CN102391122A - Method for preparing hexahydro phthalic acid bis(2-ethyl hexyl)ester serving as environment-friendly plasticizer - Google Patents
Method for preparing hexahydro phthalic acid bis(2-ethyl hexyl)ester serving as environment-friendly plasticizer Download PDFInfo
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- CN102391122A CN102391122A CN2011103006701A CN201110300670A CN102391122A CN 102391122 A CN102391122 A CN 102391122A CN 2011103006701 A CN2011103006701 A CN 2011103006701A CN 201110300670 A CN201110300670 A CN 201110300670A CN 102391122 A CN102391122 A CN 102391122A
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- phthalic acid
- ethyl hexyl
- acid bis
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Abstract
The invention discloses a method for preparing hexahydro phthalic acid bis(2-ethyl hexyl)ester serving as an environment-friendly plasticizer. The method comprises the following steps of: 1) adding 1 mole of phthalic anhydride, 2.0 to 2.2 moles of 2-ethylhexyl alcohol and a solid super acid SO4 <2->/TiO2-Al2O3 catalyst in amount which is 0.04 to 0.06 percent of total quantity of kettle materials into a reactor, stirring, heating to the temperature of 210 DEG C to perform esterification reaction for 2 to 3 hours, and performing dealcoholization to obtain a rough product of the hexahydro phthalic acid bis(2-ethyl hexyl)ester; and 2) performing steam stripping on the rough product of the hexahydro phthalic acid bis(2-ethyl hexyl)ester under reduced pressure for 3 to 4 hours, and adding active carbon in amount which is 0.1 to 0.2 percent of the total quantity of the kettle materials, adsorbing and decolorating for 20 to 30 minutes, and performing filter pressing to obtain a purified product of the hexahydro phthalic acid bis(2-ethyl hexyl)ester. The method has a simple process, the pollution is reduced, and water is saved. The hexahydro phthalic acid bis(2-ethyl hexyl)ester plasticizer can be used for plastic products with high sanitary requirements such as medicinal packages, medical equipment, foot packaging, articles for daily use, toys and the like.
Description
Technical field
The present invention relates to the Minute Organic Synthesis technical field, relate in particular to the preparation method of a kind of environment-friendly plasticizer hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester.
Background technology
The main raw material that is used for increasing the PVC product softness is a softening agent; The kind and the output of softening agent all rank first in additives for plastics; In recent years; European Union successively puts into effect a plurality of bills and instruction, and strict restriction phthalic ester plasticizer (DOP etc.) is used for food product pack, medical treatment product and toy for children and other and the PVC goods that human body contacts closely, and China's softening agent industry and downstream manufacturing enterprise have been caused enormous impact; Industry development is restricted and challenges, and it is imperative therefore to develop the environmental type softening agent.The hexahydrobenzene dioctyl phthalate two of the inventive method preparation (2-ethyl oneself) ester plasticizer is that the susceptibility that aims at PVC is used (like medical facilities, food product pack, toy for children etc.) and a kind of non-phthalic ester plasticizer of exploitation; It has DOP (DOP) and the similar structure of DINP (DINP); The performance that possesses DOP and DINP; And function is more outstanding; Be embodied in: transport property is little, water white transparency, fully environmental protection, can hold mutually with common organic solvent and common plasticizers, its elasticity, the transparency, low-temperature performance is much better than primary plasticizers such as DOP and DINP; The more important thing is that hexahydrobenzene dioctyl phthalate acid two (2-ethyl oneself) ester product has excellent toxicological characteristics, can be medicine equipment, food product pack, medical treatment product, toy for children and other and desirable solution that reaches safety requirements is provided with the PVC product manufacturer that human body contacts closely.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, the preparation method of a kind of environment-friendly plasticizer hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester is provided.
The preparing method's of environment-friendly plasticizer hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester step is following:
1) with 1 mole of hexahydrophthalic acid anhydride, 2.0～2.2 moles of 2-ethylhexanols and relative still material total amount 0.4 ‰～0.6 ‰ solid super-strong acid SO
4 2-/ TiO
2-A1
2O
3Catalyzer joins in the reactor drum and stirs, and is warming up to 210 ℃ and carries out esterification 2～3 hours, and dealcoholysis obtains hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) the thick product of ester;
2) with the refining 3～4h of hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) the thick product of ester stripping under reduced pressure; The charcoal absorption decolouring 20～30min that adds relative still material total amount 0.1%～0.2% again obtains hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester purified product through press filtration.
The present invention adopts strict process control, the production technology of optimization to guarantee the high purity and the wholesomeness of product.The hexahydrobenzene dioctyl phthalate two that employing the inventive method makes (the 2-ethyl is own) ester plasticizer is when granulation or plasticising production, and good with the compatibleness of PVC material, its plastifying the finished product transport property is very low, has long work-ing life and excellent properties.
Embodiment
The technical process that the present invention adopts is: feed intake → esterification → dealcoholysis → make with extra care → adsorption bleaching → press filtration → finished product.
The preparing method's of environment-friendly plasticizer hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester step is following:
1) with 1 mole of hexahydrophthalic acid anhydride, 2.0～2.2 moles of 2-ethylhexanols and relative still material total amount 0.4 ‰～0.6 ‰ solid super-strong acid SO
4 2-/ TiO
2-A1
2O
3Catalyzer joins in the reactor drum and stirs, and is warming up to 210 ℃ and carries out esterification 2～3 hours, and dealcoholysis obtains hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) the thick product of ester;
2) with the refining 3～4h of hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) the thick product of ester stripping under reduced pressure; The charcoal absorption decolouring 20～30min that adds relative still material total amount 0.1%～0.2% again obtains hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester purified product through press filtration.
Hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) the ester plasticizer product gas purity that adopts above method to make can be through the gas chromatograph test, and product purity is more than or equal to 99.5%.
Embodiment 1
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.0 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.4 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3Catalyzer is warming up to 210 ℃ of reaction dealcoholysis after 3 hours, again with the refining 4h of open steam stripping; The charcoal absorption decolouring 20min that adds relative still material total amount 0.1% gets hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration, and its yield is 97.1%; Purity is 99.0%; Colourity (Pt-Co) is No. 15, and acid number is 0.14mgKOH/g, and specific density (20 ℃) is 0.958g/cm
3, flash-point (open cup) is 219 ℃.
Embodiment 2
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.1 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.4 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3Catalyzer is warming up to 210 ℃ of reaction dealcoholysis after 3 hours, again with the refining 4h of open steam stripping; The charcoal absorption decolouring 20min that adds relative still material total amount 0.1% gets hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration, and its yield is 98.3%; Purity is 99.1%; Colourity (Pt-Co) is No. 10, and acid number is 0.12mgKOH/g, and specific density (20 ℃) is 0.957g/cm
3, flash-point (open cup) is 221 ℃.
Embodiment 3
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.2 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.4 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3Catalyzer is warming up to 210 ℃ of reaction dealcoholysis after 3 hours, again with the refining 4h of open steam stripping; The charcoal absorption decolouring 20min that adds relative still material total amount 0.1% gets hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration, and its yield is 98.2%; Purity is 99.1%; Colourity (Pt-Co) is No. 15, and acid number is 0.10mgKOH/g, and specific density (20 ℃) is 0.958g/cm
3, flash-point (open cup) is 220 ℃.
Embodiment 4
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.0 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.5 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3Catalyzer is warming up to 210 ℃ of reaction dealcoholysis after 2.5 hours, again with the refining 3.5h of open steam stripping; The charcoal absorption decolouring 25min that adds relative still material total amount 0.15% gets hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration, and its yield is 98.5%; Purity is 99.1%; Colourity (Pt-Co) is No. 15, and acid number is 0.12mgKOH/g, and specific density (20 ℃) is 0.959g/cm
3, flash-point (open cup) is 220 ℃.
Embodiment 5
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.1 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.5 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3, be warming up to 210 ℃ of reaction dealcoholysis after 2.5 hours, again with the refining 3.5h of open steam stripping; The charcoal absorption decolouring 25min that adds relative still material total amount 0.15% gets hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration, and its yield is 99.4%; Purity is 99.6%; Colourity (Pt-Co) is No. 10, and acid number is 0.05mgKOH/g, and specific density (20 ℃) is 0.959g/cm
3, flash-point (open cup) is 222 ℃.
Embodiment 6
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.2 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.5 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3Catalyzer is warming up to thermotonus dealcoholysis after 2.5 hours of 210 ℃, again with the refining 3.5h of open steam stripping; The charcoal absorption decolouring 25min that adds relative still material total amount 0.15% gets hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration, and its yield is 99.2%; Purity is 99.5%; Colourity (Pt-Co) is No. 10, and acid number is 0.06mgKOH/g, and specific density (20 ℃) is 0.958g/cm
3, flash-point (open cup) is 221 ℃.
Embodiment 7
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.0 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.6 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3Catalyzer is warming up to 210 ℃ temperature and reacts dealcoholysis after 3 hours, again with the refining 3h of open steam stripping; The charcoal absorption decolouring 30min that adds relative still material total amount 0.2% gets hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration, and its yield is 98.3%; Purity is 99.0%; Colourity (Pt-Co) is No. 15, and acid number is 0.12mgKOH/g, and specific density (20 ℃) is 0.959g/cm
3, flash-point (open cup) is 219 ℃.
Embodiment 8
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.1 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.6 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3Catalyzer is warming up to 210 ℃ of reaction dealcoholysis after 2 hours, again with the refining 3h of open steam stripping; The charcoal absorption decolouring 30min that adds relative still material total amount 0.2% gets hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration, and its yield is 99.3%; Purity is 99.5%; Colourity (Pt-Co) is No. 10, and acid number is 0.08mgKOH/g, and specific density (20 ℃) is 0.957g/cm
3, flash-point (open cup) is 223 ℃.
Embodiment 9
With hexahydrophthalic acid anhydride, the 2-Ethylhexyl Alcohol mol ratio is that 1/2.2 hexahydrophthalic acid anhydride and 2-Ethylhexyl Alcohol add in the reactor drum and heat, and adds relative still material total amount 0.6 ‰ solid super-strong acid SO again
4 2-/ TiO
2-A1
2O
3,, be warming up to thermotonus dealcoholysis after 3 hours of 210 ℃; With the refining 3h of open steam stripping, add the charcoal absorption decolouring 30min of relative still material total amount 0.2% again, get hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester through press filtration; Its yield is 99.1%, and purity is 99.4%, and colourity (Pt-Co) is No. 10; Acid number is 0.07mgKOH/g, and specific density (20 ℃) is 0.958g/cm
3, flash-point (open cup) is 221 ℃.
Claims (1)
1. the preparation method of an environment-friendly plasticizer hexahydrobenzene dioctyl phthalate two (2-ethyl oneself) ester is characterized in that its step is following:
1) with 1 mole of hexahydrophthalic acid anhydride, 2.0～2.2 moles of 2-ethylhexanols and relative still material total amount 0.4 ‰～0.6 ‰ solid super-strong acid SO
4 2-/ TiO
2-A1
2O
3Catalyzer joins in the reactor drum and stirs, and is warming up to 210 ℃ and carries out esterification 2～3 hours, and dealcoholysis obtains hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) the thick product of ester;
2) with the refining 3～4h of hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) the thick product of ester stripping under reduced pressure; The charcoal absorption decolouring 20～30min that adds relative still material total amount 0.1%～0.2% again obtains hexahydrobenzene dioctyl phthalate two (the 2-ethyl is own) ester purified product through press filtration.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103006701A CN102391122A (en) | 2011-10-09 | 2011-10-09 | Method for preparing hexahydro phthalic acid bis(2-ethyl hexyl)ester serving as environment-friendly plasticizer |
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| CN2011103006701A CN102391122A (en) | 2011-10-09 | 2011-10-09 | Method for preparing hexahydro phthalic acid bis(2-ethyl hexyl)ester serving as environment-friendly plasticizer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701980A (en) * | 2012-06-29 | 2012-10-03 | 太仓市新星轻工助剂厂 | Synthetic method of environmental-friendly plasticizer hexahydrobenzene diisononyl phthalate |
| CN110483295A (en) * | 2019-09-09 | 2019-11-22 | 安徽香枫新材料股份有限公司 | A kind of DINP catalytic hydrogenation prepares the refining methd of DINCH |
| CN110713439A (en) * | 2019-10-31 | 2020-01-21 | 濮阳市盛源能源科技股份有限公司 | Preparation method of cyclohexane-1, 2-dicarboxylate environment-friendly plasticizer |
Citations (1)
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| CN101613282A (en) * | 2009-07-30 | 2009-12-30 | 杭州临安商通塑化有限公司 | A kind of environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester |
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2011
- 2011-10-09 CN CN2011103006701A patent/CN102391122A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613282A (en) * | 2009-07-30 | 2009-12-30 | 杭州临安商通塑化有限公司 | A kind of environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester |
Non-Patent Citations (1)
| Title |
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| 方猷泉: "《环己烷-1,2-二羧酸二异辛酯的合成与应用》", 《增塑剂》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701980A (en) * | 2012-06-29 | 2012-10-03 | 太仓市新星轻工助剂厂 | Synthetic method of environmental-friendly plasticizer hexahydrobenzene diisononyl phthalate |
| CN110483295A (en) * | 2019-09-09 | 2019-11-22 | 安徽香枫新材料股份有限公司 | A kind of DINP catalytic hydrogenation prepares the refining methd of DINCH |
| CN110713439A (en) * | 2019-10-31 | 2020-01-21 | 濮阳市盛源能源科技股份有限公司 | Preparation method of cyclohexane-1, 2-dicarboxylate environment-friendly plasticizer |
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Application publication date: 20120328 |