CN101880226A - Synthetic method for dihydric alcohol-isomeric tridecanol diester - Google Patents
Synthetic method for dihydric alcohol-isomeric tridecanol diester Download PDFInfo
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- CN101880226A CN101880226A CN2010102016133A CN201010201613A CN101880226A CN 101880226 A CN101880226 A CN 101880226A CN 2010102016133 A CN2010102016133 A CN 2010102016133A CN 201010201613 A CN201010201613 A CN 201010201613A CN 101880226 A CN101880226 A CN 101880226A
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- dibasic
- isomerous tridecanol
- dibasic alcohol
- synthetic method
- acid esters
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Abstract
The invention discloses a synthetic method for dihydric alcohol-isomeric tridecanol diester, comprising the following steps of: adding a dihydric alcohol, a diacid monomer containing carboxyl and a dehydrant and a catalyst in a reaction container for esterification to obtain an esterified substance; then cooling the esterified substance to a temperature below 45 DEG C; adding the isomeric tridecanol in the cooled esterified substance, adding the dehydrant and the catalyst, then raising the temperature for reflux, gradually raising the temperature to 120-190 DEG C; maintaining the temperature 1-2 hours, measuring hydroxyl value in the process of temperature maintaining reaction till the hydroxyl is fully reacted; cooling to a temperature below 45 DEG C to obtain the diester, wherein the mol ratio of the isomeric tridecanol to the diacid monomer containing carboxyl to the dihydric alcohol is 1-1.1:1:0.5-0.495. The invention has the advantages of less steps, simple operation, easy implementation of industrialized production, low investment and high economy and feasibility. Because the compound catalyst is adopted, therefore, the yield of the dihydric alcohol-isomeric tridecanol diester is increased from original 50% to 85%.
Description
Technical field
The present invention relates to fine chemical technology, be specifically related to the synthetic method of a kind of dibasic alcohol-isomerous tridecanol dibasic acid esters.
Background technology
Along with the growing tension of the energy and increasingly sharpening of environmental issue, the Water-borne modification problem of needed acrylic resin of all industries such as weaving, leather, packing, coating, printing ink and auxiliary agent is urgent day by day.But cause producing because of a large amount of hydrophilic surfactant actives' utilization in the aqueous product, bring a large amount of foams in the process such as use, foamy exists to producing and use has brought a large amount of harm, and special defoamer improves with regard to needing some performances for this.
Be that main defoamer kind is more about organosilicon type, polyether-type function monomer in the market, but with isomery alcohol-binary alcohol esters is that the monomeric defoamer kind of major function is few, because of singularity, its property as the function raw material of defoamer of isomery alcohol structure is that polyethers, organosilicon etc. are not replaced.The objective of the invention is to improve market product, for water-based defoamer product provides special functional type raw material.
Summary of the invention
Goal of the invention: at the deficiencies in the prior art, the synthetic method that the purpose of this invention is to provide simple, the easy suitability for industrialized production of a kind of technology and can improve the dibasic alcohol-isomerous tridecanol dibasic acid esters of product yield.
Technical scheme: in order to realize the foregoing invention purpose, the technical solution used in the present invention is: the synthetic method of a kind of dibasic alcohol-isomerous tridecanol dibasic acid esters may further comprise the steps:
(1) dibasic alcohol, carboxylic dicarboxylic acid monomer and dewatering agent, catalyzer are added in the reaction vessel, be warming up to reflux temperature, control return velocity then, make return velocity, progressively be warming up to 120～190 ℃ less than 1 droplet/second;
(2) insulation is 1～2 hour, surveys hydroxyl value in the insulation reaction process, and until hydroxyl value＜5, promptly hydroxyl reaction obtains carboxylate fully;
(3) carboxylate in the step (2) is cooled to below 45 ℃;
(4) with in the carboxylate after the isomerous tridecanol adding cooling, add dewatering agent, catalyzer, be warming up to reflux temperature, control return velocity then, make return velocity, progressively be warming up to 120～190 ℃ less than 1 droplet/second;
(5) insulation is 1～2 hour, surveys hydroxyl value in the insulation reaction process, and is complete until hydroxyl reaction;
(6) be cooled to and promptly get described dibasic alcohol-isomerous tridecanol dibasic acid esters below 45 ℃;
Wherein the mol ratio between isomerous tridecanol, carboxylic dicarboxylic acid monomer, the dibasic alcohol is 1～1.1: 1: 0.5～0.495; Dewatering agent and catalyst consumption are different and decide according to kind.
Described carboxylic dicarboxylic acid monomer is one or more in hexanodioic acid, maleic anhydride, the Succinic Acid.
Described dewatering agent is one or both in toluene, dimethylbenzene, the hexanaphthene.
Described catalyzer is one or more in dibutyl tin laurate (T12), the vitriol oil, tosic acid, the heteropolyacid.
Described dibasic alcohol is in 600～1000 polyether Glycols any of ethylene glycol, propylene glycol, hexylene glycol, molecular weight.
Beneficial effect: compared with prior art, step of the present invention is few, simple to operate, realize suitability for industrialized production easily, and facility investment is few, economically feasible; Owing to adopted composite catalyst, the yield that makes dibasic alcohol-isomerous tridecanol dibasic acid esters is brought up to more than 85% by original 50%.
Embodiment
The invention will be described in further detail below in conjunction with embodiment, should understand these embodiment and only be used to the present invention is described and be not used in and limit the scope of the invention.
Embodiment 1: composition of raw materials: isomerous tridecanol: 150g, Succinic Acid: 89g, composite catalyst: 0.4g+1.5g, toluene: 200g+300g, polyether glycol (PPG600): 225g; Wherein composite catalyst is the mixture of heteropolyacid and T12.
The synthetic method of a kind of dibasic alcohol of the present invention-isomerous tridecanol dibasic acid esters: in the 1000ml four-hole boiling flask, add PPG600, Succinic Acid, 200g toluene successively, warming while stirring; 75 ℃ add composite catalyst 0.4g, continue to heat up; 114 ℃ begin to reflux, be incubated 0.5 hour; 116 ℃ of less, continuation intensifications of backflow, the control return velocity makes return velocity less than 1 droplet/second; 132 ℃, be incubated 0.5 hour; 133 ℃ of continuation slowly heat up while stirring; 178 ℃ are incubated 1 hour; Measure hydroxyl value for 176 ℃; 170 ℃ of hydroxyl values are 3.3, lower the temperature; 55 ℃ add toluene 300g, isomerous tridecanol warming while stirring; 82 ℃ add composite catalyst 1.5g, continue to heat up; 117 ℃ begin to reflux, be incubated 0.5 hour; 115 ℃ of less, continuation intensifications of backflow, the control return velocity makes return velocity less than 1 droplet/second; 135 ℃, be incubated 0.5 hour; 136 ℃ of continuation slowly heat up while stirring; 181 ℃ are incubated 1 hour; Measure hydroxyl value for 185 ℃; 182 ℃ of hydroxyl values are qualified, and promptly hydroxyl value＜5 are cooled to 45 ℃ and promptly get described dibasic alcohol-isomerous tridecanol dibasic acid esters, and dibasic alcohol-isomerous tridecanol dibasic acid esters yield is 86.2%.
Embodiment 2: composition of raw materials: isomerous tridecanol: 110g, hexanodioic acid: 80g, composite catalyst: 0.3g+1.5g, dewatering agent: 200g+350g, polyether glycol (PPG1000): 274g; Wherein composite catalyst is the mixture of heteropolyacid and T12; Dewatering agent is the mixture of toluene and dimethylbenzene, toluene: the mass ratio of dimethylbenzene is 1: 1.
The synthetic method of a kind of dibasic alcohol of the present invention-isomerous tridecanol dibasic acid esters: in the 1000ml four-hole boiling flask, add PPG1000,80g hexanodioic acid, the 200g dewatering agent of 274g successively, warming while stirring; 75 ℃ add the 0.3g composite catalyst, continue to heat up; 114 ℃ begin to reflux, be incubated 0.5 hour; 116 ℃ of less, continuation intensifications of backflow, the control return velocity makes return velocity less than 1 droplet/second; 132 ℃, be incubated 0.5 hour; 133 ℃ of continuation slowly heat up while stirring; 178 ℃ are incubated 1 hour; Measure hydroxyl value for 176 ℃; 170 ℃ of hydroxyl values are qualified, and promptly hydroxyl value＜5 lower the temperature; 55 ℃ add dewatering agent 300g, isomerous tridecanol warming while stirring; 82 ℃ add the 1.5g composite catalyst, continue to heat up; 117 ℃ begin to reflux, be incubated 0.5 hour; 115 ℃ of less, continuation intensifications of backflow, the control return velocity makes return velocity less than 1 droplet/second; Be warming up to 120 ℃, be incubated 0.5 hour; 136 ℃ of continuation slowly are warming up to 190 ℃ while stirring; 190 ℃ are incubated 1 hour then; In insulating process, measure hydroxyl value; Qualified until hydroxyl value, promptly hydroxyl value＜5 are cooled to 45 ℃ and promptly get described dibasic alcohol-isomerous tridecanol dibasic acid esters, and dibasic alcohol-isomerous tridecanol dibasic acid esters yield is 85.7%.
Embodiment 3: substantially the same manner as Example 1, different is composition of raw materials: the mol ratio between isomerous tridecanol, carboxylic dicarboxylic acid monomer, the dibasic alcohol is 1.1: 1: 0.5; Wherein carboxylic dicarboxylic acid monomer is that Succinic Acid, hexanodioic acid and maleic anhydride are with arbitrary proportion blended mixture; Catalyzer is any in T12, the vitriol oil, tosic acid, the heteropolyacid; Dibasic alcohol is any in ethylene glycol, propylene glycol, the hexylene glycol, and dewatering agent is a hexanaphthene.
Embodiment 4: substantially the same manner as Example 2, different is composition of raw materials: the mol ratio between isomerous tridecanol, carboxylic dicarboxylic acid monomer, the dibasic alcohol is 1.05: 1: 0.495; Wherein carboxylic dicarboxylic acid monomer is that Succinic Acid, hexanodioic acid are with arbitrary proportion blended mixture; Catalyzer is the mixture of T12, tosic acid, heteropolyacid, and dewatering agent is a toluene.
The present invention also is applicable to the method for the synthetic dibasic acid esters of raw material such as the isomery alcohol, diprotic acid, dibasic alcohol of all hydroxyls.
Claims (5)
1. the synthetic method of dibasic alcohol-isomerous tridecanol dibasic acid esters is characterized in that, may further comprise the steps:
(1) dibasic alcohol, carboxylic dicarboxylic acid monomer and dewatering agent, catalyzer are added in the reaction vessel, be warming up to reflux temperature, control return velocity then, make return velocity, progressively be warming up to 120～190 ℃ less than 1 droplet/second;
(2) insulation is 1～2 hour, surveys hydroxyl value in the insulation reaction process, and until hydroxyl value＜5, promptly hydroxyl reaction obtains carboxylate fully;
(3) carboxylate in the step (2) is cooled to below 45 ℃;
(4) with in the carboxylate after the isomerous tridecanol adding cooling, add dewatering agent, catalyzer, be warming up to reflux temperature, control return velocity then, make return velocity, progressively be warming up to 120～190 ℃ less than 1 droplet/second;
(5) insulation is 1～2 hour, surveys hydroxyl value in the insulation reaction process, and is complete until hydroxyl reaction;
(6) be cooled to and promptly get described dibasic alcohol-isomerous tridecanol dibasic acid esters below 45 ℃;
Wherein the mol ratio between isomerous tridecanol, carboxylic dicarboxylic acid monomer, the dibasic alcohol is 1～1.1: 1: 0.5～0.495.
2. the synthetic method of dibasic alcohol according to claim 1-isomerous tridecanol dibasic acid esters is characterized in that, described carboxylic dicarboxylic acid monomer is one or more in hexanodioic acid, maleic anhydride, the Succinic Acid.
3. the synthetic method of dibasic alcohol according to claim 1-isomerous tridecanol dibasic acid esters is characterized in that, described dewatering agent is one or both in toluene, dimethylbenzene, the hexanaphthene.
4. the synthetic method of dibasic alcohol according to claim 1-isomerous tridecanol dibasic acid esters is characterized in that, described catalyzer is one or more in dibutyl tin laurate, the vitriol oil, tosic acid, the heteropolyacid.
5. the synthetic method of dibasic alcohol according to claim 1-isomerous tridecanol dibasic acid esters is characterized in that, described dibasic alcohol is in 600～1000 polyether Glycols any of ethylene glycol, propylene glycol, hexylene glycol, molecular weight.
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| CN 201010201613 CN101880226B (en) | 2010-06-13 | 2010-06-13 | Synthetic method for dihydric alcohol-isomeric tridecanol diester |
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| CN 201010201613 CN101880226B (en) | 2010-06-13 | 2010-06-13 | Synthetic method for dihydric alcohol-isomeric tridecanol diester |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2734864A (en) * | 1952-05-31 | 1956-02-14 | Stabilized lubricating compositions | |
| WO1994021757A1 (en) * | 1993-03-22 | 1994-09-29 | Akzo Nobel N.V. | High-viscous lubricant copolymer compatible with non-polar base fluids |
| CN1244520A (en) * | 1999-08-08 | 2000-02-16 | 浙江皇马化工集团有限公司 | Synthesis of isotridecyl fatty ester |
| US6153783A (en) * | 2000-01-06 | 2000-11-28 | Cognis Corporation | Method for preparing a difunctional aliphatic organic compound |
| CN1440378A (en) * | 2000-07-05 | 2003-09-03 | 巴斯福股份公司 | Method for producing blends of phthalic acid diesters, decanols and tridecanols |
| CN101368124A (en) * | 2008-09-05 | 2009-02-18 | 金骄特种新材料（集团）有限公司 | High viscosity dibasic acid esters oil and method of producing the same |
-
2010
- 2010-06-13 CN CN 201010201613 patent/CN101880226B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2734864A (en) * | 1952-05-31 | 1956-02-14 | Stabilized lubricating compositions | |
| WO1994021757A1 (en) * | 1993-03-22 | 1994-09-29 | Akzo Nobel N.V. | High-viscous lubricant copolymer compatible with non-polar base fluids |
| CN1244520A (en) * | 1999-08-08 | 2000-02-16 | 浙江皇马化工集团有限公司 | Synthesis of isotridecyl fatty ester |
| US6153783A (en) * | 2000-01-06 | 2000-11-28 | Cognis Corporation | Method for preparing a difunctional aliphatic organic compound |
| CN1440378A (en) * | 2000-07-05 | 2003-09-03 | 巴斯福股份公司 | Method for producing blends of phthalic acid diesters, decanols and tridecanols |
| CN101368124A (en) * | 2008-09-05 | 2009-02-18 | 金骄特种新材料（集团）有限公司 | High viscosity dibasic acid esters oil and method of producing the same |
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