CN101709032A - Lauryl alcohol polyoxyethylene ether acetate and cleaning agent taking lauryl alcohol polyoxyethylene ether acetate as main component - Google Patents

Abstract

The invention discloses a lauryl alcohol polyoxyethylene ether acetate, which uses lauryl alcohol polyoxyethylene to carry out esterification reaction with acetyl chloride under the condition of microwave radiation without solvent, and the process condition is: the ratio of raw materials is 1:1.00 ~1.10, the microwave radiation rate is 375W, the reaction time is 5min, the reaction product is extracted with chloroform, washed twice with 5% sodium carbonate solution, dried, and the lauryl alcohol polyoxyethylene ether acetate product is obtained through detection and analysis, and then added with 8-10 %d of propylene glycol n-propyl ether, 4-5% of hydroxypropyl cellulose sodium, 5-6% of sodium chloride, 45-50% of water, and high-speed stirring can obtain non-ionic cleaning agent products. The product has special degreasing ability and excellent wettability, compatibility with anionic and cationic surfactants, and high solubility in water, which makes it have a wide application prospect.

Description

Lauryl polyoxyethylene ether acetate and cleaning agents mainly composed of it

technical field

The invention relates to an alcohol-based nonionic surfactant, in particular to a lauryl alcohol polyoxyethylene ether acetate and a cleaning agent mainly composed of it, belonging to the technical field of chemical auxiliaries.

Background technique

In the process of industrial production, all kinds of dirt will be produced in the equipment and pipelines of the production process, such as coking, oil dirt, scale, sediment, corrosive dirt, etc. These dirt usually lead to failure of equipment and pipelines, devices System production efficiency decreases, energy consumption increases, etc., and even safety accidents occur in severe cases.

In recent years, with the rapid development of the new synthetic industry, new types of industrial dirt are also emerging, and their molecular structure is becoming more and more complex; in addition, the bonding mechanism and bonding form between industrial dirt and different washing objects often depend on It depends on the type of dirt and the structural composition and surface physical and chemical properties of the object to be cleaned. Due to the needs of environmental protection, the biodegradability and non-toxic and harmless requirements of chemical agents are increasing day by day. Therefore, new challenges are continuously raised for chemical cleaning technology.

With the increasing awareness of environmental protection, more and more attention has been paid to the environmental safety of surfactants, such as the discussion on whether surfactants are harmful to environmental safety, the ecology and toxicity assessment of surfactants, etc. At the same time, many people worry that as a wide variety of daily chemical products continue to become people's daily necessities, such as toothpaste, soap, dishwashing detergent, washing powder (agent) and various cosmetics, etc., everyone will use them more or less every day. Take a certain amount of surfactant in a small amount. Therefore, there is a growing demand for research and development of biodegradable and environmentally friendly green surfactants with low toxicity to the human body.

my country's surfactant industry is currently in the development stage, and scientific research, production, application, and development are all valued by relevant departments. With the development of my country's economy and petroleum industry, the application fields of domestic surfactants are gradually expanding, and the status of surfactants in the national economy is also increasing. The development and application of alcohol-based nonionic surfactants is more important. People such as Gao Lixin in China once reported that a kind of surfactant was synthesized with carbon tetrachloride as a solvent -- lauryl alcohol polyoxyethylene ether phosphate (published in the 5th issue, the 30th volume, daily chemical industry magazine No. 63 in 2000 -66 pages), this reaction is carried out in the organic solvent carbon tetrachloride, not only can bring harm to the environment in the reaction process, also wasted resources and energy etc. simultaneously. People such as Dou Jianmin once reported to use polyoxyethylene lauryl ether and benzoyl chloride to react and synthesize polyoxyethylene lauryl ether benzoate (applying for a Chinese national invention patent, the patent number is: ZL 200610086679.6, and the publication number is CN1896046), which has It has special degreasing ability and superior wettability, but the reaction time is long, which takes 3 hours, and the solubility of the product in water is not large, which brings certain problems to practical application.

Compared with traditional heating reactions, organic synthesis under microwave radiation has the advantages of fast reaction speed, high yield, less side reactions, and easy purification of products. It can also save energy and realize atom-economical synthesis and eco-friendly green synthesis. So far, there are many types of microwave-accelerated organic synthesis reactions. In addition, the amount of conventional organic reaction solvent is generally 50 to 100 times the amount of raw materials, while the combination of microwave radiation and new technology of solvent-free organic synthesis avoids the use of a large number of toxic and volatile organic compounds, which not only reduces pollution, but also simplifies the production process. The reaction operation and post-treatment process shorten the reaction time, reduce the production cost, and have the advantages of high yield and strong selectivity. Therefore, this kind of organic reaction has become an important way to realize "green chemistry".

Contents of the invention

For above-mentioned prior art, the purpose of the present invention is in order to overcome the deficiencies in the prior art, thereby proposes to synthesize a kind of substantially nontoxic under microwave radiation solvent-free condition, non-polluting alcohol series nonionic surfactant-lauryl alcohol polyoxygen Vinyl ether acetate and a new cleaning agent based on it. The cleaning agent has potential broad prospects in industrial application.

The present invention is achieved through the following technical solutions:

Lauryl alcohol polyoxyethylene ether acetate is a non-toxic, non-polluting alcohol-based nonionic surfactant, and its molecular structure is as follows:

General nonionic surfactant molecules have an asymmetric amphiphilic structure, that is, one end of the molecule is lipophilic and the other end is hydrophilic. However, the polyoxyethylene lauryl ether acetate of the present invention has both ends lipophilic and the middle hydrophilic, and the hydrophilic group in the molecule is a polyoxyethyl ether chain, ie (OCH ₂ CH 2 ) _n OH. Both the oxygen atom and the hydroxyl group in the chain have the ability to form hydrogen bonds with water molecules, so that the compound has some special properties. It is a special alcohol-based nonionic surfactant. Compared with the lauryl alcohol polyoxyethylene ether benzene For formate, the solubility of this product in water is greater than that of benzoate, and it can be miscible with water, which brings great prospects for its application.

The product has an acid value (mgKOH/g)≤10, an ester content (%)≥95, and a refractive index (20°C) of 1.450-1.459.

The synthetic method of polyoxyethylene lauryl ether acetate, step is as follows:

First put lauryl alcohol polyoxyethylene ether into the reaction container, put the reaction container in a microwave oven, and install the reaction device; then slowly add acetyl chloride dropwise into the round bottom flask, after the dropwise addition, set the microwave radiation power It is 375-450W, and the reaction time is 5-7min; after the reaction is completed, cool to room temperature and let stand; add 5% sodium carbonate solution to the reaction container containing the reaction product for the first washing, let stand; % sodium carbonate solution for the second washing, standing, after standing, place the reaction product in a desiccator to dry, and finally characterize the product after detection and analysis.

The invention uses lauryl alcohol polyoxyethylene ether as a raw material to carry out substitution reaction with acetyl chloride under solvent-free conditions. The reaction itself is a reversible reaction. In order to improve the reaction yield, the ratio of raw materials is very important. If the acid chloride is used in excess, the reaction will proceed in the positive direction, but the problem is that the acid chloride is easy to hydrolyze. The resulting acetic acid is soluble in water. If the acid chloride is excessive, it will bring many difficulties to the post-processing of the product. After repeated tests, the molar ratio of polyoxyethylene lauryl ether to acid chloride is preferably 1:1.05-1.10, and the HCl generated by the reaction can be absorbed by the hydrochloric acid absorber, so no pollutants are produced during the reaction.

Lauryl alcohol polyoxyethylene ether and acetyl chloride can react at room temperature, and the product is almost colorless. However, it needs to react for more than 24 hours at normal temperature, and the conversion rate is only below 80%. In order to improve the reaction speed and shorten the reaction time, we adopt the solvent-free method of microwave radiation in order to shorten the reaction time and achieve a higher conversion rate. The experiment proves that microwave radiation is used in combination with solvent-free organic synthesis technology, and the yield can reach 95% when the radiation power is 375W and the radiation time is 5min.

In the synthesis method of the present invention, the heating container may be a microwave organic synthesizer with a radiation power of 375W. The radiation time is 5 minutes, the reaction is microwave radiation-solvent-free combined organic synthesis technology, the reaction instrument is a round bottom flask with a condenser tube, and the heating method is microwave radiation heating.

A cleaning agent mainly composed of polyoxyethylene lauryl ether acetate is composed of the following raw materials in parts by weight: 25-30 parts of polyoxyethylene lauryl ether acetate, 8-10 parts of propylene glycol n-propyl ether 4-5 parts of sodium hydroxypropyl cellulose, 5-6 parts of sodium chloride, and 45-50 parts of water.

The method for preparing the above-mentioned cleaning agent: add lauryl alcohol polyoxyethylene ether acetate in the ratio of raw materials to the container, and add water in the ratio of raw materials, stir evenly, and then add propylene glycol n-propyl ether and hydroxypropyl ether in the ratio of raw materials in sequence Base cellulose sodium and sodium chloride, stir evenly to obtain a colorless, transparent, viscous product.

Cleaning agent of the present invention has following advantage and performance:

(1) It has excellent oil solubility and water solubility, and can be miscible with crude oil, diesel oil, kerosene, engine oil, lubricating oil, vegetable oil, etc. in any proportion, and miscible with water;

(2) Miscible with various organic solvents;

(3) It has dispersing, wetting, penetrating, solubilizing and antistatic properties, and is stable in acidic and alkaline solutions;

(4) It is a phosphorus-free environmental cleaning agent, which is mild, safe and non-irritating, and has a protective effect on skin, clothing, machines and various metal surfaces.

(5) Strong compounding performance, excellent compounding performance with other admixtures, can fully reflect the "synergy effect".

Description of drawings

Fig. 1 is a process flow diagram of the present invention.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

As shown in Figure 1, firstly, polyoxyethylene lauryl ether is added into a round-bottomed flask, the round-bottomed flask is placed in a microwave oven, and the reaction device is installed. Then slowly add acetyl chloride dropwise into the round bottom flask, after the dropwise addition, set the microwave radiation power to 375W, and the reaction time is 5min. After the reaction is completed, cool to room temperature and stand still. Add 5% sodium carbonate solution to wash twice, extract and separate, dry, and then characterize the product.

Example 1:

Put the measured 1mmol of polyoxyethylene lauryl ether (n=9) into a 50ml round-bottomed flask for heating; add the measured 1.00mmol of acetyl chloride into the constant pressure dropping funnel, slowly add the acetyl chloride dropwise, and the dropwise addition is completed Finally, set the microwave radiation power to 300W for 5 minutes to start the reaction. After the reaction is completed, cool to room temperature and stand still.

Example 2:

Put the measured 1mmol of polyoxyethylene lauryl ether (n=9) into a 50ml round-bottomed flask for heating; add the measured 1.00mmol of acetyl chloride into the constant pressure dropping funnel, slowly add the acetyl chloride dropwise, and the dropwise addition is completed Finally, set the microwave radiation power to 375W for 5 minutes to start the reaction. After the reaction is completed, cool to room temperature and stand still.

Example 3:

Put the measured 1mmol of polyoxyethylene lauryl ether (n=9) into a 50ml round-bottomed flask for heating; add the measured 1.00mmol of acetyl chloride into the constant pressure dropping funnel, slowly add the acetyl chloride dropwise, and the dropwise addition is completed Finally, set the microwave radiation power to 450W for 5 minutes to start the reaction. After the reaction is completed, cool to room temperature and stand still.

Example 4:

Put the measured 1mmol of polyoxyethylene lauryl ether (n=9) into a 50ml round-bottomed flask for heating; add the measured 1.00mmol of acetyl chloride into the constant pressure dropping funnel, slowly add the acetyl chloride dropwise, and the dropwise addition is completed Finally, set the microwave radiation power to 375W for 4 minutes to start the reaction. After the reaction is completed, cool to room temperature and stand still.

Example 5:

Put the measured 1mmol of polyoxyethylene lauryl ether (n=9) into a 50ml round-bottomed flask for heating; add the measured 1.00mmol of acetyl chloride into the constant pressure dropping funnel, slowly add the acetyl chloride dropwise, and the dropwise addition is completed Finally, set the microwave radiation power to 375W for 6 minutes to start the reaction. After the reaction is completed, cool to room temperature and stand still.

Embodiment 6:

Put the measured 1mmol of polyoxyethylene lauryl ether (n=9) into a 50ml round-bottomed flask for heating; add the measured 1.05mmol of acetyl chloride into the constant pressure dropping funnel, slowly add the acetyl chloride dropwise, and the dropwise addition is completed Finally, set the microwave radiation power to 375W for 5 minutes to start the reaction. After the reaction is completed, cool to room temperature and stand still.

Embodiment 7:

Put the measured 1mmol of polyoxyethylene lauryl ether (n=9) into a 50ml round-bottomed flask for heating; add the measured 1.2mmol of acetyl chloride into the constant pressure dropping funnel, slowly add the acetyl chloride dropwise, and the dropwise addition is completed Finally, set the microwave radiation power to 375W for 5 minutes to start the reaction. After the reaction is completed, cool to room temperature and stand still.

After above-mentioned embodiment 1～7 reaction finishes, use refractometer to measure the refractive index of product and judge whether the degree of esterification is good according to refractive index; Find that when the formula of raw material ratio is in the scope of 1:1.05～1:1.10, microwave radiation power is 375W , when the reaction time is 5min, the yield is higher, and the refractive index of the product is respectively 1.4520 and 1.4560, which meet the requirements of technical indicators. The product needs to be washed twice with sodium carbonate solution, the concentration is 5% sodium carbonate solution, the acid value of the measured product is respectively 1.023, 1.038mg.KOH/g, and the acid value is below 10mg.KOH/g, then the reaction The conversion rate is above 95%, which has reached the expected goal.

The assessment index of gained polyoxyethylene lauryl ether acetate product is as follows:

Appearance: colorless transparent liquid

Color≤180

Acid value (mgKOH/g)≤10

Ester content (%)≥95

Refractive index (20°C) 1.450～1.459

The nuclear magnetic data of gained product is as follows:

NMR data of polyoxyethylene lauryl ether acetate:

¹ H NMR (400MHz, CDCl ₃ ), δ=5.31(m, 2H), 4.24-4.21(m, 2H), 3.72-3.43(m, 32H), 2.09(m, 2H), 1.59-1.56(m, 2H), 1.25-1.29(m, 21H), 0.89-0.86(m, 3H).

¹³ C NMR (400MHz, CDCl ₃ ), δ=171.37, 72.74, 71.80, 70.84, 70.78, 70.55, 70.26, 69.34, 63.86, 61.94, 53.72, 32.16, 29.91, 29.88, 29.85, 29.75, 29.621, 2.6 21.26, 14.41.

Infrared analysis is as follows: IR (υ/cm ^-1 ): 2934, 2875, 1732, 1441, 1262, 1141.

It can be seen from the nuclear magnetic resonance data that there are two hydrogens in the chemical shift of 4.24-4.21ppm, which are hydrogens on the methylene of PhCOOCH ₂ -, indicating that polyoxyethylene lauryl ether reacts with acid chlorides. In addition, this point can also be explained from the infrared data. There are strong absorption peaks at 1262 and 1224 cm ^-1 , indicating the existence of ester groups. This point can also be explained from other absorption peaks.

Embodiment 8 prepares a kind of cleaning agent

The formula is: 25 grams of polyoxyethylene lauryl ether acetate, 10 grams of propylene glycol n-propyl ether, 4 grams of sodium hydroxypropyl cellulose, 6 grams of sodium chloride, and 45 grams of water.

The preparation method is: in a clean 200ml beaker, add polyoxyethylene lauryl ether acetate and water, place it on an adjustable high-speed homogenizer, stir evenly, then add propylene glycol n-propyl ether, hydroxypropyl fiber Sodium plain and sodium chloride, set the rotation speed at 12,000 rpm, and stirred for 0.5 hour to obtain a colorless, transparent, viscous product.

Embodiment 9 prepares a kind of cleaning agent

The formula is: 30 grams of polyoxyethylene lauryl ether acetate, 8 grams of propylene glycol n-propyl ether, 5 grams of sodium hydroxypropyl cellulose, 5 grams of sodium chloride, and 50 grams of water.

The preparation method is the same as in Example 8.

Embodiment 10 prepares a kind of cleaning agent

The formula is: 28 grams of lauryl polyoxyethylene ether acetate, 9 grams of propylene glycol n-propyl ether, 4.5 grams of hydroxypropyl cellulose sodium, 5.5 grams of sodium chloride, and 48 grams of water.

The preparation method is the same as in Example 8.

The colorless transparent viscous product that above-mentioned embodiment 8～10 obtains is detected, and its technical index is as follows:

Appearance: Colorless transparent viscous liquid

Color≤100

Odor: no peculiar smell,

PH value (20°C): 7-8.

Claims (6)

1. a polyoxyethylene lauryl ether acetate, is characterized in that: molecular structure is

2. the synthetic method of lauryl alcohol polyoxyethylene ether acetate described in claim 1 is characterized in that: first lauryl alcohol polyoxyethylene ether is dropped in the reaction vessel, reaction vessel is placed in the microwave oven, then ethyl Slowly add the acid chloride dropwise into the round bottom flask. After the dropwise addition, set the microwave radiation power to 375~450W, and the reaction time is 5~7min; after the reaction is completed, cool to room temperature and let stand; Add 5% sodium carbonate solution to wash for the first time, let stand; then add 5% sodium carbonate solution to wash for the second time, let stand, after standing, put the reaction product in a desiccator to dry, after detection and analysis Finally, characterize the product. 3. the synthetic method of polyoxyethylene lauryl ether acetate according to claim 2 is characterized in that: the mol ratio of polyoxyethylene lauryl ether to acetyl chloride is 1: 1.05～1.10. 4. the synthetic method of polyoxyethylene lauryl ether acetate according to claim 2, is characterized in that: described reaction vessel is the round-bottomed flask that has condensation tube. 5. a kind of cleaning agent with polyoxyethylene lauryl ether acetate as claimed in claim 1 is characterized in that: be made up of the raw material of following weight part: polyoxyethylene lauryl ether acetate 25-30 parts, 8-10 parts of propylene glycol n-propyl ether, 4-5 parts of hydroxypropyl cellulose sodium, 5-6 parts of sodium chloride, 45-50 parts of water. 6. The preparation method of the cleaning agent as claimed in claim 5, characterized in that: the lauryl alcohol polyoxyethylene ether acetate of the raw material ratio is added in the container, and the water of the raw material ratio is added, stirred evenly, and then sequentially added Propylene Glycol N-Propyl Ether, Sodium Hydroxypropyl Cellulose and Sodium Chloride are mixed evenly to obtain a colorless, transparent and viscous product.

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