CN106431913A - Method for preparing cyclohexane phthalate high-carbon alcohol ester - Google Patents
Method for preparing cyclohexane phthalate high-carbon alcohol ester Download PDFInfo
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- CN106431913A CN106431913A CN201610735044.8A CN201610735044A CN106431913A CN 106431913 A CN106431913 A CN 106431913A CN 201610735044 A CN201610735044 A CN 201610735044A CN 106431913 A CN106431913 A CN 106431913A
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- carbon alcohol
- alcohol ester
- phthalic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing a cyclohexane phthalate high-carbon alcohol ester, wherein the method comprises the following steps: 1) choosing phthalic anhydride and high alcohol; 2) implementing an esterification reaction at the temperature of 280 DEG C to obtain a phthalate high-carbon alcohol ester; 3) implementing a synthesis reaction, carrying out a hydrogenation reaction on the phthalate high-carbon alcohol ester to synthesize the cyclohexane phthalate high-carbon alcohol ester, wherein hydrogen is a mixture of hydrogen and an inert gas at the volume ratio of 5:1, the catalytic hydrogenation reaction is performed for 1-1.5 hours at the temperature of 280 DEG C at the pressure of 10MPa in the synthesis reaction, wherein the molar ratio of the hydrogen to the phthalate high-carbon alcohol ester is (500-600):1; and 4) synthesizing and obtaining the cyclohexane phthalate high-carbon alcohol ester.
Description
Technical field
The invention belongs to the synthesis technical field of plasticizer, more particularly to one kind prepare two higher alcohols of hexahydro-phthalic acid
The method of ester.
Background technology
Plasticizer is the auxiliary agent kind of application amount maximum in plastics industry, to promoting plastics industry to be particularly polrvinyl chloride work
The development of industry plays conclusive effect.At present various novel plastics penetrated into industrial or agricultural, transport, traffic, medicine, food,
The every field such as clothing, building, national defence.With the raising of countries in the world environmental consciousness, medical parcel, medical apparatus and instruments, food bag
The plastics such as dress, article of everyday use, toy processing propose higher hygienic requirements to primary plasticizer, and the whole world has accelerated environmental protection increasing
Mould agent product and meet the applied research of the plastic of hygienic requirements.But the primary plasticizer of domestic enterprise's production at present is in many
In performance, particularly wholesomeness, avirulence etc. is difficult to meet the requirement of environmental protection.
Content of the invention
It is an object of the invention to provide a kind of method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid, the method production effect
Rate height, production purity height.
For solve above-mentioned technical problem, the present invention adopt technological means be,
A kind of method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid, comprises the following steps, it is characterised in that
1）. sorting phthalic anhydride and higher alcohols；
2）. esterification, esterification reaction temperature condition is 280 degree, to obtain two high-carbon alcohol ester of phthalic acid；
3）. synthetic reaction, two higher alcohols ester through hydrogenation of phthalic acid is synthesized two high-carbon alcohol ester of hexahydro-phthalic acid；Hydrogen
For hydrogen and the mixture of noble gases, the volume ratio of hydrogen and noble gases is 5：1；
In synthetic reaction, catalytic hydrogenation reaction is carried out under the conditions of 280 DEG C, 10MPa, reacts 1-1.5h, hydrogen and O-phthalic
The mol ratio of sour two high-carbon alcohol esters is 500-600： 1；
4）. synthesize to obtain two high-carbon alcohol ester of hexahydro-phthalic acid.
The following is the improvement further to technique scheme：
Comprise the following steps, it is characterised in that the noble gas mixtures are helium, argon, the mixture of neon, the helium
Gas, argon, the mass ratio of neon are 3：1：2.
In the catalytic hydrogenation reaction, catalyst used is the loaded catalyst with rhodium as active component.
The catalytic hydrogenation reaction temperature is 280 DEG C.
Catalytic hydrogenation reaction pressure is 10MPa.
Hydrogen is 500 with the mol ratio of two high-carbon alcohol ester of phthalic acid.
The higher alcohols are isononyl alcohol, the mixture of isodecanol, and the isononyl alcohol, the mass ratio of isodecanol are 3：2.
Product has that hygienic environment-protecting, plasticizing efficiency be high, animal migration is little, nonpoisonous and tasteless, its product elasticity, the transparency, low temperature
Superior performance, performance is better than similar ester of low-carbon alcohol, can be widely applied to medical packaging, toy for children, medical apparatus, food bag
The fields such as dress, article of everyday use, and product meets every strict demand of REACH comprehensively, the product with which as raw material also easily can be answered
Challenge to REACH.Taken due to the esterification stage of the present invention is higher alcohols, thus with respect to similar ester of low-carbon alcohol,
Its product elasticity, the transparency, cryogenic property are more superior.
Specific embodiment
Technical scheme is described below in conjunction with specific embodiment, but protection scope of the present invention not limited to this.
In following examples, tetraisopropyl titanate, rhodium for the loaded catalyst addition catalytically effective amount of active component are
Can, have no special requirements.
Embodiment 1, a kind of method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid, comprise the following steps,
1）. sorting phthalic anhydride and higher alcohols；In a kettle., by phthalic anhydride: isononyl alcohol（Mol ratio）Feed intake for 1: 2.8；
2）. esterification, make catalyst with tetraisopropyl titanate, esterification reaction temperature condition is 280 degree, reacts 2h, Ran Houjing
Cross dealcoholysis, refined post processing and obtain diisononyl phthalate；Obtain two high-carbon alcohol ester of phthalic acid；
3）. synthetic reaction, two higher alcohols ester through hydrogenation of phthalic acid is synthesized two high-carbon alcohol ester of hexahydro-phthalic acid；Hydrogen
For hydrogen and the mixture of noble gases, the volume ratio of hydrogen and noble gases is 5：1；
In synthetic reaction, catalyst is added, hydrogen is passed through, catalytic hydrogenation reaction is carried out, catalytic hydrogenation reaction is in 280 DEG C, 10MPa
Under the conditions of carry out, react 1-1.5h, the mol ratio of hydrogen and two high-carbon alcohol ester of phthalic acid is 500-600： 1；
4）. synthesize to obtain two high-carbon alcohol ester of hexahydro-phthalic acid.
Comprise the following steps, it is characterised in that the noble gas mixtures are helium, argon, the mixture of neon, institute
State helium, argon, neon mass ratio be 3：1：2.
In the catalytic hydrogenation reaction, catalyst used is the loaded catalyst with rhodium as active component.
The catalytic hydrogenation reaction temperature is 280 DEG C.
Catalytic hydrogenation reaction pressure is 10MPa.
Hydrogen is 500 with the mol ratio of two high-carbon alcohol ester of phthalic acid.
The higher alcohols are isononyl alcohol, the mixture of isodecanol, and the isononyl alcohol, the mass ratio of isodecanol are 3：2.
Embodiment 2, a kind of method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid, comprise the following steps,
1）. sorting phthalic anhydride and higher alcohols；In a kettle., by phthalic anhydride: isononyl alcohol（Mol ratio）Feed intake for 1: 2.8；
2）. esterification, make catalyst with tetraisopropyl titanate, esterification reaction temperature condition is 280 degree, reacts 4h, Ran Houjing
Cross dealcoholysis, refined post processing and obtain diisononyl phthalate；Obtain two high-carbon alcohol ester of phthalic acid；
3）. synthetic reaction, two higher alcohols ester through hydrogenation of phthalic acid is synthesized two high-carbon alcohol ester of hexahydro-phthalic acid；Hydrogen
For hydrogen and the mixture of noble gases, the volume ratio of hydrogen and noble gases is 5：1；
In synthetic reaction, catalyst is added, hydrogen is passed through, catalytic hydrogenation reaction is carried out, catalytic hydrogenation reaction is in 280 DEG C, 10MPa
Under the conditions of carry out, react 2h, the mol ratio of hydrogen and two high-carbon alcohol ester of phthalic acid is 500-600： 1；
4）. synthesize to obtain two high-carbon alcohol ester of hexahydro-phthalic acid.
Comprise the following steps, it is characterised in that the noble gas mixtures are helium, argon, the mixture of neon, institute
State helium, argon, neon mass ratio be 3：1：2.
In the catalytic hydrogenation reaction, catalyst used is the loaded catalyst with rhodium as active component.
The catalytic hydrogenation reaction temperature is 280 DEG C.
Catalytic hydrogenation reaction pressure is 10MPa.
Hydrogen is 500 with the mol ratio of two high-carbon alcohol ester of phthalic acid.
The higher alcohols are isononyl alcohol, the mixture of isodecanol, and the isononyl alcohol, the mass ratio of isodecanol are 3：2.
Embodiment 3, a kind of method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid, comprise the following steps,
1）. sorting phthalic anhydride and higher alcohols；In a kettle., by phthalic anhydride: isononyl alcohol（Mol ratio）Feed intake for 1: 2.8；
2）. esterification, make catalyst with tetraisopropyl titanate, esterification reaction temperature condition is 280 degree, reacts 4h, Ran Houjing
Cross dealcoholysis, refined post processing and obtain diisononyl phthalate；Obtain two high-carbon alcohol ester of phthalic acid；
3）. synthetic reaction, two higher alcohols ester through hydrogenation of phthalic acid is synthesized two high-carbon alcohol ester of hexahydro-phthalic acid；Hydrogen
For hydrogen and the mixture of noble gases, the volume ratio of hydrogen and noble gases is 5：1；
In synthetic reaction, catalyst is added, hydrogen is passed through, catalytic hydrogenation reaction is carried out, catalytic hydrogenation reaction is in 280 DEG C, 10MPa
Under the conditions of carry out, react 2h, the mol ratio of hydrogen and two high-carbon alcohol ester of phthalic acid is 500-600： 1；
4）. synthesize to obtain two high-carbon alcohol ester of hexahydro-phthalic acid.
Comprise the following steps, it is characterised in that the noble gas mixtures are helium, argon, the mixture of neon, institute
State helium, argon, neon mass ratio be 3：1：2.
In the catalytic hydrogenation reaction, catalyst used is the loaded catalyst with rhodium as active component.
The catalytic hydrogenation reaction temperature is 280 DEG C.
Catalytic hydrogenation reaction pressure is 10MPa.
Hydrogen is 500 with the mol ratio of two high-carbon alcohol ester of phthalic acid.
The higher alcohols are isononyl alcohol, the mixture of isodecanol, and the isononyl alcohol, the mass ratio of isodecanol are 3：2.
Embodiment 4, a kind of method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid, comprise the following steps,
1）. sorting phthalic anhydride and higher alcohols；In a kettle., by phthalic anhydride: isononyl alcohol（Mol ratio）Feed intake for 1: 2.8；
2）. esterification, make catalyst with tetraisopropyl titanate, esterification reaction temperature condition is 280 degree, reacts 4h, Ran Houjing
Cross dealcoholysis, refined post processing and obtain diisononyl phthalate；Obtain two high-carbon alcohol ester of phthalic acid；
3）. synthetic reaction, two higher alcohols ester through hydrogenation of phthalic acid is synthesized two high-carbon alcohol ester of hexahydro-phthalic acid；Hydrogen
For hydrogen and the mixture of noble gases, the volume ratio of hydrogen and noble gases is 4：1；
In synthetic reaction, catalyst is added, hydrogen is passed through, catalytic hydrogenation reaction is carried out, catalytic hydrogenation reaction is in 280 DEG C, 10MPa
Under the conditions of carry out, react 2h, the mol ratio of hydrogen and two high-carbon alcohol ester of phthalic acid is 500-600： 1；
4）. synthesize to obtain two high-carbon alcohol ester of hexahydro-phthalic acid.
Comprise the following steps, it is characterised in that the noble gas mixtures are helium, argon, the mixture of neon, institute
State helium, argon, neon mass ratio be 3：1：2.
In the catalytic hydrogenation reaction, catalyst used is the loaded catalyst with rhodium as active component.
The catalytic hydrogenation reaction temperature is 280 DEG C.
Catalytic hydrogenation reaction pressure is 10MPa.
Hydrogen is 500 with the mol ratio of two high-carbon alcohol ester of phthalic acid.
The higher alcohols are isononyl alcohol, the mixture of isodecanol, and the isononyl alcohol, the mass ratio of isodecanol are 3：2.
Neighbour's two high-carbon alcohol ester of dioctyl phthalate,
| Two high-carbon alcohol ester of adjacent dioctyl phthalate | Conversion ratio | Yield |
| Embodiment 1 | 99.91% | 99.89% |
| Embodiment 1 | 99.94% | 99.92% |
| Embodiment 3 | 99.95% | 99.91% |
| Embodiment 4 | 99.99% | 99.99% |
Claims (7)
1. a kind of method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid, comprises the following steps, it is characterised in that
1）. sorting phthalic anhydride and higher alcohols；
2）. esterification, esterification reaction temperature condition is 280 degree, to obtain two high-carbon alcohol ester of phthalic acid；
3）. synthetic reaction, two higher alcohols ester through hydrogenation of phthalic acid is synthesized two high-carbon alcohol ester of hexahydro-phthalic acid；Hydrogen
For hydrogen and the mixture of noble gases, the volume ratio of hydrogen and noble gases is 5：1；
In synthetic reaction, catalytic hydrogenation reaction is carried out under the conditions of 280 DEG C, 10MPa, reacts 1-1.5h, hydrogen and O-phthalic
The mol ratio of sour two high-carbon alcohol esters is 500-600： 1；
4）. synthesize to obtain two high-carbon alcohol ester of hexahydro-phthalic acid.
2. a kind of method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid as claimed in claim 1, comprises the following steps, its
It is characterised by, the noble gas mixtures are helium, argon, the mixture of neon, the helium, argon, the quality of neon
Than for 3：1：2.
3. the method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid as described in claim 2, it is characterised in that described
Urge
Change the loaded catalyst that catalyst used in hydrogenation reaction is with rhodium as active component.
4. the method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid as described in claim 1, it is characterised in that described
Urge
Change hydrogenation reaction temperature and be 280 DEG C.
5. the method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid as described in claim 1, it is characterised in that catalysis plus
Hydrogen reaction pressure is 10MPa.
6. the method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid as described in claim 1, it is characterised in that hydrogen
With
The mol ratio of two high-carbon alcohol ester of phthalic acid is 500.
7. the method for preparing two high-carbon alcohol ester of hexahydro-phthalic acid as claimed in claim 6, it is characterised in that the height
Carbon alcohol is isononyl alcohol, the mixture of isodecanol, and the isononyl alcohol, the mass ratio of isodecanol are 3：2.
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| CN201610735044.8A CN106431913A (en) | 2016-08-28 | 2016-08-28 | Method for preparing cyclohexane phthalate high-carbon alcohol ester |
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| CN201610735044.8A CN106431913A (en) | 2016-08-28 | 2016-08-28 | Method for preparing cyclohexane phthalate high-carbon alcohol ester |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285815A (en) * | 1997-12-19 | 2001-02-28 | 巴斯福股份公司 | Method for hydrogenating benzene polycarboxylic acids or derivatives thereof by using catalyst containing macropores |
| WO2014053618A1 (en) * | 2012-10-05 | 2014-04-10 | Basf Se | Method for producing cyclohexanecarboxylic acid derivatives with a low proportion of by-products |
| CN103739492A (en) * | 2013-12-31 | 2014-04-23 | 河南庆安化工高科技股份有限公司 | Method for preparing cyclohexane higher aliphatic phthalate |
-
2016
- 2016-08-28 CN CN201610735044.8A patent/CN106431913A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285815A (en) * | 1997-12-19 | 2001-02-28 | 巴斯福股份公司 | Method for hydrogenating benzene polycarboxylic acids or derivatives thereof by using catalyst containing macropores |
| WO2014053618A1 (en) * | 2012-10-05 | 2014-04-10 | Basf Se | Method for producing cyclohexanecarboxylic acid derivatives with a low proportion of by-products |
| CN103739492A (en) * | 2013-12-31 | 2014-04-23 | 河南庆安化工高科技股份有限公司 | Method for preparing cyclohexane higher aliphatic phthalate |
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