CN102381965A - Method for ultrasonically synthesizing diester nylon acid - Google Patents
Method for ultrasonically synthesizing diester nylon acid Download PDFInfo
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- CN102381965A CN102381965A CN2011102583519A CN201110258351A CN102381965A CN 102381965 A CN102381965 A CN 102381965A CN 2011102583519 A CN2011102583519 A CN 2011102583519A CN 201110258351 A CN201110258351 A CN 201110258351A CN 102381965 A CN102381965 A CN 102381965A
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Abstract
The invention belongs to the organic chemistry field, and relates to a method for ultrasonically synthesizing diester nylon acid. The method comprises the following steps: 1) esterification reaction: putting nylon acid, dihydric alcohol and concentrated sulfuric acid in a reaction vessel according to proportion, unlatching supersonic wave and keeping the temperature, taking out the reaction vessel after finishing the reaction, transferring milky emulsified mother liquor in a separator; 2) alkali liquor washing and neutralization: standing and layering, separating and removing sulfuric acid at a lower layer, washing mother liquor to pH>3, adding alkali liquor and washing to alkalescence of pH, and washing to neutrality of pH. 3) underpressure distillation, dealcoholization and refinement: drying the washed mother liquor, performing underpressure distillation at low temperature, removing dihydric alcohol, and continuously heating the dealcoholized mother liquor until the dealcoholization is steamed, wherein the product is colorless transparent liquid. According to the invention, the method uses ultrasonic preparation, low temperature condition and heterogeneous phase esterification after feeding, so that the method for ultrasonically synthesizing diester nylon acid is capable of saving equipment investment, reducing the cost, shortening the production time, raising production efficiency and raising product quality.
Description
Technical field
The invention belongs to organic chemistry filed, relate to a kind of method with UW synthetic nylon acid dibasic acid esters.
Background technology
Fatty group dibasic acid is as cold resistant plasticizer, have that low-temperature performance is good, shock-resistance good, plasticizing efficiency is high and characteristics such as viscosity performance is good, but the cost of fatty group dibasic acid is higher.The by product nylon acid of synthesizing adipic acid (mixture of Succinic Acid, pentanedioic acid and hexanodioic acid) has caused people's attention as the raw material of softening agent, is that mixed dibasic acid ester more than this C4 of raw material production is as the PVC softening agent by nylon acid; Has good low-temperature resistance property; Plasticizing efficiency is high, and heated discoloration is little, advantages such as environment-protecting asepsis; Can be used as the surrogate of Octyl adipate (DOA) and dioctyl sebacate (DOS), but also have the effect that prevents that surface electrostatic from gathering.
The method of synthetic fat family dibasic acid esters is mainly the direct heating esterification process at present: be homogeneous system with the sample mix uniform dissolution in advance; Temperature of reaction higher (greater than 150 ℃); Need to add band aqua (toluene, benzene, hexanaphthene etc.) and catalyst sulfuric acid; The alkali lye neutralization, underpressure distillation, the product colour that obtains is yellow partially.The shortcoming of this method is 1. complex manufacturing as follows, and cost is high; 2. product is yellow partially, needs further refining; 3. temperature of reaction is high, and the PT is long, and efficient is low etc.
Summary of the invention
The objective of the invention is to overcome 1. complex manufacturing, cost is high; 2. product is yellow partially, needs further refining; The deficiency of prior aries such as 3. temperature of reaction is high, and the PT is long, and efficient is low provides a kind of ultrasonic method for preparing the nylon acid dibasic acid esters.
A kind of ultrasonic method for preparing the nylon acid dibasic acid esters may further comprise the steps:
1) esterification: nylon acid and divalent alcohol ingredient proportion are 1:2-1:3.5, and the catalyzer vitriol oil volume that feeds intake is that the mole number ratio of the vitriol oil and nylon acid is 10-40mL/mol, drops in the reaction kettle; Need not dissolve mixing in advance is homogeneous system, and the direct unlatching in the back UW that feeds intake (40Hz, 500W); Pick up counting, temperature keeps 30-70 ℃ in the reaction process, and the reaction times is about 1.5h-4h; Close UW; The milk sap that reacted mother liquor is creamy white takes out the mother liquor in the reaction kettle, and it is transferred in the tripping device.
2) washing neutralizes: leave standstill after pouring the mother liquor after the esterification into tripping device, and system layering, lower floor is a catalyst sulfuric acid; The upper strata is colourless organic mixture; Separate to remove lower floor's sulfuric acid, isolated sulfuric acid is reusable, and residual sulfuric acid and the first water of organic acid or saturated NaCl solution washing are to PH in the reaction solution>3; Add the alkali lye repeated oscillation again to alkalescence, water or saturated NaCl solution washing are to neutral again.
3) dealcoholysis: after the mother liquor drying after will washing, divalent alcohol is sloughed in oil pump underpressure distillation at low temperatures, and the divalent alcohol that steams is reusable.
4) underpressure distillation is refining: the mother liquor after the dealcoholysis continues to heat up, and can steam pure nylon acid dibasic acid esters until the boiling range temperature, and product is a colourless transparent liquid.
Present method is used ultrasonic preparation, coldcondition, and the back direct esterification that feeds intake can be practiced thrift facility investment, reduces cost, and shortens the PT and enhances productivity and improve product quality.
Advantage of the present invention and innovative point are following:
1) this preparation method has used supersonic method to carry out esterification, and temperature is more much lower than direct heating esterification process, and temperature of reaction is at 30-70 ℃, side reaction seldom, the mother liquor color that obtains is very shallow; Supersonic method is a kind of effective ways of synthetic fat family dibasic ester, and action of ultrasonic waves only for reaction provides energy, does not play direct katalysis in reaction.
2) this preparation method has saved when producing in advance that biased sample is the step of homogeneous system, and the back that feeds intake is heterogeneous directly to begin reaction, has practiced thrift facility investment, has saved the PT.
3) the static back of this preparing method's esterification mother liquor natural layering; Reuse after can telling vitriolization, the normal temperature alkali lye neutralization of washing back, the alkali lye consumption is few; Cost is practiced thrift in i.e. recycling, problems such as saponification of having avoided again occurring in the N-process and emulsification.
4) mother liquor need not made with extra care and can be used as the product sale after this preparation method dealcoholysis; Suitable with the product quality after the snead process underpressure distillation; The product that obtains after the underpressure distillation of present method mother liquor is a colourless transparent liquid, and quality product meets the technical requirements fully.
Embodiment
Through specific embodiment the present invention is done further detailed description below, following examples are descriptive, are not determinate, can not limit protection scope of the present invention with this.
Embodiment 1
The method of UW synthetic nylon acid dibasic acid esters may further comprise the steps:
1) esterification: in the 1:2 ratio, the mole number ratio of catalyst sulfuric acid volume and nylon acid is 10mL/mol with nylon acid, divalent alcohol, drops in the reaction kettle, and need not dissolve mixing in advance is homogeneous system; Feeding intake, (the 40Hz's direct unlatching in back UW 500W), picks up counting; Temperature keeps 30 ℃ in the reaction process, and the reaction times is about 4h, closes UW; Take out reaction kettle, the milk sap that reacted mother liquor is creamy white, and it is transferred in the tripping device.
2) washing neutralizes: leave standstill after pouring the mother liquor after the esterification into tripping device, and system layering, lower floor is a catalyst sulfuric acid; The upper strata is colourless organic mixture; Separate to remove lower floor's sulfuric acid, isolated sulfuric acid is reusable, and residual sulfuric acid and the first water of organic acid or saturated NaCl solution washing are to PH in the reaction solution>3; Add the alkali lye repeated oscillation again to alkalescence, water or saturated NaCl solution washing are to neutral again.
3) dealcoholysis: after the mother liquor drying after will washing, divalent alcohol is sloughed in oil pump underpressure distillation at low temperatures, and the divalent alcohol that steams is reusable.
4) underpressure distillation is refining: the mother liquor after the dealcoholysis continues to heat up, and can steam pure nylon acid dibasic acid esters until the boiling range temperature, and product is a colourless transparent liquid.
Embodiment 2
The method of UW synthetic nylon acid dibasic acid esters may further comprise the steps:
1) esterification: in the 1:2.5 ratio, the mole number ratio of catalyst sulfuric acid volume and nylon acid is 20mL/mol with nylon acid, divalent alcohol, drops in the reaction kettle, and need not dissolve mixing in advance is homogeneous system; Feeding intake, (the 40Hz's direct unlatching in back UW 500W), picks up counting; Keep 45 ℃ of temperature in the reaction process, the reaction times is about 3h, closes UW; Take out reaction kettle, the milk sap that reacted mother liquor is creamy white, and it is transferred in the tripping device.
2) washing neutralizes: leave standstill after pouring the mother liquor after the esterification into tripping device, and system layering, lower floor is a catalyst sulfuric acid; The upper strata is colourless organic mixture; Separate to remove lower floor's sulfuric acid, isolated sulfuric acid is reusable, and residual sulfuric acid and the first water of organic acid or saturated NaCl solution washing are to PH in the reaction solution>3; Add the alkali lye repeated oscillation again to alkalescence, water or saturated NaCl solution washing are to neutral again.
3) dealcoholysis: after the mother liquor drying after will washing, divalent alcohol is sloughed in oil pump underpressure distillation at low temperatures, and the divalent alcohol that steams is reusable.
4) underpressure distillation is refining: the mother liquor after the dealcoholysis continues to heat up, and can steam pure nylon acid dibasic acid esters until the boiling range temperature, and product is a colourless transparent liquid.
Embodiment 3
The method of UW synthetic nylon acid dibasic acid esters may further comprise the steps:
1) esterification: in the 1:3 ratio, the mole number ratio of catalyst sulfuric acid volume and nylon acid is 30mL/mol with nylon acid, divalent alcohol, drops in the reaction kettle, and need not dissolve mixing in advance is homogeneous system; Feeding intake, (the 40Hz's direct unlatching in back UW 500W), picks up counting; Keep 55 ℃ of temperature in the reaction process, the reaction times is about 2h, closes UW; Take out reaction kettle, the milk sap that reacted mother liquor is creamy white, and it is transferred in the tripping device.
2) washing neutralizes: leave standstill after pouring the mother liquor after the esterification into tripping device, and system layering, lower floor is a catalyst sulfuric acid; The upper strata is colourless organic mixture; Separate to remove lower floor's sulfuric acid, isolated sulfuric acid is reusable, and residual sulfuric acid and the first water of organic acid or saturated NaCl solution washing are to PH in the reaction solution>3; Add the alkali lye repeated oscillation again to alkalescence, water or saturated NaCl solution washing are to neutral again.
3) dealcoholysis: after the mother liquor drying after will washing, divalent alcohol is sloughed in oil pump underpressure distillation at low temperatures, and the divalent alcohol that steams is reusable.
4) underpressure distillation is refining: the mother liquor after the dealcoholysis continues to heat up, and can steam pure nylon acid dibasic acid esters until the boiling range temperature, and product is a colourless transparent liquid.
Embodiment 4
The method of UW synthetic nylon acid dibasic acid esters may further comprise the steps:
1) esterification: in the 1:3.5 ratio, the mole number ratio of catalyst sulfuric acid volume and nylon acid is 40mL/mol with nylon acid, divalent alcohol, drops in the reaction kettle, and need not dissolve mixing in advance is homogeneous system; Feeding intake, (the 40Hz's direct unlatching in back UW 500W), picks up counting; Keep 70 ℃ of temperature in the reaction process, the reaction times is about 1.5h, closes UW; Take out reaction kettle, the milk sap that reacted mother liquor is creamy white, and it is transferred in the tripping device.
2) washing neutralizes: leave standstill after pouring the mother liquor after the esterification into tripping device, and system layering, lower floor is a catalyst sulfuric acid; The upper strata is colourless organic mixture; Separate to remove lower floor's sulfuric acid, isolated sulfuric acid is reusable, and residual sulfuric acid and the first water of organic acid or saturated NaCl solution washing are to PH in the reaction solution>3; Add the alkali lye repeated oscillation again to alkalescence, water or saturated NaCl solution washing are to neutral again.
3) dealcoholysis: after the mother liquor drying after will washing, divalent alcohol is sloughed in oil pump underpressure distillation at low temperatures, and the divalent alcohol that steams is reusable.
Underpressure distillation is refining: the mother liquor after the dealcoholysis continues to heat up, and can steam pure nylon acid dibasic acid esters until the boiling range temperature, and product is a colourless transparent liquid.
Claims (3)
1. the method for UW synthetic nylon acid dibasic acid esters is characterized in that: may further comprise the steps:
Esterification: nylon acid and divalent alcohol ingredient proportion are 1:2-1:3.5, and the catalyzer vitriol oil volume that feeds intake is that the mole number ratio of the vitriol oil and nylon acid is 10-40mL/mol, drops in the reaction kettle; Directly unlatching UW of back feeds intake; Keep certain temperature in the reaction process, close UW, the milk sap that reacted mother liquor is creamy white behind the reaction certain hour; Take out the mother liquor in the reaction kettle, it is transferred in the tripping device;
The neutralization of washing alkali lye: behind the standing demix, separate and remove sub-cloud sulfuric acid, water or saturated NaCl solution washing mother liquor are to PH>3, add alkali lye again and be washed till alkalescence, water or saturated NaCl solution washing are to neutral again;
Dealcoholysis: the mother liquor after will washing is dry, and divalent alcohol is sloughed in oil pump underpressure distillation at low temperatures;
Underpressure distillation is refining: the mother liquor after the dealcoholysis continues to heat up, and until steaming pure nylon acid dibasic acid esters, product is a colourless transparent liquid.
2. the method for UW synthetic nylon acid dibasic acid esters according to claim 1, it is characterized in that: esterification reaction temperature is 30-70 ℃.
3. the method for UW synthetic nylon acid dibasic acid esters according to claim 1, it is characterized in that: reaction time of esterification is 1.5h-4h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102583519A CN102381965A (en) | 2011-09-02 | 2011-09-02 | Method for ultrasonically synthesizing diester nylon acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011102583519A CN102381965A (en) | 2011-09-02 | 2011-09-02 | Method for ultrasonically synthesizing diester nylon acid |
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| CN102381965A true CN102381965A (en) | 2012-03-21 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997031967A1 (en) * | 1996-02-29 | 1997-09-04 | Rhone-Poulenc Fibres & Polymeres S.A. | Method for producing polyester |
| CN101003707A (en) * | 2006-01-20 | 2007-07-25 | 郭颖 | High performance, environmental protective composition of insulating coating prepared by using recycling resources |
| CN101318905A (en) * | 2008-07-15 | 2008-12-10 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing gallic acid terpene alcohol ester with auxiliary supersonic wave |
| EP2270065A2 (en) * | 2004-12-21 | 2011-01-05 | E. I. du Pont de Nemours and Company | Poly(trimethylene terephthalate) composition and shaped articles prepared therefrom |
| CN101955577A (en) * | 2010-10-13 | 2011-01-26 | 东华大学 | Method for preparing polyester material with secondary yield stress |
-
2011
- 2011-09-02 CN CN2011102583519A patent/CN102381965A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997031967A1 (en) * | 1996-02-29 | 1997-09-04 | Rhone-Poulenc Fibres & Polymeres S.A. | Method for producing polyester |
| EP2270065A2 (en) * | 2004-12-21 | 2011-01-05 | E. I. du Pont de Nemours and Company | Poly(trimethylene terephthalate) composition and shaped articles prepared therefrom |
| CN101003707A (en) * | 2006-01-20 | 2007-07-25 | 郭颖 | High performance, environmental protective composition of insulating coating prepared by using recycling resources |
| CN101318905A (en) * | 2008-07-15 | 2008-12-10 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing gallic acid terpene alcohol ester with auxiliary supersonic wave |
| CN101955577A (en) * | 2010-10-13 | 2011-01-26 | 东华大学 | Method for preparing polyester material with secondary yield stress |
Non-Patent Citations (2)
| Title |
|---|
| 周勇 等: "催化合成二元酸酯的研究", 《河南师范大学学报(自然科学版)》 * |
| 崔慧 等: "尼龙酸二甲酯的色质联用分析", 《聊城大学学报（自然科学版）》 * |
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Application publication date: 20120321 |