CN1197057A - Method of preparing fatty group dibasic acid - Google Patents
Method of preparing fatty group dibasic acid Download PDFInfo
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- CN1197057A CN1197057A CN 97104061 CN97104061A CN1197057A CN 1197057 A CN1197057 A CN 1197057A CN 97104061 CN97104061 CN 97104061 CN 97104061 A CN97104061 A CN 97104061A CN 1197057 A CN1197057 A CN 1197057A
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- dibasic acid
- acid
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- aliphatic dibasic
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Abstract
A process for preparing ester of aliphatic dibasic acid is a reaction of aliphatic dibasic acid on emtrol under the existance of silica gel born heteropoly acid as catalyst, and features high selectivity (100%) and transform rate (over 97%) and easy recovery of catalyst.
Description
The present invention relates to the preparation method of fatty group dibasic acid, particularly prepare the method for fatty group dibasic acid with carried heteropoly acid catalyst.
Fatty group dibasic acid is the cold resistant plasticizer of a quasi-representative, is subjected to very big welcome because of it has good low-temperature performance.At present, produce fatty group dibasic acid both at home and abroad and generally all adopt liquid acid, as sulfuric acid or tosic acid as esterifying catalyst, although they have higher reaction conversion ratio (95-98%) to reaction system, but exist following problem, (1) have side reaction to take place in the production, target product selectivity is not high; (2) complex manufacturing needs alkali neutralization, washing etc., and the production cycle is long; (3) catalyzer heavy corrosion production unit, contaminate environment.In recent years, a kind of multifunctional novel solid super acid catalyst---heteropolyacid (HPA) and its esters obtain very big attention in catalytic field.In the esterification field, some heteropolyacid catalyst shows excellent catalytic performance, has industrialized prospect." fine chemistry industry " 1992 the 9th volumes the 1st phase 43-44 page or leaf has published with heteropoly acid catalysis and has prepared toxilic acid two different methods of defending ester, and this method is directly to mix with reactant with heteropolyacid to carry out the homogeneous esterification, and esterification yield can reach 95%; But catalyzer is difficult to separate from reaction system, is difficult to recycling, also causes the pollution of product.
The object of the present invention is to provide a kind of preparation method of fatty group dibasic acid, adopt carried heteropoly acid to make catalyzer, improve the selectivity of target product, simplify production process, and make catalyzer be easy to recycling, product is not contaminated.
Main points of the present invention:
The present invention is the preparation method of fatty group dibasic acid, is raw material with aliphatic dibasic acid and Fatty Alcohol(C12-C14 and C12-C18), and primitive reaction is an esterification.Adopt silica gel load type heteropolyacid as catalyzer, the essentially consist of this catalyzer and weight percent are:
Silica gel 70-90%
Phosphorus heteropoly tungstic acid H
3[P (W
3O
10)
4] XH
2O 5-25%
Phosphato-molybdic heteropolyacid H
7[P (Mo
2O
7)
6] XH
2Reactions steps that O 5-25% is concrete and condition are:
A, material ratio:
The mol ratio of aliphatic dibasic acid and Fatty Alcohol(C12-C14 and C12-C18) is 2.0-4.0, and catalyst consumption is the 1.5-3.5% of aliphatic dibasic acid weight;
B, reaction process process:
Catalyzer and reaction mass are joined in the conventional esterification container by material ratio given among the above-mentioned A, be heated to temperature of reaction 120-190 ℃, question response carries out getting final product in 1.5-3 hour complete reaction, with the mixture filtering recovering catalyst in the container, with filtrate decompression rectifying dealcoholysis after press filtration promptly gets product.
In reaction system, Fatty Alcohol(C12-C14 and C12-C18) can be excessive greatly as the band aqua, takes reaction product water out of reaction system, and molecular balance is moved to target product.
Above-mentioned Preparation of catalysts adopts dipping method, silica gel is joined in the mixed aqueous solution of phosphato-molybdic heteropolyacid that concentration is 0.3-2.1g/mol and phosphorus heteropoly tungstic acid, stirs 3-5h under room temperature, and heteropolyacid is immersed in the carrier; Then unnecessary water is boiled off, can take slow heating, unnecessary water is boiled off, be beneficial to heteropolyacid and in carrier, spread as heating in water bath; Sample will wet at last at 120-150 ℃ of dry 10-15h, promptly become silica gel load type heteropolyacid catalyst.
The mol ratio of above-mentioned aliphatic dibasic acid and Fatty Alcohol(C12-C14 and C12-C18) is preferably 3.4-3.8, and aliphatic dibasic acid is preferably C
6-C
10Aliphatic dibasic acid, Fatty Alcohol(C12-C14 and C12-C18) is preferably C
6-C
10Fatty Alcohol(C12-C14 and C12-C18); Catalyst consumption is preferably the 2.0-3.0% of aliphatic dibasic acid weight.
Effect of the present invention: the invention provides a kind of novel method for preparing fatty group dibasic acid, owing to adopted silica gel load type heteropolyacid catalyst, reaction conversion ratio can reach 97-99%, the selectivity of the target product of catalyzer is 100%, simplified technology, and compared as the Preparation of catalysts method with tosic acid with sulfuric acid, the production cycle reduced to about 2 hours, reduce equipment such as alkali neutralization, washing, also do not had problems such as production unit burn into discharge of wastewater, environmental pollution.And, crucial composition phosphorus tungsten, phosphato-molybdic heteropolyacid in the catalyzer, there is significant katalysis in its B acid site to esterification, after loading on the carrier securely, avoided the loss of catalytic active component, be convenient to recycle, and have long work-ing life, product is not contaminated.Product of the present invention all can be done cold resistant plasticizer and use.
The present invention is further elaborated below in conjunction with embodiment.
Embodiment 1:
Reaction mass is formed (weight part);
50 parts of hexanodioic acids
150 parts of isooctyl alcohol
1.0 parts of catalyzer
Wherein catalyzer consists of: carrier silica gel 83 (wt%), phospho-wolframic acid 11 (wt%) and phospho-molybdic acid 6 (wt%).
Various materials are added in the reaction vessel, be heated to 150 ℃ of temperature of reaction, carrying out along with reaction process, be warming up to 190 ℃ gradually, reaction was carried out 2.5 hours, to react the synthetic mixture filtering recovering catalyst then, with filtrate decompression rectifying dealcoholysis after press filtration obtains product hexanodioic acid two different hot vinegar.Reaction conversion ratio is 97.6%, target product selectivity 100%.
Embodiment 2:
Reaction mass is formed (weight part):
60 parts of nonane diacids
150 parts of isooctyl alcohol
1.4 parts of catalyzer
Wherein catalyzer consists of: carrier silica gel 85 (wt%), phospho-wolframic acid 10 (wt%) and phospho-molybdic acid 5 (wt%).
Various materials are added in the reaction vessel, be heated to 138 ℃ of temperature of reaction, carrying out along with reaction process, be warming up to 180 ℃ gradually, reaction was carried out 1.5 hours, to react the synthetic mixture filtering recovering catalyst then, with filtrate decompression rectifying dealcoholysis after press filtration obtains the product of nonane diacid di-isooctyl.Reaction conversion ratio is 98.1%, target product selectivity 100%.
Embodiment 3:
Reaction mass is formed (weight part):
65 parts of sebacic acid
150 parts of isooctyl alcohol
1.5 parts of catalyzer
Wherein catalyzer consists of: carrier silica gel 87 (wt%), phospho-wolframic acid 5 (wt%) and phospho-molybdic acid 8 (wt%).
Various materials are added in the reaction vessel, be heated to 135 ℃ of temperature of reaction, carrying out along with reaction process, be warming up to 176 ℃ gradually, reaction was carried out 2.0 hours, to react the synthetic mixture filtering recovering catalyst then, with filtrate decompression rectifying dealcoholysis after press filtration obtains the product diisooctyl sebacate.Reaction conversion ratio is 99%, target product selectivity 100%.
Embodiment 4:
Reaction mass is formed (weight part):
50 parts of hexanodioic acids
160 parts of isooctyl alcohol
1.1 parts of catalyzer
Wherein catalyzer consists of: carrier silica gel 75 (wt%), phospho-wolframic acid 16 (wt%) and phospho-molybdic acid 9 (wt%).
Various materials are added in the reaction vessel, be heated to 155 ℃ of temperature of reaction, along with, answer the carrying out of process, be warming up to 190 ℃ gradually, the reaction carried out 2 hours 20 minutes, will react the synthetic mixture filtering recovering catalyst then, with filtrate decompression rectifying dealcoholysis after press filtration obtains product hexanodioic acid two isodecyl monooctyl esters.Reaction conversion ratio is 97.9%, target product selectivity nearly 100%.
Embodiment 5:
Reaction mass is formed (weight part):
60 parts of nonane diacids
150 parts of 2-Ethylhexyl Alcohols
1.2 parts of catalyzer
Wherein catalyzer consists of: carrier silica gel 78 (wt%), phospho-wolframic acid 6 (wt%) and phospho-molybdic acid 16 (wt%).
Various materials are added in the reaction vessel, be heated to 133 ℃ of temperature of reaction, carrying out along with reaction process, be warming up to 175 ℃ gradually, reaction was carried out 1 hour 40 minutes, to react the synthetic mixture filtering recovering catalyst then, with filtrate decompression rectifying dealcoholysis after press filtration obtains product of nonane diacid two (2-ethylhexyl.Reaction conversion ratio is 98.8%, target product selectivity nearly 100%.
Embodiment 6:
Reaction mass is formed (weight part):
65 parts of sebacic acid
1,130 parts of 3-dimethyl butyrate alcohols
Catalyzer 1.3 minutes
Wherein catalyzer consists of: carrier silica gel 81 (wt%), phospho-wolframic acid 10 (wt%) and phospho-molybdic acid 9 (wt%).
Various materials are added in the reaction vessel, be heated to 120 ℃ of temperature of reaction, carrying out along with reaction process, be warming up to 164 ℃ gradually, reaction was carried out 1 hour 50 minutes, to react the synthetic mixture filtering recovering catalyst then, with filtrate decompression rectifying dealcoholysis after press filtration promptly gets product sebacic acid two (1, the 3-dimethyl butyrate) ester.Reaction conversion ratio is 99%, target product selectivity nearly 100%.
Claims (4)
1, a kind of preparation method of fatty group dibasic acid, the acid alcohol esterification process for traditional is characterized in that: the heteropolyacid that adopts silica gel load is as catalyzer, and the essentially consist of this catalyzer and weight percent are:
Silica gel 70-90%
Phosphorus heteropoly tungstic acid H
3[P (W
3O
10)
4] XH
2O 5-25%
Phosphato-molybdic heteropolyacid H
7[P (Mo
2O
7)
6] XH
2Reactions steps that O 5-25% is concrete and condition are:
A, material ratio:
The mol ratio of aliphatic dibasic acid and Fatty Alcohol(C12-C14 and C12-C18) is 2.0-4.0, and catalyst consumption is the 1.5-3.5% of aliphatic dibasic acid weight;
B, reaction process process:
Catalyzer and reaction mass are joined in the conventional esterification container by material ratio given among the above-mentioned A, be heated to temperature of reaction 120-190 ℃, question response carries out 1.5-3h, respectively collection catalyst and product.
2, method according to claim 1, it is characterized in that: catalyzer adopts dipping method, silica gel is joined in the mixed aqueous solution of phosphato-molybdic heteropolyacid that concentration is 0.3-2.1g/mol and phosphorus heteropoly tungstic acid, at room temperature stir 3-5h, boil off unnecessary water, dry 10-15h makes under 120-150 ℃.
3, method according to claim 2 is characterized in that: when the preparation catalyzer, adopt the water-bath cushioning to boil off unnecessary water.
4, according to claim 1 or 2 or 3 described methods, it is characterized in that: the mol ratio of aliphatic dibasic acid and Fatty Alcohol(C12-C14 and C12-C18) is 3.4-3.8, and said aliphatic dibasic acid is C
6-C
10Aliphatic dibasic acid, Fatty Alcohol(C12-C14 and C12-C18) is C
6-C
10Fatty Alcohol(C12-C14 and C12-C18); Catalyst consumption is the 2.0-3.0% of aliphatic dibasic acid weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97104061A CN1062261C (en) | 1997-04-23 | 1997-04-23 | Method of preparing fatty group dibasic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97104061A CN1062261C (en) | 1997-04-23 | 1997-04-23 | Method of preparing fatty group dibasic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1197057A true CN1197057A (en) | 1998-10-28 |
| CN1062261C CN1062261C (en) | 2001-02-21 |
Family
ID=5167099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97104061A Expired - Fee Related CN1062261C (en) | 1997-04-23 | 1997-04-23 | Method of preparing fatty group dibasic acid |
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| CN (1) | CN1062261C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441495C (en) * | 2003-12-19 | 2008-12-10 | 华东师范大学 | Silicon gel coated poly metal oxygen-containing cluster compound nano particle material and its preparing method |
| CN101265184B (en) * | 2007-03-12 | 2010-09-01 | 中国石油天然气股份有限公司 | Method for preparing dibasic acid ester |
| CN103274938A (en) * | 2013-06-09 | 2013-09-04 | 南通众诚生物技术有限公司 | Method for catalytically synthesizing diisooctyl dodecanedioate base oil by solid superacid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57130954A (en) * | 1981-02-09 | 1982-08-13 | Tokuyama Soda Co Ltd | Esterification |
-
1997
- 1997-04-23 CN CN97104061A patent/CN1062261C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441495C (en) * | 2003-12-19 | 2008-12-10 | 华东师范大学 | Silicon gel coated poly metal oxygen-containing cluster compound nano particle material and its preparing method |
| CN101265184B (en) * | 2007-03-12 | 2010-09-01 | 中国石油天然气股份有限公司 | Method for preparing dibasic acid ester |
| CN103274938A (en) * | 2013-06-09 | 2013-09-04 | 南通众诚生物技术有限公司 | Method for catalytically synthesizing diisooctyl dodecanedioate base oil by solid superacid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1062261C (en) | 2001-02-21 |
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