CN104163760A - Poly triethyl citrate and preparation method thereof - Google Patents

Poly triethyl citrate and preparation method thereof Download PDF

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CN104163760A
CN104163760A CN201410341025.8A CN201410341025A CN104163760A CN 104163760 A CN104163760 A CN 104163760A CN 201410341025 A CN201410341025 A CN 201410341025A CN 104163760 A CN104163760 A CN 104163760A
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acid
citric acid
preparation
ester
acyl chlorides
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CN104163760B (en
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潘春跃
喻桂朋
崔霁第
刘青山
郑大田
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Central South University
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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
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • 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
    • 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
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids

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Abstract

The invention discloses a poly triethyl citrate and a preparation method thereof, and the preparation method of the poly triethyl citrate is as follows: first, citric acid reacts with an alcohol to prepare triethyl citrate, poly acyl chloride is prepared by acylation of the poly carboxylic acid, and then the poly triethyl citrate is prepared by esterification reaction of the poly acyl chloride and the triethyl citrate; the preparation method has the advantages of simple operation, wide source of raw materials, and mild reaction conditions, and can meet the industrial production, the prepared poly triethyl citrate has both good plasticizing effect and excellent thermal stability, low temperature flexibility, solvent extraction resistance and transfer resistance, and can be widely used for plastic rubber plasticizers.

Description

A kind of many citric acid three esters and preparation method thereof
Technical field
The present invention relates to a kind of many citric acid three esters and preparation method thereof, belong to plastic, rubber plasticizer technical field.
Background technology
Softening agent has been production capacity and since consumption maximum classification, especially eighties in 20th century in plastic processing additives, and along with continually developing of polyvinyl chloride (PVC) goods, softening agent industry more presents the situation of advancing by leaps and bounds.With abroad comparing, China's softening agent kind is single a little, and mainly taking phthalic ester as main, wherein dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP) proportion are larger.Due to the toxicity problem that softening agent exists, some Application Areass of traditional primary plasticizer are restricted, as research shows that DOP, DBP may exist potential carcinogenic danger, and can be carcinogenic containing phenyl ring in bis phthalate (DEHP) structure.A lot of countries have taked corresponding restriction, forbid that this type of softening agent is applied to the plastics such as food product pack, makeup and toy for children.
Citric acid three ester class softening agent is synthetic taking citric acid as main raw material, because it is nontoxic, safety, now become one of environment-friendly type softening agent of domestic and international plastics industry first-selection, its main kind has triethyl citrate (TEC), acetyl triethyl citrate (ATEC), ATBC (ATBC), tri-n-butyl citrate (TBC), citric acid tri-n-hexyl ester (THC), ATHC (ATHC) etc.But because molecular weight is little, the number ratio (A of nonpolar fatty carbonatoms and polarity ester group p/ A o) reason such as improper, still there is thermostability in current citric acid three ester softening agent, low temperature kindliness, the shortcoming such as the extractable of resistance to solvent and anti-transport property are not good in actual use.Researcher has been made improvement to citric acid three ester softening agent, as Octadecanoyl tributyl citrate (CN101255240A), oleoyl tributyl citrate (CN101255114A), the exploitation of a series of products such as maleic acid tributyl citrate diester (CN101781213A); Developed two citric acid three esters (US3239555, CN1037350A) is that two citric acid three ester molecules are connected to form to a two citric acid three ester molecule by aliphatic chain (carbonatoms is generally 1～12) simultaneously; Although the two citric acid three ester molecules of this class have improved plasticization effect to a certain extent, but still do not overcome the shortcomings such as thermostability, low temperature kindliness, the extractable of resistance to solvent and anti-transport property be poor, its application is limited to, can not be met current demand.
Summary of the invention
For the defect of of the prior art pair of citric acid three ester class softening agent existence, the object of the invention is to be to provide a kind of many citric acid three esters of the thermostability, low temperature kindliness, the extractable of resistance to solvent and the anti-transport property that simultaneously have good plasticization effect and excellence concurrently.
Another object of the present invention is to be to provide that a kind of raw material sources are wide, simple to operate, the method for the described many citric acid three esters of the gentle preparation of reaction conditions.
The invention provides a kind of many citric acid three esters, these many citric acid three esters have structure shown in formula 1 or formula 2:
Wherein,
In formula 1 and formula 2, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 11, R 12, R 13be selected from independently of one another the alkyl of C4～C12;
R 10for a kind of in the substituted radical of following center:
R 14for a kind of in the substituted radical of following center:
R in preferred many citric acid three esters 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 11, R 12, R 13be selected from independently of one another the one in C4～C12 straight chain or branch alkyl group.
Further R in preferred many citric acid three esters 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 11, R 12, R 13for identical group.
The preparation method of the many citric acid three esters described in the present invention also provides, this preparation method comprises the following steps:
Step (1): prepare citric acid three ester
C4～C12 alcohol excessive with carboxyl in relative citric acid citric acid is carried out to esterification under to the catalysis of benzene methanesulfonic acid and obtain citric acid three ester;
Step (2): prepare polynary acyl chlorides
Polycarboxylic acid is obtained to polynary acyl chlorides by phosphorus trichloride acidylate, and described polycarboxylic acid is trimesic acid, equal benzene nitrilotriacetic, 1,3,5-hexanaphthene tricarboxylic acid, 1,1, three acid of 2-second, the third three acid, 1,2,4-butane tricarboxylic acid, 1,3,5-penta tricarboxylic acid, pyromellitic acid, 1,2,3,4-BTCA, 1,2,3,4-tetramethylene tetracarboxylic acid or season penta tetracid;
Step (3): prepare many citric acid three esters
The polynary acyl chlorides that step (2) is made is slowly added drop-wise in the mixed system of citric acid three ester that step (1) makes and acid binding agent triethylamine and carries out esterification, to obtain final product.
The preparation method of many citric acid three esters of the present invention also comprises following preferred version:
In preferred scheme, in step (1), the reaction conditions of esterification is to react 3～6h under the temperature condition of 110～160 DEG C.
In preferred scheme, the mol ratio of the middle citric acid of step (1) and alcohol is 1:3～5.
In preferred scheme, polycarboxylic acid reacts 4～6h with excessive phosphorus trichloride and makes polynary acyl chlorides at the temperature of 50～70 DEG C.
In preferred scheme, in step (3), in polynary acyl chlorides and citric acid three ester, the mol ratio of acid chloride groups and hydroxyl is 1～1.2:1.
In preferred scheme, in step (3), the reaction conditions of esterification is first polynary acyl chlorides to be slowly added drop-wise in the mixed solution of citric acid three ester and acid binding agent to react in ice-water bath, and after being added dropwise to complete, 2～4h is reacted in continuation in ice-water bath.
The alcohol mixture that can add by a certain percentage C4～C12 in preferred scheme in step (1), obtains the citric acid three ester that different alkyl replace, and more preferably adds C4～C12 single alcohol.
The preparation method of many citric acid three esters of the present invention, comprises following concrete steps:
Step (1): prepare citric acid three ester
In reactor, add the single alcohol of alcohol mixture or the C4～C12 of C4～C12, add again benzene methanesulfonic acid, P-TOLUENE SULFO ACID 99's massfraction be citric acid and alcohol total mass 1～5%, and be with in right amount aqua toluene or hexanaphthene, under agitation be warming up to 110 DEG C～160 DEG C, reaction 3～6h; Reacted rear underpressure distillation and reclaimed alcohol excess, obtained citric acid three ester crude product, the sodium hydrogen carbonate solution washing citric acid three ester crude product of rear use 1%～4%, removes benzene methanesulfonic acid, reclaims organic phase and obtains citric acid three ester;
Step (2): prepare polynary acyl chlorides
Polycarboxylic acid is joined in reactor, in reactor, drip excessive phosphorus trichloride, at 50～70 DEG C of temperature, react 4～6h and obtain polynary acyl chlorides; Described polycarboxylic acid is trimesic acid, equal benzene nitrilotriacetics, 1,3,5-hexanaphthene tricarboxylic acid, 1,1, three acid of 2-second, the third three acid, 1,2,4-butane tricarboxylic acid, 1,3,5-penta tricarboxylic acid, pyromellitic acid, 1,2,3,4-BTCA, 1,2,3,4-tetramethylene tetracarboxylic acid or season penta tetracid;
Step (3): prepare many citric acid three esters
Reactor is placed in to ice-water bath, to the citric acid three ester that adds in reactor step (1) to make and the acid binding agent triethylamine of respective amount, in reactor, pass into nitrogen, the dichloromethane solution of the polynary acyl chlorides that slowly dropping step (2) makes, in polynary acyl chlorides and citric acid three ester, the mol ratio of acid chloride groups and hydroxyl is 1～1.2:1; After dripping, continue to react 2～4h in ice-water bath; Reaction product is washed to neutrality and is transferred to extracting and separating in ethyl acetate through the sodium hydrogen carbonate solution of 1wt%～8wt%, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 4～10h, filtrate obtains the many citric acid three esters of product through distillation except after desolventizing.
Beneficial effect of the present invention: the present invention connects traditional citric acid three ester to have synthesized a kind of novel many citric acid three esters by hydroxyl using polynary acyl group as bridge chain first; many citric acid three esters of this branching are as softening agent; citric acid three ester softening agent relatively of the prior art has better plasticization effect; and volatility is less; the performances such as anti-transport property, resistance to extractable, low temperature kindliness, weathering resistance and yellowing resistance improve simultaneously, have using value widely.The invention has the advantages that by polynary acyl group traditional citric acid three ester is connected into novel many citric acid three esters by hydroxyl; the relative molecular mass of citric acid three ester can be increased, the number ratio (A of nonpolar fatty carbonatoms and polarity ester group can be improved simultaneously p/ A o); Particularly many citric acid three esters of the preferred C4～C12 of the present patent application alkyl modified, volatility is little, plasticising for plastics and rubber has the advantages such as good anti-transport property, resistance to extractable, low temperature kindliness, weathering resistance and yellowing resistance, and nontoxic, can meet the plasticising requirement in food product pack, toy for children, the contour hygienic requirements of medicine equipment field.Whole preparation technology's raw material of the present invention is easy to get, with low cost, and simple to operate, and the product purity of acquisition is high, and productive rate is high, meets industrialization production requirements.
Brief description of the drawings
The third three infrared figure of sour three trioctyl lemon acid that [Fig. 1] embodiment 2 makes.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of limit the scope of the invention.Embodiment 1
The preparation of trimesic acid three tributyl citrates, comprises the following steps:
1) preparation of tributyl citrate: add 100mol citric acid in reactor, 380mol butanols, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 120 DEG C, back flow reaction 4h, alcohol excess is reclaimed in underpressure distillation, obtain tributyl citrate crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain tributyl citrate.
2) preparation of trimesoyl chloride: add 70mol trimesic acid in reactor, drip 210mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains trimesoyl chloride.
3) preparation of trimesic acid three tributyl citrates: add 100mol tributyl citrate and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 34mol trimesoyl chloride, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product trimesic acid three tributyl citrates through distillation except after desolventizing.
Embodiment 2
The preparation of the third three sour three tributyl citrates, comprises the following steps:
1) preparation of tributyl citrate: add 100mol citric acid in reactor, 400mol butanols, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 140 DEG C, back flow reaction 4h, alcohol excess is reclaimed in underpressure distillation, obtain tributyl citrate crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain tributyl citrate.
2) preparation of the third three acyl chlorides: add 70mol the third three acid in reactor, drip 210mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains the third three acyl chlorides.
3) preparation of the third three sour three tributyl citrates: add 100mol tributyl citrate and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 34mol the third three acyl chlorides, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate through distillation except obtaining product the third three sour three tributyl citrates after desolventizing.
Embodiment 3
The preparation of trimesic acid three trioctyl lemon acids, comprises the following steps:
1) preparation of trioctyl lemon acid: add 100mol citric acid in reactor, 380mol octanol, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 150 DEG C, back flow reaction 4h, alcohol excess is reclaimed in underpressure distillation, obtain trioctyl lemon acid crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain trioctyl lemon acid.
2) preparation of trimesoyl chloride: add 70mol trimesic acid in reactor, drip 200mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains trimesoyl chloride.
3) preparation of trimesic acid three trioctyl lemon acids: add 100mol trioctyl lemon acid and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 34mol trimesoyl chloride, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product trimesic acid three trioctyl lemon acids through distillation except after desolventizing.
Embodiment 4
The preparation of the third three sour three trioctyl lemon acids, comprises the following steps:
1) preparation of trioctyl lemon acid: add 100mol citric acid in reactor, 400mol octanol, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 150 DEG C, back flow reaction 5h, alcohol excess is reclaimed in underpressure distillation, obtain trioctyl lemon acid crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain trioctyl lemon acid.
2) preparation of the third three acyl chlorides: add 70mol the third three acid in reactor, drip 240mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains the third three acyl chlorides.
3) preparation of the third three sour three trioctyl lemon acids: add 100mol trioctyl lemon acid and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 34mol the third three acyl chlorides, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate through distillation except obtaining product the third three sour three trioctyl lemon acids after desolventizing.
Embodiment 5
The preparation of pyromellitic acid four trioctyl lemon acids, comprises the following steps:
1) preparation of trioctyl lemon acid: add 100mol citric acid in reactor, 380mol octanol, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 150 DEG C, back flow reaction 3h, alcohol excess is reclaimed in underpressure distillation, obtain trioctyl lemon acid crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain trioctyl lemon acid.
2) all preparations of benzene four acyl chlorides: add 70mol pyromellitic acid in reactor, drip 250mol phosphorus trichloride, stir and be warming up to 60 DEG C, reaction 5h, is cooled to room temperature, and stratification obtains equal benzene four acyl chlorides.
3) preparation of pyromellitic acid four trioctyl lemon acids: add 100mol trioctyl lemon acid and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains equal benzene four acyl chlorides of 25mol, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product pyromellitic acid four trioctyl lemon acids through distillation except after desolventizing.
Embodiment 6
Season penta tetracid four trioctyl lemon acids preparation, comprise the following steps:
1) preparation of trioctyl lemon acid: add 100mol citric acid in reactor, 380mol octanol, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 150 DEG C, back flow reaction 4h, alcohol excess is reclaimed in underpressure distillation, obtain trioctyl lemon acid crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain trioctyl lemon acid.
2) preparation of Ji Wusi acyl chlorides: add 70mol season penta tetracid in reactor, drip 250mol phosphorus trichloride, stir and be warming up to 60 DEG C, reaction 5h, is cooled to room temperature, and stratification obtains equal benzene four acyl chlorides.Stirring is warming up to 60 DEG C, and reaction 5h, is cooled to room temperature, and stratification obtains Ji Wusi acyl chlorides.
3) season penta tetracid four trioctyl lemon acids preparation: in reactor, add 100mol trioctyl lemon acid and appropriate acid binding agent anhydrous triethylamine, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 25mol seasons penta 4 acyl chlorides, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product season penta tetracid four trioctyl lemon acids through distillation except after desolventizing.
Embodiment 7
The preparation of trimesic acid three citric acid three bays (12) esters, comprises the following steps:
1) preparation of trioctyl lemon acid: add 100mol citric acid in reactor, 380mol lauryl alcohol (lauryl alcohol), to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 150 DEG C, back flow reaction 4h, alcohol excess is reclaimed in underpressure distillation, obtain citric acid three lauryl crude products, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain citric acid three lauryls.
2) preparation of trimesoyl chloride: add 70mol trimesic acid in reactor, drip 210mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains trimesoyl chloride.
3) preparation of trimesic acid three citric acid three lauryls: add 100mol citric acid three lauryls and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 34mol trimesoyl chloride, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product trimesic acid three citric acid three lauryls through distillation except after desolventizing.
Comparative example 1
The preparation of oxalic acid two trioctyl lemon acids, comprises the following steps:
1) preparation of trioctyl lemon acid: add 100mol citric acid in reactor, 380mol octanol, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 150 DEG C, back flow reaction 4h, alcohol excess is reclaimed in underpressure distillation, obtain trioctyl lemon acid crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain trioctyl lemon acid.
2) preparation of oxalyl chloride: add 70mol oxalic acid in reactor, drip 170mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains oxalyl chloride.
3) preparation of oxalic acid two tripentyl citrates: add 100mol tripentyl citrates and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 50mol oxalyl chloride, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product oxalic acid two trioctyl lemon acids through distillation except after desolventizing.
Comparative example 2
The preparation of succinic acid two trioctyl lemon acids, comprises the following steps:
1) preparation of trioctyl lemon acid: add 100mol citric acid in reactor, 380mol octanol, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 150 DEG C, back flow reaction 4h, alcohol excess is reclaimed in underpressure distillation, obtain trioctyl lemon acid crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain trioctyl lemon acid.
2) preparation of succinic chloride: add 70mol succinic acid in reactor, drip 170mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains diacid chloride.
3) preparation of succinic acid two trioctyl lemon acids: add 100mol trioctyl lemon acid and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 50mol succinic chloride, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product succinic acid two trioctyl lemon acids through distillation except after desolventizing.
Comparative example 3
The preparation of trimesic acid three trimethyl citrates, comprises the following steps:
1) preparation of trimethyl citrate: add 100mol citric acid in reactor, 380mol methyl alcohol, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 110 DEG C, back flow reaction 4h, Distillation recovery alcohol excess, obtain trimethyl citrate crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain trimethyl citrate.
2) preparation of trimesoyl chloride: add 70mol trimesic acid in reactor, drip 210mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains trimesoyl chloride.
3) preparation of trimesic acid three trimethyl citrates: add 100mol trimethyl citrate and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 34mol trimesoyl chloride, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product trimesic acid three trimethyl citrates through distillation except after desolventizing.
Comparative example 4
The preparation of trimesic acid three triethyl citrates, comprises the following steps:
1) preparation of triethyl citrate: add 100mol citric acid in reactor, 380mol ethanol, to benzene methanesulfonic acid (massfraction be citric acid and alcohol total mass 2%) and 40L band aqua hexanaphthene, under stirring, be warming up to 110 DEG C, back flow reaction 4h, Distillation recovery alcohol excess, obtain triethyl citrate crude product, wash citric acid three ester crude product with 2% sodium hydrogen carbonate solution afterwards, remove catalyzer, reclaim organic phase and obtain triethyl citrate.
2) preparation of trimesoyl chloride: add 70mol trimesic acid in reactor, drip 210mol phosphorus trichloride, stir and be warming up to 60 DEG C, be cooled to room temperature, stratification obtains trimesoyl chloride.
3) preparation of trimesic acid three triethyl citrates: add 100mol triethyl citrate and appropriate acid binding agent anhydrous triethylamine in reactor, in reactor, pass into nitrogen, at 0 DEG C, drip the dichloromethane solution that contains 34mol trimesoyl chloride, after dripping, reactant reacts 3h at 0 DEG C, reaction product is washed to pH=7 and is transferred to extracting and separating in ethyl acetate through 4% sodium hydrogen carbonate solution, organic phase is dry with Calcium Chloride Powder Anhydrous after distilled water wash, filtration under diminished pressure after dry 8h, filtrate obtains product trimesic acid three triethyl citrates through distillation except after desolventizing.
The physical and chemical index of novel many citric acid three esters that table 1 embodiment of the present invention 1～7 and comparative example 1～4 synthesize is as follows:
Novel many citric acid three esters softening agent of the present invention, for food product pack, toy for children, medicine equipment, has less volatility, and good anti-transport property, resistance to extractable, meet the plasticising requirement in high hygienic requirements field.Application comparative example measurement result is as follows: formula (in mass): PVC100 part, 50 parts, softening agent, 2 parts of Ca-Zn thermo-stabilizers, 0.2 part of stearic acid.
Table 2 embodiment of the present invention 1～7 and the synthetic novel many citric acid three esters of comparative example 1～4 are used for PVC plastic plastification effect:
In sum, the present invention is connected to become citric acid three ester molecule more than by nontoxic, safe citric acid three ester molecule by polynary acyl chlorides, has also greatly improved the number ratio (A of nonpolar fatty carbonatoms and polarity ester group in molecule in putting forward high molecular degree of branching p/ A o), therefore, the novel many citric acid three esters softening agent the present invention relates to has good plasticization effect and excellent thermostability, low temperature kindliness, the extractable of resistance to solvent and anti-transport property concurrently simultaneously.

Claims (8)

1. a citric acid three ester more than, is characterized in that, has structure shown in formula 1 or formula 2:
Wherein,
In formula 1 and formula 2, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 11, R 12, R 13be selected from independently of one another the alkyl of C4～C12;
R 10for a kind of in the substituted radical of following center:
R 14for a kind of in the substituted radical of following center:
2. many citric acid three esters as claimed in claim 1, is characterized in that R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 11, R 12, R 13be selected from independently of one another the one in C4～C12 straight chain or branch alkyl group.
3. many citric acid three esters as claimed in claim 2, is characterized in that R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 11, R 12, R 13for identical group.
4. the preparation method of the many citric acid three esters described in claim 1～3 any one, is characterized in that, comprises the following steps:
Step (1): prepare citric acid three ester
C4～C12 alcohol excessive with carboxyl in relative citric acid citric acid is carried out to esterification under to the catalysis of benzene methanesulfonic acid and obtain citric acid three ester;
Step (2): prepare polynary acyl chlorides
Polycarboxylic acid is obtained to polynary acyl chlorides by phosphorus trichloride acidylate, and described polycarboxylic acid is trimesic acid, equal benzene nitrilotriacetic, 1,3,5-hexanaphthene tricarboxylic acid, 1,1, three acid of 2-second, the third three acid, 1,2,4-butane tricarboxylic acid, 1,3,5-penta tricarboxylic acid, pyromellitic acid, 1,2,3,4-BTCA, 1,2,3,4-tetramethylene tetracarboxylic acid or season penta tetracid;
Step (3): prepare many citric acid three esters
The polynary acyl chlorides that step (2) is made is slowly added drop-wise in the mixed system of citric acid three ester that step (1) makes and acid binding agent triethylamine and carries out esterification, to obtain final product.
5. preparation method as claimed in claim 4, is characterized in that, in step (1), the reaction conditions of esterification is to react 3～6h under the temperature condition of 110～160 DEG C.
6. preparation method as claimed in claim 4, is characterized in that, polycarboxylic acid reacts 4～6h with excessive phosphorus trichloride and makes polynary acyl chlorides at the temperature of 50～70 DEG C.
7. preparation method as claimed in claim 4, is characterized in that, in step (3), in polynary acyl chlorides and citric acid three ester, the mol ratio of acid chloride groups and hydroxyl is 1～1.2:1.
8. preparation method as claimed in claim 4, it is characterized in that, the reaction conditions of esterification is first polynary acyl chlorides to be slowly added drop-wise in the mixed solution of citric acid three ester and acid binding agent to react in ice-water bath in step (3), and after being added dropwise to complete, 2～4h is reacted in continuation in ice-water bath.
CN201410341025.8A 2014-07-17 A kind of many citric acid three esters and preparation method thereof Expired - Fee Related CN104163760B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107418651A (en) * 2017-08-30 2017-12-01 黄山学院 A kind of heptyl ester calcium salt detergent for lubricating oil of carboxylated citric acid three and preparation method thereof
CN107652987A (en) * 2017-10-17 2018-02-02 太原理工大学 The preparation method of maleic acid cholesterol monoesters base citric acid three ester liquid crystal
CN108409574A (en) * 2018-04-16 2018-08-17 山东万图高分子材料股份有限公司 A kind of citrate and its preparation method and application
CN111647298A (en) * 2020-06-22 2020-09-11 徐毓敏 Cable fireproof coating and preparation method thereof
CN111647335A (en) * 2020-06-22 2020-09-11 徐松波 Flame-retardant fireproof epoxy coating and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239555A (en) * 1960-12-09 1966-03-08 Benckiser Gmbh Joh A Bis-citric acid esters
CN1275975A (en) * 1997-05-12 2000-12-06 莱利工业公司 Processes for producing citrate esters
US6200724B1 (en) * 1995-09-20 2001-03-13 Fujitsu Limited Chemical amplification resist compositions and process for the formation of resist patterns

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239555A (en) * 1960-12-09 1966-03-08 Benckiser Gmbh Joh A Bis-citric acid esters
US6200724B1 (en) * 1995-09-20 2001-03-13 Fujitsu Limited Chemical amplification resist compositions and process for the formation of resist patterns
CN1275975A (en) * 1997-05-12 2000-12-06 莱利工业公司 Processes for producing citrate esters

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107418651A (en) * 2017-08-30 2017-12-01 黄山学院 A kind of heptyl ester calcium salt detergent for lubricating oil of carboxylated citric acid three and preparation method thereof
CN107418651B (en) * 2017-08-30 2020-02-14 黄山学院 Carboxylated triheptyl citrate calcium salt lubricating oil detergent and preparation method thereof
CN107652987A (en) * 2017-10-17 2018-02-02 太原理工大学 The preparation method of maleic acid cholesterol monoesters base citric acid three ester liquid crystal
CN107652987B (en) * 2017-10-17 2020-06-23 太原理工大学 Preparation method of maleic acid cholesterol monoester group citric acid triester liquid crystal
CN108409574A (en) * 2018-04-16 2018-08-17 山东万图高分子材料股份有限公司 A kind of citrate and its preparation method and application
CN111647298A (en) * 2020-06-22 2020-09-11 徐毓敏 Cable fireproof coating and preparation method thereof
CN111647335A (en) * 2020-06-22 2020-09-11 徐松波 Flame-retardant fireproof epoxy coating and preparation method thereof

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