CN106146311A - A kind of preparation method of 1,2-cyclohexyldicarboxylic acids ester plasticiser - Google Patents
A kind of preparation method of 1,2-cyclohexyldicarboxylic acids ester plasticiser Download PDFInfo
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- CN106146311A CN106146311A CN201510203138.6A CN201510203138A CN106146311A CN 106146311 A CN106146311 A CN 106146311A CN 201510203138 A CN201510203138 A CN 201510203138A CN 106146311 A CN106146311 A CN 106146311A
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- cyclohexyldicarboxylic acids
- oac
- cyclohexyldicarboxylic
- ester
- monohydric alcohol
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Abstract
A kind of 1, the preparation method of 2-cyclohexyldicarboxylic acids ester plasticiser, the method is with 1, and 2-cyclohexyldicarboxylic acids and monohydric alcohol are raw material, under catalytic action, 80-250 DEG C, carries out esterification, reacts 0.5-48h.Through decompression distillation, obtain 1,2-cyclohexyldicarboxylic acids ester product.1,2-cyclohexyldicarboxylic acids ester is a kind of nontoxic plasticizer, and alternative phthalic acid ester is used for the industry field such as plastics, rubber.Product yield prepared by the method is high, and product is easily isolated, environmental friendliness, has good application prospect.
Description
Technical field
The present invention relates to macromolecular material and chemical field, in particular it relates to 1,2-cyclohexyldicarboxylic acids and
Monohydric alcohol carries out esterification under catalytic action, prepares 1, the method for 2-cyclohexyldicarboxylic acids ester.
Background technology
Plasticizer is widely used in the plasticising of plastics such as polrvinyl chloride etc., thus improves the processing characteristics of plastics.
Phthalic ester plasticizer, dioctyl phthalate (DOP) is most widely used.In the last few years,
Because of the carcinogenecity that phthalic ester plasticizer is potential, the developed country such as American-European, Japanese has limited use neighbour
Phthalic easter plastizer, the widely used DOP especially as primary plasticizer.China also specifies,
Forbid that phthalic ester plasticizer uses in fields such as food, medicine, toys for children.Therefore, exploitation
Low toxicity, nontoxic plasticiser have important scientific meaning and application prospect.
1,2-cyclohexyldicarboxylic acids ester is the selection hydrogenation products of phthalic acid ester, has good with most polymers
The good compatibility, is expected to become the nontoxic plasticizer that a class is new.
The Research Thinking of the present invention is, by 1,2-cyclohexyldicarboxylic acids, as binary acid, is esterified with monohydric alcohol
Reaction, obtains 1, and 2-cyclohexyldicarboxylic acids ester, the physicochemical properties of these esters of research, develop a class further
Nontoxic plasticizer, substitutes the phthalic ester plasticizer having carcinogenesis, has important scientific meaning
And using value.
Summary of the invention
It is an object of the invention to, develop a class nontoxic plasticizer, substitute the phthalate having carcinogenesis
Plasticizer, for the synthesis of polymer material of specific use, it is provided that new skill sustainable development, eco-friendly
Art and new method.
Specifically, it is simply that 1,2-cyclohexyldicarboxylic acids and monohydric alcohol carry out esterification under catalytic action, and
By reduced pressure distillation technique separating-purifying 1,2-cyclohexyldicarboxylic acids ester, and to its purity test, provide for application
Reference and foundation.
The method provided according to the present invention, the catalyst that the present invention uses is Zn (OAc)2、Mn(OAc)2、
Co(OAc)2、Mg(OAc)2、Ca(OAc)2、Sb(OAc)2In one or more compounding ingredients.
The method provided according to the present invention, described 1,2-cyclohexyldicarboxylic acids with the esterification reaction temperature of monohydric alcohol is
90-260 DEG C, the response time is 0.1-24h.
Monohydric alcohol includes: butanol, amylalcohol, hexanol, Hexalin, enanthol, capryl alcohol, 2-Ethylhexyl Alcohol, nonyl alcohol,
One or two or more kinds in decanol, 2-propyl enanthol.
Catalyst amount is the 0.01-5.0mol% of dihydroxylic alcohols；Hexahydrobenzoid acid in reaction raw materials and dihydroxylic alcohols
Mol ratio 2.1-4.0:1 of consumption.
Described esterification is carried out under nitrogen protection.
The method for purifying and separating of 1,2-cyclohexyldicarboxylic acids ester is decompression distillation.
1,2-cyclohexyldicarboxylic acids ester is a kind of nontoxic plasticizer, and alternative phthalic acid ester is used for plastics, rubber
The industry fields such as glue.Product yield prepared by the method is high, and product is easily isolated, and environmental friendliness has very
Good application prospect.
The method provided according to the present invention, in order to check the effect of esterification, final ester is determined by the present invention
Property, purity use Gas chromatographyMass spectrometry (GC-MS) analyze, yield use gas chromatograph (GC)
Inner mark method ration.
By specific embodiments in detail the present invention is described in detail below, but the present invention implements to be not limited to these embodiments:
Detailed description of the invention
Embodiment 1: by 10mmol 1,2-cyclohexyldicarboxylic acids, 21mmol butanol, 0.01mmol Zn (OAc)2Add
Enter in 50mL round-bottomed flask.It is heated to 200 DEG C；React 4h at such a temperature.Then carry out decompression to steam
Evaporate and obtain 1,2-cyclohexyldicarboxylic acids dibutyl ester.According to 1, the inventory of 2-cyclohexyldicarboxylic acids calculates, this ester
Separating molar yield is 98%, and purity is 99.4%.
Embodiment 2: by 10mmol 1,2-cyclohexyldicarboxylic acids, 25mmol amylalcohol, 0.1mmol Zn (OAc)2Add
Enter in 50mL round-bottomed flask.It is heated to 180 DEG C；React 6h at such a temperature.Then carry out decompression to steam
Evaporate and obtain 1,2-cyclohexyldicarboxylic acids diamyl ester.According to 1, the inventory of 2-cyclohexyldicarboxylic acids calculates, this ester
Separating molar yield is 96%, and purity is 99.9%.
Embodiment 3: by 10mmol 1,2-cyclohexyldicarboxylic acids, 22mmol hexanol, 0.05mmol Mn (OAc)2
Join in 50mL round-bottomed flask.It is heated to 255 DEG C；React 0.1h at such a temperature.Then reduce pressure
Distillation obtains 1,2-cyclohexyldicarboxylic acids dihexyl.According to 1, the inventory of 2-cyclohexyldicarboxylic acids calculates, this ester
Separation molar yield be 95%, purity is 99.6%.
Embodiment 4: by 10mmol 1,2-cyclohexyldicarboxylic acids, 30mmol enanthol, 0.5mmol Co (OAc)2Add
Enter in 50mL round-bottomed flask.It is heated to 155 DEG C；React 10h at such a temperature.Then carry out decompression to steam
Evaporate and obtain 1,2-cyclohexyldicarboxylic acids two heptyl ester.According to 1, the inventory of 2-cyclohexyldicarboxylic acids calculates, this ester
Separating molar yield is 99%, and purity is 99.9%.
Embodiment 5: by 10mmol 1,2-cyclohexyldicarboxylic acids, 35mmol capryl alcohol, 0.4mmol Mg (OAc)2Add
Enter in 50mL round-bottomed flask.It is heated to 95 DEG C；React 24h at such a temperature.Then carry out decompression to steam
Evaporate and obtain 1,2-cyclohexyldicarboxylic acids dioctyl ester.According to 1, the inventory of 2-cyclohexyldicarboxylic acids calculates, this ester
Separating molar yield is 97%, and purity is 99.8%.
Embodiment 6: by 10mmol 1,2-cyclohexyldicarboxylic acids, 38mmol 2-Ethylhexyl Alcohol, 0.15mmol
Ca(OAc)2Join in 50mL round-bottomed flask.It is heated to 195 DEG C；React 8h at such a temperature.Then
Carry out decompression distillation and obtain 1,2-cyclohexyldicarboxylic acids two (2-ethyl) own ester.According to 1,2-cyclohexyldicarboxylic acids
Inventory calculate, the separation molar yield of this ester is 94%, and purity is 99.1%.
Embodiment 7: by 10mmol 1,2-cyclohexyldicarboxylic acids, 21mmol nonyl alcohol, 0.35mmol Sb (OAc)2Add
Enter in 50mL round-bottomed flask.It is heated to 225 DEG C；React 5h at such a temperature.Then carry out decompression to steam
Evaporate and obtain 1,2-cyclohexyldicarboxylic acids two nonyl ester.According to 1, the inventory of 2-cyclohexyldicarboxylic acids calculates, this ester
Separating molar yield is 91%, and purity is 98.1%.
Embodiment 8: by 10mmol 1,2-cyclohexyldicarboxylic acids, 22mmol 2-propyl enanthol, 0.015mmol
Sb(OAc)2Join in 50mL round-bottomed flask.It is heated to 228 DEG C；React 6h at such a temperature.Then
Carry out decompression distillation and obtain 1,2-cyclohexyldicarboxylic acids two (2-propyl group) heptyl ester.According to 1,2-cyclohexyldicarboxylic acids
Inventory calculate, the separation molar yield of this ester is 90%, and purity is 99.7%.
Embodiment 9: by 10mmol 1,2-cyclohexyldicarboxylic acids, 21mmol decanol, 0.012mmol Sb (OAc)2
With 0.012mmol Zn (OAc)2Join in 50mL round-bottomed flask.It is heated to 236 DEG C；The most anti-
Answer 14h.Then carry out decompression distillation and obtain 1,2-cyclohexyldicarboxylic acids didecyl.According to 1,2-cyclohexyldicarboxylic acids
Inventory calculate, the separation molar yield of this ester is 98%, and purity is 99.9%.
The present invention develops technology of preparing and the method for a 1,2-cyclohexyldicarboxylic acids ester.At catalyst action
Under, by 1,2-cyclohexyldicarboxylic acids and the esterification of monohydric alcohol, product separation purification process, efficiently,
High-quality prepares 1,2-cyclohexyldicarboxylic acids ester.For exploitation novel non-toxic plasticizer, it is provided that sustainable development
New technique and innovative approach, there is important scientific meaning and using value.
Claims (6)
1. one kind 1, the preparation method of 2-cyclohexyldicarboxylic acids ester plasticiser, it is characterised in that: with 1,2-cyclohexyl
Dioctyl phthalate and monohydric alcohol are raw material, and at catalyst action, 1,2-cyclohexyldicarboxylic acids and monohydric alcohol are anti-by esterification
Should, through purifies and separates, obtain 1,2-cyclohexyldicarboxylic acids ester product；
The catalyst of described use is: Zn (OAc)2、Mn(OAc)2、Co(OAc)2、Mg(OAc)2、
Ca(OAc)2、Sb(OAc)2In one or two or more kinds compounding ingredients.
Method the most according to claim 1, it is characterised in that:
Described 1,2-cyclohexyldicarboxylic acids is 90-260 DEG C, during reaction with the reaction temperature of the esterification of monohydric alcohol
Between be 0.1-24h.
Method the most according to claim 1, it is characterised in that: monohydric alcohol includes: butanol, amylalcohol,
One in hexanol, Hexalin, enanthol, capryl alcohol, 2-Ethylhexyl Alcohol, nonyl alcohol, decanol, 2-propyl enanthol or
More than two kinds.
Method the most according to claim 1, it is characterised in that: catalyst amount is 1,2-cyclohexyl diformazan
The 0.01-5.0mol% of acid；1,2-cyclohexyldicarboxylic acids in reaction raw materials and the mol ratio of monohydric alcohol consumption
1:2.1-4.0。
Method the most according to claim 1, it is characterised in that: described esterification is protected at nitrogen
Under carry out.
Method the most according to claim 1, it is characterised in that: the purification of 1,2-cyclohexyldicarboxylic acids ester divides
It is decompression distillation from method.
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| CN201510203138.6A CN106146311A (en) | 2015-04-24 | 2015-04-24 | A kind of preparation method of 1,2-cyclohexyldicarboxylic acids ester plasticiser |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| CN101774919A (en) * | 2010-02-04 | 2010-07-14 | 江南大学 | Method for preparing cyclohexane 1,2-dicarboxylate using organic acid as catalyst |
| CN102239198A (en) * | 2008-12-05 | 2011-11-09 | 巴斯夫欧洲公司 | Cyclohexane polycarboxylic acid derivatives as plasticizers for adhesives and sealants |
| CN102731755A (en) * | 2012-07-19 | 2012-10-17 | 中国科学院长春应用化学研究所 | Method for preparing plasticizer |
| CN103086878A (en) * | 2013-01-14 | 2013-05-08 | 浙江大学 | Preparation method of cyclohexyl compound by aromatic compound catalytic hydrogenation |
| CN103130640A (en) * | 2013-01-16 | 2013-06-05 | 宁波东来化工有限公司 | Device and method for preparing 1, 2-cyclohexane didecyl phthalate |
| CN103130647A (en) * | 2013-01-16 | 2013-06-05 | 宁波东来化工有限公司 | Device and method for preparing 1, 2-cyclohexane dicyclohexyl phthalate |
| CN103896776A (en) * | 2012-12-26 | 2014-07-02 | 上海华明高技术（集团）有限公司 | Calcium carbonate surface modifier, and preparation method and use method thereof |
| CN104478722A (en) * | 2014-12-12 | 2015-04-01 | 江南大学 | Preparation method of di(2-propylheptyl) cyclohexyl-1,2-diformate |
-
2015
- 2015-04-24 CN CN201510203138.6A patent/CN106146311A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| CN102239198A (en) * | 2008-12-05 | 2011-11-09 | 巴斯夫欧洲公司 | Cyclohexane polycarboxylic acid derivatives as plasticizers for adhesives and sealants |
| CN101774919A (en) * | 2010-02-04 | 2010-07-14 | 江南大学 | Method for preparing cyclohexane 1,2-dicarboxylate using organic acid as catalyst |
| CN102731755A (en) * | 2012-07-19 | 2012-10-17 | 中国科学院长春应用化学研究所 | Method for preparing plasticizer |
| CN103896776A (en) * | 2012-12-26 | 2014-07-02 | 上海华明高技术（集团）有限公司 | Calcium carbonate surface modifier, and preparation method and use method thereof |
| CN103086878A (en) * | 2013-01-14 | 2013-05-08 | 浙江大学 | Preparation method of cyclohexyl compound by aromatic compound catalytic hydrogenation |
| CN103130640A (en) * | 2013-01-16 | 2013-06-05 | 宁波东来化工有限公司 | Device and method for preparing 1, 2-cyclohexane didecyl phthalate |
| CN103130647A (en) * | 2013-01-16 | 2013-06-05 | 宁波东来化工有限公司 | Device and method for preparing 1, 2-cyclohexane dicyclohexyl phthalate |
| CN104478722A (en) * | 2014-12-12 | 2015-04-01 | 江南大学 | Preparation method of di(2-propylheptyl) cyclohexyl-1,2-diformate |
Non-Patent Citations (3)
| Title |
|---|
| 李孝国等: "环保增塑剂环己烷1,2-二甲酸二异辛酯的合成", 《石油化工高等学校学报》 * |
| 李成成等: "环保增塑剂环己烷1,2-二甲酸二异辛酯的合成", 《精细化工》 * |
| 欧远辉等: "环保增塑剂环己烷-1，2-二甲酸二异辛酯的合成与应用", 《中国塑料》 * |
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