CN105384630B - Hexylene glycol ester of citric acid three and preparation method thereof - Google Patents
Hexylene glycol ester of citric acid three and preparation method thereof Download PDFInfo
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- CN105384630B CN105384630B CN201510790012.3A CN201510790012A CN105384630B CN 105384630 B CN105384630 B CN 105384630B CN 201510790012 A CN201510790012 A CN 201510790012A CN 105384630 B CN105384630 B CN 105384630B
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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
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
- C07C69/704—Citric acid esters
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Abstract
The present invention relates to a kind of preparation method of the hexylene glycol ester of citric acid three, comprise the following steps：200ml acetonitrile solutions are added in the reaction vessel with thermometer, 0.1mol citric acids and 0.1 ~ 0.14mol condensing agent TBTU is added, after stirring and evenly mixing, to 0.18 ~ 0.22mol triethylamines are added in above reaction solution, stirred 0.4 ~ 1.0 hour at room temperature；Addition 0.3 ~ 0.44mol hexylene glycols in mixed liquor are stated then up, are stirred at 40 ~ 55 DEG C 0.4 ~ 0.8 hour to the prepared hexylene glycol ester finished product of citric acid three of reaction end.Present invention process esterification yield is high, and temperature is low needed for reaction, the time is short, while the accessory substance of condensing agent TBTU is dissolved in water, can be removed by washing, and the obtained hexylene glycol ester of citric acid three has the advantages that volatility is small, resistance to migration is good.
Description
Technical field
The present invention relates to a kind of citrate and preparation method thereof, and in particular to a kind of hexylene glycol ester of citric acid three and its system
Preparation Method.
Background technology
Plasticizer, is called plasticiser, is added to increase material plasticity in high molecular polymer, is allowed to easy processing, assigns
The functional product of product softness, is widely used in the plastic products such as toy, construction material, auto parts machinery.Plasticizer
Species is various, and the kind of current commercialization has kind more than 50, and major product is with dioctyl phthalate（DOP）, phthalic acid
Dibutyl ester（DBP）Based on phthalate, 90% of overall consumption or so is accounted in real consumption.
The volatility and animal migration of phthalic ester plasticizer are strong, belong to carcinogen, toxic to human heart
Effect, can cause " estrogen effect ".2012, domestic all multi-brand white wine was exceeded by exposure plasticizer loading, and case-involving is exactly
Such plasticizer.Because phthalic ester plasticizer has the developed countries such as above-mentioned harmfulness, North America, West Europe, Japan equal
Corresponding laws and regulations are promulgated, has been used for having made strict regulations.
Citric acid ester plasticizer has the advantages that good compatibility, speedup efficiency high, volatility are good, nontoxic, belongs to green
Environmentally friendly class plasticizer, its speedup effect is suitable with phthalic ester plasticizer, it is considered to be the tradition such as phthalic acid ester
The ideal substitute of plasticizer.Citric acid ester plasticizer principal item includes triethyl citrate（TEC）, acetyl tributyl citrate three
Ethyl ester（ATEC）, tri-n-butyl citrate（TBC）, the secondary butyl ester of citric acid three, tripentyl citrates, ATBC
（ATBC）, trioctyl lemon acid, ATOC, citric acid tri-n-hexyl ester（THC）, ATHC
（ATHC）, butyryl citric acid tri-n-hexyl ester etc..Wherein, it is the most commonly used with TBC and ATBC.But low-carbon alcohols esters, exist and easily wave
Hair, non-refractory and the shortcoming for easily migrating.
Citrate is esterified under catalyst action by citric acid and corresponding alcohol and obtained, and the most frequently used catalyst is mainly dense
Sulfuric acid, its cheap, catalysis activity is high, but has that equipment corrosion is serious, side reaction is more, waste liquid is difficult.With research
Deepen continuously, it has been found that multiple catalysts have good catalysis activity to esterification, such as：
1）Organic acid：Such as aminobenzenesulfonic acid and to pyrovinic acid, catalysis activity and selectivity are very high, and side reaction is less, right
The advantages of corrosivity of equipment and smaller environmental pollution, using wider；
2）Solid super-strong acid：Such as SO4 2-/MxOyType and S2O8 2-/MxOyType solid acid catalyst, with not etching apparatus, no
Pollution environment, high income, selectivity is good, can reuse, it is easy to the advantages of reactants separate；
3）Heteropoly acid：It is polyacid complex that a class contains oxygen bridge, active high, reaction speed is fast, to equipment
Corrosion-free the features such as；
4）Ionic liquid：Clear superiority is that product ester does not dissolve in ionic liquid, and product is easily isolated with catalyst, from
Sub- liquid can be reused through dewater treatment.
The defect such as more or less there is short life, be easy to run off in addition to possessing the advantage of itself uniqueness in above-mentioned catalyst,
Using limited or relatively costly, it is unfavorable for industrialized production.
TBTU is a kind of urea ionic polypeptide condensation reagent, is commonly applied to the coupling reagent of the synthesis of solid-phase polypeptide.
At present, TBTU condensing agents have been achieved for certain application in organic synthesis, and it has selectivity to alcoholic extract hydroxyl group, only
The esterification of the tertiary alcohol and primary alconol and carboxylic acid can be catalyzed, and the reaction for promoting not only has yield higher, also with conventional
The holding time of organic solvent is long, and the accessory substance of reaction is water-soluble, reacts the advantages of being carried out at general temperature, at present not
See that the material is applied in the reaction of the hexylene glycol ester of synthesizing citric acid three.
The molecular structure and tautomeric forms of TBTU are as follows：
The content of the invention
The present invention is directed to disadvantage mentioned above, it is desirable to provide a kind of to prepare low new of resistance to migration, volatility by condensing agent of TBTU
Type citric acid ester plasticizer.The new plasticizer chemical constitution is as follows：
。
It is the hexylene glycol ester of citric acid three by the Compound nomenclature according to nomenclature of organic compound rule.
To achieve the above object, the present invention is adopted the following technical scheme that：
The preparation method of the hexylene glycol ester of citric acid three, esterification is carried out with citric acid and hexylene glycol raw material, is with TBTU
Condensing agent, acetonitrile solution are solvent, and add triethylamine, and reaction is obtained the hexylene glycol ester of citric acid three.
Described condensing agent TBTU is 2-（1H- benzo trisazo- L-1- bases）- 1,1,3,3- tetramethylurea tetrafluoro boric acid ester,
It is a kind of urea ionic polypeptide condensation reagent.
The ratio between described citric acid and the amount of material of condensing agent TBTU are 1:1.0~1.4.
Preferably, the ratio between amount of material of described citric acid and condensing agent TBTU is 1:1.2.
The ratio between described citric acid and the amount of material of hexylene glycol are 1:3.0~4.4.
Described triethylamine can provide alkaline environment for solution, and the amount for adding the material of triethylamine is the amount of lemon acid substance
2.0 ~ 2.2 times.
Described esterification is concretely comprised the following steps：200ml acetonitrile solutions are added to the reaction vessel with thermometer
In, add 0.1mol citric acids and 0.1 ~ 0.14mol condensing agent TBTU, after stirring and evenly mixing, in above reaction solution add 0.18 ~
0.22mol triethylamines, stir 0.4 ~ 1.0 hour at room temperature；State then up add in mixed liquor 0.3 ~ 0.44mol oneself two
Alcohol, extremely reaction in 0.4 ~ 0.8 hour is stirred at 40 ~ 55 DEG C and is terminated.
After described reaction terminates, by solution left standstill, treat that temperature is down to room temperature, after being cleaned with distilled water, use dichloromethane
Extraction, gained organic layer is cleaned with the saturated common salt aqueous solution.
Solution after described cleaning is also dried through anhydrous magnesium sulfate, filtering, vacuum concentration, obtain citric acid three oneself two
Alcohol ester sterling.
Compared with prior art, it is an advantage of the invention that：
1st, esterification yield of the present invention is high, the reaction time is short, and reaction can be carried out under general temperature, usual pressure, be reacted
Journey condition is not harsh, while simpler to the purification processes of reactant；
2nd, present invention condensing agent TBTU used, shelf lives are long in conventional organic solvent, good stability, what reaction was produced
Accessory substance HOBt is dissolved in water, can be removed by washing, small to environmental hazard；
3rd, present invention condensing agent TBTU used has selectivity to alcoholic extract hydroxyl group, and the esterification of the tertiary alcohol and primary alconol can only be facilitated anti-
Should, expand the range of choice of alcohol in esterification；
4th, this method economy, environmental protection, are adapted to industrialized production, and the hexylene glycol ester of citric acid three of synthesis has plasticising performance good
Well, the advantages of volatility is small, resistance to migration is good, can be used as the preferred product of environmental protection plasticizer.
Brief description of the drawings
Accompanying drawing 1 is 2 tensile property testing results of experiment.
Specific embodiment
Following several specific embodiments are now enumerated to further illustrate the present invention program.It should be noted that following implement
Example is only used for help and understands the present invention program, is not the further restriction to the present invention program.
Embodiment 1
200ml acetonitrile solutions are added in the reaction bulb with thermometer, 0.1mol citric acids and 0.10mol contractings is added
Mixture TBTU, after stirring and evenly mixing, to 0.20mol triethylamines are added in above reaction solution, stirs 0.4 hour at room temperature；Then
To 0.30mol hexylene glycols are added in above-mentioned mixed liquor, extremely reaction in 0.4 hour is stirred at 40 DEG C and is terminated.After reaction terminates, will be molten
Liquid stands, and treats that temperature is down to room temperature, after being cleaned with distilled water, is extracted with dichloromethane, and gained organic layer is water-soluble with saturated common salt
Liquid is cleaned.Solution after cleaning is also dried through anhydrous magnesium sulfate, filtered, vacuum concentration, obtains the hexylene glycol ester of citric acid three pure
Product.
Embodiment 2
200ml acetonitrile solutions are added in the reaction bulb with thermometer, 0.1mol citric acids and 0.12mol contractings is added
Mixture TBTU, after stirring and evenly mixing, to 0.21mol triethylamines are added in above reaction solution, stirs 0.5 hour at room temperature；Then
To 0.34mol hexylene glycols are added in above-mentioned mixed liquor, extremely reaction in 0.5 hour is stirred at 44 DEG C and is terminated.After reaction terminates, will be molten
Liquid stands, and treats that temperature is down to room temperature, after being cleaned with distilled water, is extracted with dichloromethane, and gained organic layer is water-soluble with saturated common salt
Liquid is cleaned.Solution after cleaning is also dried through anhydrous magnesium sulfate, filtered, vacuum concentration, obtains the hexylene glycol ester of citric acid three pure
Product.
Embodiment 3
200ml acetonitrile solutions are added in the reaction bulb with thermometer, 0.1mol citric acids and 0.13mol contractings is added
Mixture TBTU, after stirring and evenly mixing, to 0.21mol triethylamines are added in above reaction solution, stirs 0.8 hour at room temperature；Then
To 0.38mol hexylene glycols are added in above-mentioned mixed liquor, extremely reaction in 0.6 hour is stirred at 48 DEG C and is terminated.Other steps are with implementation
Example 1.
Embodiment 4
200ml acetonitrile solutions are added in two mouthfuls of flasks with thermometer, 0.1mol citric acids and 0.14mol is added
Condensing agent TBTU, after stirring and evenly mixing, to 0.22mol triethylamines are added in above reaction solution, stirs 1.0 hours at room temperature；So
0.40mol hexylene glycols are added in backward above-mentioned mixed liquor, extremely reaction in 0.8 hour is stirred at 55 DEG C and is terminated.Other steps are with real
Apply example 1.
Embodiment 5
200ml acetonitrile solutions are added in two mouthfuls of flasks with thermometer, 0.1mol citric acids and 0.14mol is added
Condensing agent TBTU, after stirring and evenly mixing, to 0.22mol triethylamines are added in above reaction solution, stirs 1.0 hours at room temperature；So
0.44mol hexylene glycols are added in backward above-mentioned mixed liquor, extremely reaction in 0.8 hour is stirred at 55 DEG C and is terminated.Other steps are with real
Apply example 1.
Experimental example 1-5
Plasticizer is mainly used in polyvinyl chloride（PVC）In, more than the 80% of aggregate consumption is accounted for, therefore by obtained by embodiment 1-5
Product is added in PVC sample, the PVC sample containing the hexylene glycol ester 5%, 10%, 20%, 30% of citric acid three is prepared, for coherent detection.
Contrast experiment's example 1-3
By triethyl citrate（TEC）, ATEC（ATEC）, tri-n-butyl citrate（TBC）Add PVC
In sample, prepare contain triethyl citrate respectively（TEC）, ATEC（ATEC）, tri-n-butyl citrate（TBC）
5%th, 10%, 20%, 30% PVC sample, for coherent detection.
Test 1 product sign
1.1 elementary analyses
Elementary analysis carbon atom mass percent is 58.5%, and hydrogen atom mass percent is 9.0%, oxygen atom quality percentage
Than being 32.5%, thus it is speculated that its molecular formula is C24H44O10。
1.2 infrared analysis
In infared spectrum, 3262cm-1The absworption peak wide and strong that place produces for O-H stretching vibrations, 2942,2868cm-1Place
It is alkyl stretching vibration absworption peak, 1726cm-1Locate to be the strong stretching vibration absworption peaks of ester bond C=O, 1471cm-1Locate to deform for alkyl
Vibration absorption peak, 1179cm-1Locate the strong stretching vibration absworption peak for C-O-C.
1.3 nuclear magnetic resonance
Proton nmr spectra structural characterization data are as follows：1H NMR (500 MHz, CDCl3) δ:1.17-1.18（D,
9H）, δ:1.43（S, 18H）, δ:1.64（D, 6H）, δ:2.74（S, 4H）, δ:3.56-3.67（M, 4H）, it is oneself at displacement 1.18
The methyl of glycol chain end；It is two methyl being connected with C-O on hexylene glycol chain at displacement 1.43；It is hexylene glycol at displacement 1.64
Methylene on chain；It is the methylene being connected with C=O on citric acid at displacement 2.74；It is the hydroxyl on citric acid at displacement 3.65
Base, there is a hydroxyl on the different alcohol of nonyl at displacement 3.57.
Test 2 tensile properties
Reference standard GB/T1040.3-2006 carries out tensile property test, testing result as shown in Figure 1, citric acid three
The tensile strength of hexylene glycol ester is 16.6Mpa, and elongation at break can match in excellence or beauty up to more than 380% with TEC, ATEC, TBC.
The mechanical property of Fig. 1 polyvinyl chloride resins
Test 3 compatibilities
Solution-casting method is that PVC and plasticizer are dissolved in common good solvent, and solution then is paved into film, is heated
Solvent is removed, then observes the filminess after evaporating solvent.Clear shows that compatibility is good.Heating precipitation is to be plasticized
PVC sample is placed in the interior heating certain hour of baking oven to observe the precipitation of PVC surface plasticizer.The good plasticized PVC table of compatibility
State is not glued in face to dry, otherwise surface has liquid precipitation.As shown in table 1, four kinds of different polyvinyl chloride resins are showed testing result
Good compatibility, and four without significant difference.
The compatibility test of the polyvinyl chloride resin of table 1
Test 4 speedup efficiency
Plasticizing efficiency is, to add a certain amount of plasticizer in resin, to reach a certain hardness number, or a certain machinery
During the physical indexs such as intensity, how much the amount of required plasticizer judges that plasticising dosage used is fewer, then it represents that plasticizing efficiency is got over
It is high.Generally using dioctyl phthalate (DOP) as standard of comparison, setting value is 1, other plasticizer compared with it, referred to as
Efficiency ratios, efficiency ratios are smaller, then it represents that the efficiency of the plasticizer is higher.By embodiment 1-5 gained plasticizer citric acid three
Hexylene glycol ester carries out speedup efficiency, and and triethyl citrate（TEC）, ATEC（ATEC）, citric acid three just
Butyl ester（TBC）Compare, as shown in table 2, efficiency ratios reduce testing result as the accounting of each plasticizer increases, and work as plasticizer
When accounting is 30%, the hexylene glycol ester efficiency ratios of citric acid three are optimal.
The speedup efficiency ratios of the plasticizer of table 2
Claims (5)
1. a kind of preparation method of plasticizer compounds, it is characterised in that compound is shown below：
Esterification is carried out with citric acid and hexylene glycol raw material, with TBTU as condensing agent, acetonitrile solution as solvent, and add three second
Amine, reaction is obtained the hexylene glycol ester of citric acid three：The ratio between amount of material of citric acid and condensing agent TBTU is 1:1.0~1.4, lemon
The ratio between amount of material of acid and hexylene glycol is 1:3.0~4.4.
2. preparation method according to claim 1, it is characterised in that：Described triethylamine can provide alkaline ring for solution
Border, the amount for adding the material of triethylamine is 2.0~2.2 times of the amount of lemon acid substance.
3. preparation method according to claim 1, it is characterised in that：The esterification is concretely comprised the following steps：By 200ml
Acetonitrile solution is added in the reaction vessel with thermometer, adds 0.1mol citric acids and 0.1~0.14mol condensing agents
TBTU, after stirring and evenly mixing, to 0.18~0.22mol triethylamines are added in above reaction solution, stirs 0.4~1.0 small at room temperature
When；State then up and 0.3~0.44mol hexylene glycols are added in mixed liquor, 0.4~0.8 hour is stirred at 40~55 DEG C to anti-
Should terminate.
4. preparation method according to claim 3, it is characterised in that：After reaction terminates, by solution left standstill, treat that temperature is down to
Room temperature, after being cleaned with distilled water, is extracted with dichloromethane, and gained organic layer is cleaned with the saturated common salt aqueous solution.
5. method according to claim 4, it is characterised in that：Solution after cleaning is also dried through anhydrous magnesium sulfate, mistake
Filter, vacuum concentration, obtain the hexylene glycol ester sterling of citric acid three.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803845A (en) * | 2014-09-29 | 2015-07-29 | 湖南尔康制药股份有限公司 | Synthetic method of medicinal citrate |
| CN104892418A (en) * | 2015-06-02 | 2015-09-09 | 湖南尔康制药股份有限公司 | Synthesis method of citric acid tributyl citrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803845A (en) * | 2014-09-29 | 2015-07-29 | 湖南尔康制药股份有限公司 | Synthetic method of medicinal citrate |
| CN104892418A (en) * | 2015-06-02 | 2015-09-09 | 湖南尔康制药股份有限公司 | Synthesis method of citric acid tributyl citrate |
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