Preparation and application of triethylene glycol diisooctanoate_Industrial additives

Background and overview^[1]

Triethylene glycol diisooctanoate has excellent low temperature properties, oil resistance, antistatic properties, etc., and has certain lubricity and other characteristics. In addition, triethylene glycol diisooctanoate has similar polarity to resin and has good compatibility. It is a solvent-based plasticizer with good performance. Currently, triethylene glycol diisooctanoate is widely used in the preparation of polyvinyl butyral (PVB) safety films, synthetic rubber, polyvinyl chloride (PVC), sealing materials, etc., and has great application value. Due to the steric hindrance of branched-chain fatty acids, it is difficult to complete the reaction. Therefore, it is very necessary to develop a synthesis process of triethylene glycol diisooctanoate suitable for industrial production. The synthesis of triethylene glycol diisooctanoate is generally synthesized in organic solvents, which does not meet the technical requirements of green chemistry and can easily cause environmental pollution. In addition, metal oxides, sulfuric acid, etc. are generally used as catalysts. In the production of reagents, there are disadvantages such as relatively expensive reagents, high corrosiveness, high safety hazards, and low yields, which are not conducive to industrial production. It can be seen that the existing synthesis routes are not easy for industrial production. There is an urgent need to seek a preparation method for triethylene glycol diisooctanoate that is easy to operate and has mild reaction conditions.

Preparation^[1-2]

Method 1:

First, use a vacuum pump to pump a certain proportion of triethylene glycol, isooctanoic acid, catalyst and cocatalyst into the esterification kettle; use steam to heat the materials. After reflux occurs, slow down the heating rate to keep the reflux relatively stable. After the reaction is completed, the reaction liquid is transferred to the cooling coarse filter kettle, and after cooling, the filter residue is filtered out through plate and frame pressure filtration; the filtrate is collected in the crude oil tank and then enters the light component removal kettle. Use steam to heat up the light component removal kettle, and evaporate the excess isooctanoic acid in the filtrate to obtain crude triethylene glycol diisooctanoate. The crude triethylene glycol diisooctanoate is subjected to cooling water washing, dehydration, distillation and filtration through a cooling water washing kettle, a dehydration kettle, a cooling rectification kettle, and an essential oil plate and frame oil filter to obtain a colorless and transparent oily triethylene glycol diisooctanoate. Caprylic acid ester finished product.

Method 2: A method of synthesizing triethylene glycol diisooctanoate, the preparation steps include.

(1) Preparation of solid superacid catalyst. Take the TiCl4 aqueous solution and hydrolyze it with dilute ammonia water to make it alkaline (PH=9-11). Let it stand for 24 hours, then filter and wash it to obtain a large amount of white precipitate. The solid is dried at 110-130℃ and ground into powder. Then add it to a 0.5M concentrated sulfuric acid solution of cerium sulfate, react for 8-14 hours, filter and dry, and place it in a muffle furnace for roasting to obtain the super acid catalyst SO42-/TiO2/Ce.

(2) Synthesis of triethylene glycol diisooctanoate. Add triethylene glycol and isooctanoic acid into the reaction vessel, and then add the catalyst prepared in the above steps into the reaction vessel. The reaction temperature is 100-200°C, and the reaction is carried out for 5-15 hours. When the reaction is completed, heating is stopped to obtain a crude product. The material mass ratio of triethylene glycol and isooctanoic acid is 1:2~1:4, preferably 1:2.5. The mass ratio of triethylene glycol to catalyst SO42-/TiO2/Ce is 1:0.1~1:0.5, preferably 1:0.2.

(3) Post-processing of products. The reaction solution is filtered, and the filtered catalyst is washed, dried and recycled. The filtrate was washed 4 times with 5% NaOH solution. The organic phase was washed with water and saturated brine, dried over anhydrous sodium sulfate, and distilled under reduced pressure to produce a yellow oily liquid with light plasticizer.

Apply^[3-6]

Triethylene glycol diisooctanoate can be used in adhesives and sealing materials, and as a plasticizer for polyvinyl chloride, cellulose products, styrene and other products. As a special plasticizer of polyvinyl butyral film, it is an indispensable raw material in the film processing process. Especially in recent years, the rapid development of construction, automobile and other industries has promoted the growing market demand for plasticizer triethylene glycol diisooctanoate.

1) Prepare a flame retardant and antibacterial coating for digitally printed fabrics, which consists of the following components: triethylene glycol diisooctanoate, phenolic epoxy resin, graphite powder, trioctyl phosphate, stearate, Zirconia powder, tribasic lead sulfate, melamine cyanurate, trioctyl trimellitate, methyl vinyl silicone rubber, triethylene glycol diisooctanoate, dioctyl phthalate, hard Glyceryl fatty acid, octamethylcyclotetrasiloxane, isophorone, polyvinyl butyral, ammonium perchlorate, ethyl paraben, antiviral alum, ammonium polyphosphate, glyceryl caprylate, benzene Vinylphenol, propylparaben, vanillin. The product of the invention has relatively superior flame retardancy, acid and alkali resistance, mildew resistance and antibacterial properties, and improves product performance.

2) Prepare a high-strength corrosion-resistant rubber material, whose raw materials include: natural rubber, zinc oxide, stearic acid, antioxidant, accelerator, silica, coumaron, sulfur, aluminum hydroxide, Ethylene glycol diisooctanoate, modified hard clay, additives. The invention utilizes the combined use of modified hard clay, natural rubber, white carbon black, aluminum hydroxide, PVC stabilizer triethylene glycol diisooctanoate, coumaron and other raw materials to make the rubber material have good elasticity. Wear resistance, tear resistance, acid and alkali resistance, chemical resistance, water resistance, anti-aging, tensile strength, elongation stress and other properties. The performance of the invention meets the material requirements of water treatment filter pipes with a crocheted structure, and can be used to make water treatment filter pipes with a crocheted structure.

3) Prepare a water-retaining long-acting slow-release compound fertilizer, which is composed of diatomaceous earth and water-based acrylic emulsion.�, Plant ash, ammonium bicarbonate, edible fungus residue, tea residue, composite biological bacteria, wheat bran, camphor dry powder, urea, potassium nitrate, ammonium lauryl ethoxy sulfate, triethylene glycol diisooctanoate, humic acid Sodium phosphate, lime powder, bamboo charcoal powder and dry artemisia annua powder are prepared by grinding edible fungus residue and tea leaf residue, adding compound biological bacteria and adding water for fermentation, then adding diatomaceous earth and lime, water-based acrylic emulsion, urea, potassium nitrate, Stir ammonium lauryl ethoxysulfate and triethylene glycol diisooctanoate evenly, add the grinding powder of the remaining raw materials, add it to the mixture, add water to adjust, granulate and dry. The fertilizer of the invention contains a variety of ingredients required by the human body and rich minerals, can provide easily absorbed mineral elements for plant growth, is environmentally friendly and safe, can effectively improve soil conditions, has good slow-release control capabilities, water absorption and drought resistance, and high utilization rate.

4) Prepare a special filler for cold-resistant and ultraviolet-resistant high-pressure rubber hoses, which is made of the following raw materials by weight: attapulgite 5-8, sepiolite 3-5, vanadium pentoxide 1-2, dimethoate Iron 13-15, barium stearate 2-3, polyamide wax powder 2-3, phytic acid 2-3, triethanolamine 2-3, triethylene glycol diisooctanoate 2-3, fly ash 50 -55, an appropriate amount of 4-6% hydrochloric acid, an appropriate amount of water, and 15-20 auxiliaries; the filler of the present invention is added with ferrocene, which has anti-ultraviolet properties and improves anti-photoaging properties; by adding triethylene glycol diisooctanoic acid The ester can improve the cold-resistant performance of the hose; by using fly ash, the cost is reduced and the reinforcing performance is good; by using the additive of the present invention, the dispersion and reinforcing performance of the filler can be improved, and the strength and strength of the high-pressure rubber hose can be improved. Impact-resistant toughness, not easy to bubble and deform.

Main reference materials

[1] Production technology of triethylene glycol diisooctanoate

[2] CN107778176-A synthesis process of triethylene glycol diisooctanoate

[3] CN201610523875.9 A flame retardant and antibacterial coating for digitally printed fabrics

[4] CN201810235060.X A high-strength, corrosion-resistant rubber material

[5] CN201610068560.X A water-retaining long-acting slow-release compound fertilizer and its preparation method

[6] CN201410292924.3 A special filler for cold-resistant and UV-resistant high-pressure rubber hose and its preparation method