CN106045857A - Preparation method for dicyclohexyl dihydric alcohol formate plasticizer - Google Patents
Preparation method for dicyclohexyl dihydric alcohol formate plasticizer Download PDFInfo
- Publication number
- CN106045857A CN106045857A CN201510202921.0A CN201510202921A CN106045857A CN 106045857 A CN106045857 A CN 106045857A CN 201510202921 A CN201510202921 A CN 201510202921A CN 106045857 A CN106045857 A CN 106045857A
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- CN
- China
- Prior art keywords
- dicyclohexyl
- dihydroxylic alcohols
- formic acid
- plasticizer
- dihydric alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
Abstract
The invention provides a preparation method for a dicyclohexyl dihydric alcohol formate plasticizer. The method comprises the following steps: subjecting cyclohexyl formic acid and dihydric alcohol to an esterification reaction at 80 to 250 DEG C under catalysis action for 0.5 to 48 h; and then carrying out pressure-reduced distillation so as to obtain a dicyclohexyl dihydric alcohol formate product. Dicyclohexyl dihydric alcohol formate is nontoxic plasticizer and can replace phthalate in the fields of plastics, rubber and the like. The preparation method is high in product yield, easy in product separation and friendly to environment, and has good application prospect.
Description
Technical field
The present invention relates to macromolecular material and chemical field, in particular it relates to hexahydrobenzoid acid
Under catalytic action, carry out esterification with dihydroxylic alcohols, prepare dicyclohexyl formic acid binary alcohol esters
Method.
Background technology
Plasticizer is widely used in the plasticising of plastics such as polrvinyl chloride etc., thus improves the processing characteristics of plastics.Adjacent
Phthalic easter plastizer is most widely used, such as dibutyl phthalate (DBP), phthalic acid two
Monooctyl ester (DOP), phthalic acid two (2-ethyl) own ester (DEHP) etc..In the last few years, because of adjacent benzene two
The toxicity of formate ester plasticizer, the developed country such as American-European has limited use phthalic ester plasticizer, especially
It is widely used DOP as primary plasticizer.China also specifies, forbids phthalic ester plasticizer
Use in fields such as food, medicine, toys for children.Therefore, exploitation low toxicity, nontoxic plasticiser have important
Scientific meaning and application prospect.
Dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester are the class nontoxic plasticizers developed in recent years,
There is the good compatibility with most polymers, detected by departments such as external relevant food, medicine, cosmetics
It is set to the primary plasticizer that can be used for packaging material for food.Benzoic hydrogenation products hexahydrobenzoid acid is as benzoic acid
Substitute, its esterification products is expected to become the nontoxic plasticizer that a class is new
The Research Thinking of the present invention is, using hexahydrobenzoid acid as monoacid, carries out esterification with dihydroxylic alcohols,
Obtain dicyclohexyl formic acid binary alcohol esters, study the physicochemical properties of these esters further, develop a class nontoxic
Plasticizer, substitutes the phthalic ester plasticizer having carcinogenesis, has important scientific meaning and application
It is worth.
Summary of the invention
It is an object of the invention to, develop a class nontoxic plasticizer, substitute and have the phthalate of carcinogenesis to increase
Mould agent, for the synthesis of polymer material of specific use, it is provided that new technique sustainable development, eco-friendly and
New method.
Specifically, it is simply that hexahydrobenzoid acid and dihydroxylic alcohols carry out esterification under catalytic action, and pass through decompression
Distillation technique separating-purifying dicyclohexyl formic acid binary alcohol esters, and to its purity test, for application provide reference and
Foundation.
The method provided according to the present invention, the catalyst that the present invention uses is Sb2O3、Sb(OAc)2、
Sb2(OCH2CH2O)3In one or more compounding ingredients.
The method provided according to the present invention, described hexahydrobenzoid acid is 100-250 with the esterification reaction temperature of dihydroxylic alcohols
DEG C, the response time is 0.5-48h.
Dihydroxylic alcohols includes: the one in two glycosides alcohol, dipropylene glycol, hexanediol, nonanediol, decanediol or two kinds
Above.
Catalyst amount is the 0.01-5.0mol% of dihydroxylic alcohols；Hexahydrobenzoid acid and dihydroxylic alcohols in reaction raw materials are used
Mol ratio 2.1-3.0:1 of amount.
Described esterification is carried out under nitrogen protection.
The method for purifying and separating of dicyclohexyl formic acid binary alcohol esters is decompression distillation.
Dicyclohexyl formic acid binary alcohol esters is a kind of nontoxic plasticizer, alternative phthalic acid ester for plastics,
The industry fields such as rubber.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, the present invention is qualitative to final ester
, 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 bis-glycosides alcohol, 21mmol hexahydrobenzoid acid, 0.005mmol Sb (OAc)2Join
In 50mL round-bottomed flask.It is heated to 220 DEG C；React 8h at such a temperature.Then carry out decompression distillation to obtain
Dicyclohexyl formic acid two glycosides alcohol ester.Calculating according to the inventory of two glycosides alcohol, the separation molar yield of this ester is 99%
, purity is 99.9%.
Embodiment 2: by 10mmol dipropylene glycol, 25mmol hexahydrobenzoid acid, 0.001mmol Sb (OAc)2With
0.001mmol Sb2(OCH2CH2O)3Join in 50mL round-bottomed flask.It is heated to 150 DEG C；In this temperature
Lower reaction 48h.Then carry out decompression distillation and obtain dicyclohexyl formic acid dipropylene glycol ester.Throwing according to dipropylene glycol
Doses calculates, and the separation molar yield of this ester is 91%, and purity is 99.5%.
Embodiment 3: by 10mmol hexanediol, 30mmol hexahydrobenzoid acid, 0.5mmol Sb2(OCH2CH2O)3
Join in 50mL round-bottomed flask.It is heated to 250 DEG C；React 0.5h at such a temperature.Then carry out decompression to steam
Evaporate and obtain dicyclohexyl formic acid hexanediol ester.Calculate according to the inventory of hexanediol, the separation molar yield of this ester
Being 93%, purity is 99.6%.
Embodiment 4: by 10mmol nonanediol, 22mmol hexahydrobenzoid acid, 0.15mmol Sb2O3Join 50mL
In round-bottomed flask.It is heated to 200 DEG C；React 5h at such a temperature.Then carry out decompression distillation and obtain two hexamethylenes
Base formic acid nonanediol ester.Calculating according to the inventory of nonanediol, the separation molar yield of this ester is 99%, purity
It is 99.9%.
Embodiment 5: by 10mmol decanediol, 24mmol hexahydrobenzoid acid, 0.2mmol Sb2(OCH2CH2O)3
Join in 50mL round-bottomed flask.It is heated to 240 DEG C；React 3h at such a temperature.Then carry out decompression to steam
Evaporate and obtain dicyclohexyl formic acid decanediol ester.Calculate according to the inventory of decanediol, the separation molar yield of this ester
Being 98%, purity is 99.8%.
Embodiment 6: by 10mmol decanediol, 26mmol hexahydrobenzoid acid, 0.3mmol Sb (OAc)2Join 50
In mL round-bottomed flask.It is heated to 210 DEG C；React 1.5h at such a temperature.Then carry out decompression distillation and obtain two
Hexahydrobenzoid acid decanediol ester.Calculating according to the inventory of decanediol, the separation molar yield of this ester is 96%,
Purity is 99.7%.
The present invention develops technology of preparing and the method for a dicyclohexyl formic acid binary alcohol esters.At catalyst action
Under, by the esterification of hexahydrobenzoid acid Yu dihydroxylic alcohols, product separation purification process, efficient, high-quality
Prepare dicyclohexyl formic acid binary alcohol esters.For exploitation novel non-toxic plasticizer, it is provided that sustainable development new
Technology and innovative approach, have important scientific meaning and using value.
Claims (6)
1. the preparation method of a dicyclohexyl formic acid binary alcohol esters plasticizer, it is characterised in that: with cyclohexyl first
Acid and dihydroxylic alcohols are raw material, at catalyst action, hexahydrobenzoid acid and dihydroxylic alcohols by esterification, Jing Guochun
Change and separate, obtain dicyclohexyl formic acid binary alcohol esters product；
The catalyst of described use is: Sb2O3、Sb(OAc)2、Sb2(OCH2CH2O)3In one or two kinds with
Upper compounding ingredients.
Method the most according to claim 1, it is characterised in that:
The reaction temperature of the esterification of described hexahydrobenzoid acid and dihydroxylic alcohols is 80-250 DEG C, and the response time is
0.5-48h。
Method the most according to claim 1, it is characterised in that: dihydroxylic alcohols includes: two glycosides alcohol, dipropyl two
One or two or more kinds in alcohol, hexanediol, nonanediol, decanediol.
Method the most according to claim 1, it is characterised in that: catalyst amount is the 0.01-5.0 of dihydroxylic alcohols
Mol%；Dicyclohexyl formic acid in reaction raw materials and mol ratio 2.1-3.0:1 of dihydroxylic alcohols consumption.
Method the most according to claim 1, it is characterised in that: described esterification is under nitrogen protection
Carry out.
Method the most according to claim 1, it is characterised in that: the purification of dicyclohexyl formic acid binary alcohol esters
Separation method is decompression distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510202921.0A CN106045857A (en) | 2015-04-24 | 2015-04-24 | Preparation method for dicyclohexyl dihydric alcohol formate plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510202921.0A CN106045857A (en) | 2015-04-24 | 2015-04-24 | Preparation method for dicyclohexyl dihydric alcohol formate plasticizer |
Publications (1)
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|---|---|
| CN106045857A true CN106045857A (en) | 2016-10-26 |
Family
ID=57179379
Family Applications (1)
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|---|---|---|---|
| CN201510202921.0A Pending CN106045857A (en) | 2015-04-24 | 2015-04-24 | Preparation method for dicyclohexyl dihydric alcohol formate plasticizer |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1519618A1 (en) * | 1966-12-08 | 1970-08-13 | Basf Ag | Carboxylic acid esters as a heat transfer agent |
| CN1032937A (en) * | 1988-10-11 | 1989-05-17 | 淄博市化工研究所 | The method for making of saturated fatty alcohol dibasic acid ester |
| CN1118158A (en) * | 1993-01-19 | 1996-03-06 | 埃克森化学专利公司 | Process for the production of plasticizer and polyol esters |
| CN1228411A (en) * | 1998-03-10 | 1999-09-15 | 辽阳市石油化工研究所 | Method for preparing mixed ester terephthalate |
| DE19927979A1 (en) * | 1999-06-18 | 2000-10-12 | Basf Ag | Preparation of alkylenediol dicyclohexanoate, useful as nontoxic plasticizers, by hydrogenation of the dibenzoate over Group 8 metal catalyst on macroporous carrier |
| CN101139293A (en) * | 2007-08-17 | 2008-03-12 | 郭立耀 | Method for producing dioctyl terephthalate |
| 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 |
| CN103086891A (en) * | 2013-02-22 | 2013-05-08 | 厦门大学 | Preparation method of plasticizer diethylene glycol dibenzoate |
-
2015
- 2015-04-24 CN CN201510202921.0A patent/CN106045857A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1519618A1 (en) * | 1966-12-08 | 1970-08-13 | Basf Ag | Carboxylic acid esters as a heat transfer agent |
| CN1032937A (en) * | 1988-10-11 | 1989-05-17 | 淄博市化工研究所 | The method for making of saturated fatty alcohol dibasic acid ester |
| CN1118158A (en) * | 1993-01-19 | 1996-03-06 | 埃克森化学专利公司 | Process for the production of plasticizer and polyol esters |
| CN1228411A (en) * | 1998-03-10 | 1999-09-15 | 辽阳市石油化工研究所 | Method for preparing mixed ester terephthalate |
| DE19927979A1 (en) * | 1999-06-18 | 2000-10-12 | Basf Ag | Preparation of alkylenediol dicyclohexanoate, useful as nontoxic plasticizers, by hydrogenation of the dibenzoate over Group 8 metal catalyst on macroporous carrier |
| CN101139293A (en) * | 2007-08-17 | 2008-03-12 | 郭立耀 | Method for producing dioctyl terephthalate |
| 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 |
| CN103086891A (en) * | 2013-02-22 | 2013-05-08 | 厦门大学 | Preparation method of plasticizer diethylene glycol dibenzoate |
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Application publication date: 20161026 |