77-94-1

Basic information

• Product Name: Tributyl citrate
• Synonyms: N-BUTYLCITRATE;TRIBUTYL CITRATE;TRI-N-BUTYL CITRATE;TRIPHENYLBENZYLPHOSPHONIUM CHLORIDE;1,2,3-Propanetricarboxylic acid, 2-hydroxy-, tributyl ester;1,2,3-Propanetricarboxylicacid,2-hydroxy-,tributylester;2,3-propanetricarboxylicacid,2-hydroxy-tributylester;2-Hydroxy-1,2,3-propanetricarboxylic acid, tributyl ester
• CAS NO: 77-94-1
• Molecular Formula: C₁₈H₃₂O₇
• Molecular Weight: 360.44
• EINECS: 201-071-2
• Product Categories: Functional Materials;Hydroxycarboxylic Acid Esters (Plasticizer);Plasticizer;Amino ester;fine chemicals
• Mol File: 77-94-1.mol
• Article Data: 26

Chemical Properties

• Melting Point: ≥300 °C(lit.)
• Boiling Point: 234 °C (17 mmHg)
• Flash Point: 300 °C
• Appearance: Clear/Liquid
• Density: 1.043 g/mL at 20 °C(lit.)
• Vapor Pressure: 1.09E-07mmHg at 25°C
• Refractive Index: n20/D 1.445
• Storage Temp.: Store below +30°C.
• Solubility: Miscible with acetone, ethanol, and vegetable oil; practically insoluble in water.
• PKA: 11.30±0.29(Predicted)
• Water Solubility: insoluble
• Merck: 14,1564
• BRN: 1806072
• CAS DataBase Reference: Tributyl citrate(CAS DataBase Reference)
• NIST Chemistry Reference: Tributyl citrate(77-94-1)
• EPA Substance Registry System: Tributyl citrate(77-94-1)

Safety Data

• Hazard Codes: T
• Statements: 25
• Safety Statements: 26-36/37/39-45-24/25
• RIDADR: UN 2811 6.1/PG 2
• WGK Germany: 3
• RTECS: TZ8608000
• TSCA: Yes
• Hazardous Substances Data: 77-94-1(Hazardous Substances Data)

Usage

Uses

Used in Plasticizer Industry:
Tributyl citrate is used as an innocuous plasticizer for non-toxic PVC, packaging materials in food production, soft toys for children, and medical products. It is also used as a plasticizer for polyvinyl chloride, vinyl chloride copolymers, and cellulose resin.
Used in Cosmetics Industry:
Tributyl citrate is used as a non-phthalate plasticizer for the preparation of resins and is also used in the synthesis of Acetyl Tributyl Citrate, a valuable biodegradable plasticizer of low toxicity, found in nail polish and other cosmetics.
Used in Pharmaceutical Industry:
Tributyl citrate is used to plasticize polymers for coating solid drug dosage forms, tablets, and capsules. It serves as a secondary standard for application in quality control, providing a convenient and cost-effective alternative to pharmacopeia primary standards.
Used in Coatings and Adhesives Industry:
Tributyl citrate is used as a plasticizer and solvent for nitrocellulose lacquers, in polishes, inks, and similar preparations. It is also used as an anti-foam agent.
Used in Biodegradable Materials:
Tributyl citrate can be used to incorporate in zein film to enhance its mechanical properties for industrial processing and as a plasticizer to improve the ductile properties of poly(lactide) polymers.

Outline

Tributyl citrate (TBC) is a good environmental plasticizers, lubricants. At room temperature, it is non-toxic, it has fruit flavor, it is colorless oily liquid. Boiling point is 170℃ (133.3Pa), flash point (open cup) is 185℃. It is soluble in most organic solvents. Volatile is small, it has good compatibility with the resin, it has high efficiency in plastification, in Europe and other countries it is allowed for food packaging and medical products, as well as children's soft toys, pharmaceuticals, medical products, flavors and fragrances, cosmetics manufacturing and other industries.Products can be given a good cold resistance, water resistance and mildew resistance. The product which is resin plasticized can exhibit good transparency and low temperature flexural properties, and has low volatility and low extraction resistance in different media, thermal stability, it does not change color when be heat. The product which prepared by lubricating oil can have good lubricating properties.

New non-toxic plasticizer

The most commonly used plasticizer is phthalate esters industrially, because it can induce cancer, the use in foreign countries has been controlled strictly , China has also formulated relevant laws and regulations, and will phase out its use in food packaging materials, medical appliances toys . Tributyl citrate (TBC) is a new non-toxic plasticizer, because it has good compatibility, high plasticizing efficiency, non-toxic and less volatile, weather resistance and other characteristics of broad interest, it is used as the preferred alternative green products in place of phthalic dimethyl esters. With the growing awareness of environmental protection and improvement of environmental regulations, the development and production of tributyl citrate has excellent prospects. Tributyl citrate is usually caused with citric acid and n-butanol in the presence of catalyst by esterifying, the conventional catalyst is concentrated sulfuric acid, although its low price, high catalytic activity, it can cause serious corrosion for equipment, post-processing process is complex, the select of reaction is poor, environmental pollution is serious and other defects, and thus the work of seeking alternative catalysts in place of concentrated sulfuric acid is very active, some better catalytic effect of the catalyst has been found: [Sodium bisulfate catalytic synthesis of tributyl citrate] Monohydrate Sodium hydroxide is a strong ionic compounds, the study found that it is soluble in water, aqueous solution is strongly acidic but it is insoluble in organic acids and alcohols reaction system, it can be used as a catalyst for esterification, studies show that the catalyst has a high activity catalytic, good stability, high yield, easy separation, convenient synthesis method, no corrosion, no pollution and other advantages. [Synthesis of solid superacid catalyst] Superacid is an acid, which the strength is greater than 100% sulfuric acid. Studies have shown that using it as a catalyst for the esterification reaction has good selectivity, fast response, high yield, easy separation, ease of operation, and the catalyst is stable, reusable, non-corrosive, non-polluting, it is a kind of promising catalyst. [Synthesis of p-toluenesulfonic acid catalysis] Toluenesulfonic acid is a strong organic acid, it can be used to instead of concentrated sulfuric acid as the esterification catalyst, and the corrosion for equipment and waste pollution is much smaller than that of sulfuric acid, it is also high activity and selectivity, cheap, dosage less, good product color, it is fit catalyst for industrial production. [Miscellaneous catalytic synthesis of tributyl citrate] Heteropolyacid is a multi-proton acid, the stronger of acidity, the more conducive to the formation of salt, it provide more favorable conditions for other nucleophilic attack, thus it speeds up the rate of the esterification reaction. It is non-volatile, the thermal stability is well, it also cause less pollution and can reduce equipment corrosion, it is an ideal esterification catalyst. The above information is edited by the lookchem of Wang Xiaodong.

Production Methods

Tributyl citrate is prepared by the esterification of citric acid with butanol.

Pharmaceutical Applications

Tributyl citrate is used to plasticize polymers in formulated pharmaceutical coatings. The coating applications include capsules, tablets, beads, and granules for taste masking, immediate release, sustained-release, and enteric formulations.

Safety

Tributyl citrate is used in oral pharmaceutical formulations. It is generally regarded as an essentially nontoxic and nonirritating material. However, ingestion of large quantities may be harmful. LD50 (cat, oral): >50 mL/kg LD50 (mouse, IP): 2.9 g/kg LD50 (rat, oral): >30 mL/kg

storage

Tributyl citrate should be stored in well-closed containers in a cool, dry location at temperatures not exceeding 38℃. When stored in accordance with these conditions, tributyl citrate is a stable material.

Incompatibilities

Tributyl citrate is incompatible with strong alkalis and oxidizing materials.

Regulatory Status

Approved in the USA for indirect food contact in food films. Included in the Canadian List of Acceptable Non-medicinal Ingredients.

InChI:InChI=1/C18H32O7/c1-4-7-10-23-15(19)13-18(22,17(21)25-12-9-6-3)14-16(20)24-11-8-5-2/h22H,4-14H2,1-3H3

Synthetic route

citric acid (77-92-9) + butan-1-ol (71-36-3) → Citroflex-4 (77-94-1)

Conditions	Yield
With 1,3-propanesultone; sulfuric acid; manganese(II) acetate; Cycloheximide In water; toluene at 65 - 100℃; for 31h; Temperature; Ionic liquid;	98.6%
With dimesitylammonium pentafluorobenzenesulfonate In n-heptane at 80℃; for 24h;	97%
With 3H(1+)*O40SiW12(4-)*C21H22O3PS(1+) Concentration; Reflux; Dean-Stark;	97.5%

sulfuric acid (7664-93-9) + citric acid (77-92-9) + butan-1-ol (71-36-3) → Citroflex-4 (77-94-1)

Conditions	Yield
at 150℃; sowie bei 175grad und 200grad;

citric acid (77-92-9) + butan-1-ol (71-36-3) → monobutyl citrate (118068-28-3) + dibutyl ether (142-96-1) + Citroflex-4 (77-94-1) + sym-di-n-butyl citrate (101996-65-0)

Conditions	Yield
Amberlyst 15 at 25 - 120℃; for 16h;

Glyoxilic acid (298-12-4) + butan-1-ol (71-36-3) → Dibutyl maleate (105-76-0) + di-n-butyl oxalate (2050-60-4) + dibutyl succinate (141-03-7) + L-(-)-di-n butyl malate (1587-18-4) + dibutyl tartrate (344268-32-2) + propane-1,2,3-tricarboxylic acid tributyl ester (38094-11-0) + Citroflex-4 (77-94-1) + dibutyl fumarate (105-75-9) + C11H20O5 (117538-83-7) + C12H22O4S3 (94086-70-1)

Conditions	Yield
Stage #1: Glyoxilic acid With sodiumsulfide nonahydrate In water at 90℃; for 168h; Stage #2: butan-1-ol With hydrogenchloride at 90℃; for 2h;

...Expand

n-Butyl chloride (109-69-3) + sodium citrate (68-04-2) → Citroflex-4 (77-94-1)

Conditions	Yield
Stage #1: n-Butyl chloride With potassium iodide In acetone for 2h; Inert atmosphere; Reflux; Stage #2: sodium citrate In N,N-dimethyl-formamide at 60℃; for 3h; Temperature;

Citroflex-4 (77-94-1) + acetic anhydride (108-24-7) → acetyltributyl citrate (77-90-7)

Conditions	Yield
dmap at 100℃; for 24h;	93%
With 1-butyl-3-methylimidazolium 4-methylbenzenenesulfonate; 1-butyl-3-methylimidazolium Tetrafluoroborate at 50℃; for 8h;	19%
at 70 - 80℃; Concentration;

vinyl acetate (108-05-4) + Citroflex-4 (77-94-1) → acetyltributyl citrate (77-90-7)

Conditions	Yield
With potassium tert-butylate; 1-ethyl-3-methylimidazolium tetrafluoroborate In tetrahydrofuran at 70℃; for 12h; Reagent/catalyst; Solvent; Time; Temperature; Concentration; Inert atmosphere;	81%

Citroflex-4 (77-94-1) + acetic acid (64-19-7) → acetyltributyl citrate (77-90-7)

Conditions	Yield
[Mes2NH2](+)[O3SC6F5](-) In n-heptane at 115℃; for 48h;	31%

Citroflex-4 (77-94-1) → 1-propene-1,2,3-tricarboxylic acid tributyl ester (343599-72-4)

Conditions	Yield
With phosphoric acid; acetic anhydride at 155℃; durch Leiten des Reaktionsprodukts durch ein auf 425grad erhitztes Rohr;
With sulfuric acid; acetic anhydride at 155℃; durch Leiten des Reaktionsprodukts durch ein auf 425grad erhitztes Rohr;

Citroflex-4 (77-94-1) + hexan-1-ol (111-27-3) → tri-n-hexyl citrate (16544-70-0)

Conditions	Yield
aluminium(III) triflate at 150 - 195℃; under 37.5038 - 7500.75 Torr; Conversion of starting material;

Citroflex-4 (77-94-1) → C22H35ClO9

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrachloromethane / 4 h / 70 °C / Inert atmosphere 2: phosphorus trichloride / 60 °C View Scheme

succinic acid anhydride (108-30-5) + Citroflex-4 (77-94-1) → C22H36O10

Conditions	Yield
In tetrachloromethane at 70℃; for 4h; Inert atmosphere;

Upstream product

• 77-92-9 citric acid 
• 71-36-3 butan-1-ol 
• 7664-93-9 sulfuric acid 
• 109-69-3 n-Butyl chloride 
• 68-04-2 sodium citrate 
• 24555-16-6 citric acid anhydride 
• 298-12-4 Glyoxilic acid 

Downstream Products

• 77-90-7 acetyltributyl citrate 
• 16544-70-0 tri-n-hexyl citrate 

Relevant articles and documents

Preparation supported heteropoly (acid)/polyaniline catalysts and catalytic synthesis of tributyl citrate

A series of polyaniline supported heteropoly acids were prepared through a simple method at room temperature. The obtained heterogeneous catalysts were comprehensively characterized by powder FTIR spectroscopy, UV-vis spectra, NH3 temperature programmed desorption (TPD) and scanning electron microscopy (SEM). The influence of various process parameters such as heteropoly loading (10 to 25 wt%), catalyst amount (3-5%), molar ratio of n-butanol to citric acid (3 to 5), and reaction time (3.5-12 h) have been investigated over heteropoly/polyaniline catalysts with the aim to maximize citric acid conversion and tributyl citrate selectivity. The different catalytic tests has shown that the catalyst exhibits high conversion and selectivity by using the as-prepared heteropoly/polyaniline catalysts for esterification under appropriate conditions. The present method of using 20% heteropoly/polyaniline catalyst for the synthesis of tributyl citrate would be environmentally benign in the reusability of catalyst.

CITRATE-BASED PLASTICIZER COMPOSITION AND RESIN COMPOSITION COMPRISING SAME

The present invention relates to a plasticizer composition, including a lower alkyl-based citrate and a higher alkyl-based citrate at the same time, as citrate, wherein the ratio of a hybrid type to a non-hybrid type and the ratio of the lower alkyl groups to the higher alkyl groups are controlled so that effects are achieved. When applying the plasticizer composition to a resin, stress resistance and mechanical properties can be maintained at an equal or higher level, the migration and volatile loss properties and the plasticization efficiency can be balanced, and the light resistance and heat resistance can be remarkably improved.

PLASTICIZER COMPOSITION AND RESIN COMPOSITION INCLUDING THE SAME

Provided is a plasticizer composition including: a cyclohexane-1,2-diester-based substance of the following Chemical Formula 1; and a citrate-based substance of the following Chemical Formula 2: wherein in Chemical Formula 1 and Chemical Formula 2: R1 and R2 each independently are a C8 to C10 alkyl group; and R3 to R5 each independently are a C5 to C10 alkyl group.

Novel cyclohexylimide ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F

The invention provides a novel cyclohexylimide ionic liquid and a method for catalyzing synthesis of butyl citrate and bisphenol F, and can solve the technical problem that the reaction yield needs tobe further improved when the traditional cyclohexylimide ionic liquid catalyzes synthesis of butyl citrate and bisphenol F. The novel cyclohexylimide ionic liquid is characterized by being prepared by the following method: S1, mixing and dissolving 1, 3-propane sultone and toluene, cooling the solution, adding Mn (OAc) 2 and reduced hexylimide, heating to 65 DEG C, and reacting for 12 hours; s2,filtering the reaction solution obtained in the step S1 to obtain a white precipitate, rinsing, and drying to obtain a white intermediate; s3, dissolving the intermediate in water, stirring, dropwiseadding concentrated sulfuric acid, heating to 80 DEG C, and reacting for 16 hours to obtain yellow transparent liquid, and S4, removing water from the transparent liquid by rotary evaporation, rinsing, washing and drying to obtain the novel cyclohexylimide ionic liquid.

Citrate plasticizer

The invention discloses a citrate plasticizer and a preparation method thereof, and the preparation method of citrate comprises the following steps: firstly, citric acid and alcohol react to prepare citric acid triester, and then dianhydride acylation is carried out to prepare carboxyl-containing citric acid triester. After chlorination, the carboxyl-containing citric acid triester and the tris(2-ethoxyl) isocyanurate are subjected to esterification reaction to prepare triester citrate containing the isocyanurate. According to the present invention, the preparation method has characteristics of simple operation, wide raw material source and mild reaction condition, and meets the industrial production, the prepared triester citrate containing isocyanurate has a good plasticizing effect and excellent thermal stability, low-temperature flexibility, solvent extraction resistance, migration resistance and flame retardance, and can be widely applied to plastic rubber plasticizers.

Citrate plasticizer and preparation method thereof

The invention discloses a citrate plasticizer and a preparation method thereof. The preparation method comprises the following steps: firstly, carrying out reaction on citric acid and alcohol to prepare citric acid triester; acylating dianhydride to prepare carboxyl-containing triester citrate; carrying out acylating chlorination on the carboxyl-containing triester citrate, and then carrying out esterification reaction on the carboxyl-containing triester citrate and tri(2-hydroxyethyl) isocyanurate to prepare triester citrate containing isocyanurate; and finally, esterifying with fatty acyl chloride to obtain the modified citrate plasticizer. The preparation method is simple to operate, wide in raw material source and mild in reaction condition, and meets industrial production. The prepared triester citrate containing isocyanurate has a good plasticizing effect and excellent thermal stability, low-temperature flexibility, solvent extraction resistance, migration resistance and flame retardance, and can be widely applied to plastic rubber plasticizers.

Method for catalytically synthesizing tributyl citrate

The invention discloses a method for catalytic synthesis of tributyl citrate. According to the method, citric acid monohydrate and butanol are used as raw materials and reaction is carried out for 6-7hours under the condition of acid catalysis to obtain tributyl citrate. Citric acid and n-butyl alcohol are used as initial raw materials, sulfonic acid resin is used as a catalyst, catalytic efficiency is high, operation is easy, reaction conditions are mild, product selectivity and yield are high, and the method has wide industrial application prospects.

Robust acidic pseudo-ionic liquid catalyst with self-separation ability for esterification and acetalization

The novel acidic pseudo-ionic liquid catalyst with self-separation ability has been synthesized through the quaternization of triphenylphosphine and the acidification with silicotungstic acid. The pseudo-IL showed high activities for the esterification with average conversions over 90%. The pseudo-IL showed even higher activities for acetalization than traditional sulfuric acid. The homogeneous catalytic process benefited the mass transfer efficiency. The pseudo-IL separated from the reaction mixture automatically after reactions, which was superior to other IL catalysts. The high catalytic activities, easy reusability and high stability were the key properties of the novel catalyst, which hold great potential for green chemical processes.

Micro-flow nanocatalysis: synergic effect of TfOH@SPIONs and micro-flow technology as an efficient and robust catalytic system for the synthesis of plasticizers

The combination of continuous flow technology with immobilizing of only 0.13?mol% of triflic acid (TfOH) on silica-encapsulated superparamagnetic iron oxide nanoparticles (SPIONs) under solvent-free conditions successfully provided a powerful, efficient, and eco-friendly route for the synthesis of plasticizers. The turnover frequency value in micro-flow conditions varied in the range of 948.7 to 7384.6 h?1 compared to 403.8 to 3099 h?1 for in-flask. This technique works efficiently, encouraging future applications of micro-flow nano-catalysis in green chemistry.

Synthetic method for auxiliary for 3D printing flexible material

The invention designs a synthetic method for a tribenzyl citrate auxiliary for a 3D printing flexible material. The preparing method includes the steps that monohydric alcohol, benzyl alcohol and citric acid are used as main raw materials, a catalyst and a water carrying agent are used, and the product tribenzyl citrate is prepared through two steps of reaction including acid alcohol esterification and ester exchange, neutralizing, washing, reduced pressure distillation and purification. the product is the auxiliary for the 3D printing flexible material.