天兴生物科技有限公司 | Preparation method for dimethyl sebacate |
| CN105555854A (en) * | 2013-09-12 | 2016-05-04 | 3M创新有限公司 | Plasticized polymeric composition |
| CN105732370A (en) * | 2016-01-28 | 2016-07-06 | 江苏清泉化学股份有限公司 | Method for preparing dioctyl 1,4-cyclohexanedicarboxylate |
| CN106810716A (en) * | 2015-12-01 | 2017-06-09 | 张海飞 | A kind of castor oil acid cyclohexanediol monomethyl ether ester plasticiser and preparation method thereof |
| CN108863781A (en) * | 2018-06-12 | 2018-11-23 | 威海金泓高分子有限公司 | A kind of production method of environment-friendly plasticizer diethylene adipate |
| CN111499507A (en) * | 2020-05-25 | 2020-08-07 | 东营市金凤凰化工股份有限公司 | Production process of diethylene glycol monobutyl ether adipate |
| CN115779982A (en) * | 2022-11-02 | 2023-03-14 | 万华化学集团股份有限公司 | Preparation method and application of catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618847A (en) * | 2003-11-20 | 2005-05-25 | 上海橡胶制品研究所 | Binary acid ester plasticizer and its manufacturing method |
-
2010
- 2010-11-30 CN CN2010105658796A patent/CN102093212A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618847A (en) * | 2003-11-20 | 2005-05-25 | 上海橡胶制品研究所 | Binary acid ester plasticizer and its manufacturing method |
Non-Patent Citations (2)
| Title |
|---|
| 王存德等: "固体超强酸TiO2/SO42-催化合成己二酸酯", 《化工时刊》 * |
| 魏荣宝等: "HZSM-5分子筛催化合成己二酸酯", 《天津理工学院学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351692A (en) * | 2011-10-10 | 2012-02-15 | 山东天兴生物科技有限公司 | Preparation method for dimethyl sebacate |
| CN102351692B (en) * | 2011-10-10 | 2013-08-21 | 山东天兴生物科技有限公司 | Preparation method for dimethyl sebacate |
| CN105555854A (en) * | 2013-09-12 | 2016-05-04 | 3M创新有限公司 | Plasticized polymeric composition |
| US9828489B2 (en) | 2013-09-12 | 2017-11-28 | 3M Innovative Properties Company | Plasticized polymeric composition |
| CN105555854B (en) * | 2013-09-12 | 2018-02-06 | 3M创新有限公司 | Plasticity polymer composition |
| CN106810716A (en) * | 2015-12-01 | 2017-06-09 | 张海飞 | A kind of castor oil acid cyclohexanediol monomethyl ether ester plasticiser and preparation method thereof |
| CN105732370A (en) * | 2016-01-28 | 2016-07-06 | 江苏清泉化学股份有限公司 | Method for preparing dioctyl 1,4-cyclohexanedicarboxylate |
| CN108863781A (en) * | 2018-06-12 | 2018-11-23 | 威海金泓高分子有限公司 | A kind of production method of environment-friendly plasticizer diethylene adipate |
| CN111499507A (en) * | 2020-05-25 | 2020-08-07 | 东营市金凤凰化工股份有限公司 | Production process of diethylene glycol monobutyl ether adipate |
| CN115779982A (en) * | 2022-11-02 | 2023-03-14 | 万华化学集团股份有限公司 | Preparation method and application of catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102093212A (en) | Synthesis method of aliphatic alkoxy oxethyl dibasic acid ethyl ester | |
| CN100513521C (en) | Preparation method of biological diesel oil | |
| CN102010329A (en) | Synthesis method for aliphatic diacid alkoxy ethyl ester or propyl ester | |
| CN101822992B (en) | Catalyst for synthesis of glycerol carbonate and preparation method thereof | |
| CN101475478B (en) | Method for synthesizing ethylene glycol monobutyl ether acetate | |
| CN101722027A (en) | Esterification catalyst for synthesizing ethylene/propylene glycol ether carboxylate, and preparation method thereof | |
| US4675434A (en) | Process for producing phthalic acid esters | |
| CN102206156A (en) | Method for comprehensive recycling of crude terephthalic acid (CTA) residue | |
| CN112264090A (en) | Double-acid type ionic liquid catalyst and preparation method and application thereof | |
| CN102775310B (en) | Synthesis method of dibasic alcohol bi-benzoate | |
| CN101906209B (en) | Method for synthesizing polyethylene glycol monomethacrylate from solid superacid by catalytic esterification | |
| CN101869847B (en) | Micro-spherical polymer solid acid esterification catalyst and preparation method thereof | |
| CN111138278B (en) | Preparation method of butanediol caprylate | |
| CN102241571A (en) | Preparation method of dibutoxy methane | |
| CN102992956A (en) | Preparation method of 2-butyl alcohol | |
| CN101092357B (en) | Method for catalyzing and synthesizing bibasic carboxylic ester by potassium hydrogen sulfate | |
| CN102391490B (en) | Preparation method and application of supported titanium-series polyester catalyst | |
| CN107188804B (en) | Method for catalytically synthesizing methyl oleate by using composite phosphotungstate | |
| CN109569579B (en) | Method for preparing tributyl citrate from attapulgite clay immobilized tungsten oxide | |
| CN101391957B (en) | Method for preparing tributyl citrate by using rare-earth salt binary complex type solid acid as catalyst | |
| CN103265429A (en) | Technical method for synthesizing methyl acetate | |
| CN102492559A (en) | Method for preparing biodiesel in novel alkaline ionic liquid | |
| CN102775301B (en) | Method for synthesizing aliphatic dibasic acid alkoxy ethyl ester by using ZSM-5 molecular sieve to catalyze | |
| CN103342643B (en) | Method for preparing alkoxylated polyol acrylate | |
| CN107876037A (en) | Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110615 |