CN106311075A - Cyclosiloxane surfactant and preparation method thereof - Google Patents

Abstract

The invention discloses a cyclosiloxane surfactant. The cyclosiloxane surfactant has the following general structural formula (please see the formula in the description). The invention further discloses a preparation method of the cyclosiloxane surfactant. The obtained cyclosiloxane surfactant has the good physicochemical property; the minimum surface tension of an aqueous solution of the cyclosiloxane surfactant is 23-32 mN/m, and the critical micelle concentration in the aqueous solution is 55-160 mg/L.

Description

A kind of cyclosiloxane surfactant and preparation method thereof

technical field

The invention belongs to the technical field of chemistry and chemical engineering, and in particular relates to a surfactant, in particular to a cyclosiloxane surfactant and a preparation method thereof.

Background technique

Silicone surfactants have been widely used in polyurethane foam products, textiles, paints and coatings, cosmetics and pesticides due to their low surface tension, good spreading and wettability and thermal stability. According to the molecular structure, silicone surfactants can be divided into four categories, namely: (1) trisiloxane type MD ¹ (R) M, (2) comb type (rake-type) MD ¹ xDyM, (3) ABA Block type M ¹ (R) DxM ¹ (R) and (4) ring structure.

Chinese patent CN103585926B, CN102972396B synthesized trisiloxane type surfactant and studied its performance; Chinese patent CN103657518B, CN101921398B etc. synthesized comb type organic silicon surfactant and studied its performance; Chinese patent CN104645877B etc. synthesized ABA capped type Silicone surfactants and study their properties. However, there are few reports on the synthesis of cyclic silicone surfactants.

Traditional silicone surfactants are composed of a hydrophobic group and a hydrophilic group, and with the research on silicone surfactants, silicone surfactants composed of a hydrophobic group and two hydrophilic groups ( Typical such as Chinese patent CN104645877B), and a silicone surfactant composed of one hydrophobic group and three hydrophilic groups (typically such as Journal of Dispersion Science and Technology, 2016, 37:846–852) have been synthesized. However, there are few reports on the research on silicone surfactants formed by one hydrophobic group and more hydrophilic groups.

Therefore, in view of the problems such as the lack of varieties of cyclosiloxane surfactants, it is necessary to develop new cyclosiloxane surfactants and study their preparation methods.

Contents of the invention

The technical problem to be solved by the present invention is to provide a cyclosiloxane surfactant with a novel structure and a preparation method thereof.

In order to solve the technical problem of the above-mentioned first aspect, the invention provides a cyclosiloxane surfactant, whose general structural formula is as follows:

where R is:

In a specific embodiment of the present invention, the minimum surface tension of the aqueous solution of the cyclosiloxane surfactant is 23 and 32 mN/m; the critical micelle concentration in the aqueous solution is 55 and 160 mg/L.

In order to embody another task of completing the present invention, a second aspect of the present invention provides a method for preparing a cyclosiloxane surfactant of formula I, which comprises the following steps:

(1) Preparation of tetraepoxy-terminated cyclosiloxane

Using tetramethyltetrahydrocyclotetrasiloxane and allyl glycidyl ether as raw materials, under the action of platinum catalyst, after reacting at a certain temperature for a certain period of time, tetraepoxy-terminated cyclosiloxane is obtained through treatment;

(2) Preparation of tetraamino-terminated cyclosiloxane

After reacting ethylenediamine and the tetraepoxy-terminated cyclosiloxane raw material obtained in step (1) for a certain period of time at a certain temperature, the tetraamino-terminated cyclosiloxane is obtained through treatment;

(3) Preparation of glycosyl-modified cyclosiloxane surfactant

The saccharides and the step (2) to obtain the tetraamino-terminated cyclosiloxane are reacted in the presence of a low-carbon alcohol solvent, and the reaction temperature and the reaction time in the presence of a low-carbon alcohol solvent are controlled. After the reaction is completed, the low-carbon alcohol is evaporated solvent to obtain a glycosyl-modified cyclosiloxane surfactant.

where R is:

In a specific technical solution of the present invention, the molar ratio of tetramethyltetrahydrocyclotetrasiloxane to allyl glycidyl ether and catalyst in the step (1) is 1:4-20:0.05-0.5; The reaction temperature is controlled to be 60-150°C; the reaction time is controlled to be 5-50h.

In yet another specific technical solution of the present invention, the platinum catalyst in the step (1) is chloroplatinic acid; after the reaction, purification is carried out by vacuum distillation.

In yet another specific technical solution of the present invention, the molar ratio of tetraepoxy-terminated cyclosiloxane to ethylenediamine in the step (2) is 1:8-60; the reaction temperature is controlled at 25-100°C, and the The reaction time is 2-50 hours. After the reaction, unreacted raw materials are removed by distillation under reduced pressure, and purified under reduced pressure to obtain tetraamino-terminated cyclosiloxane.

In another specific technical scheme of the present invention, the molar ratio of the tetraamino-terminated cyclosiloxane of the step (3) to the sugar is 1:4-12; the control of low-carbon alcohol solvent The reaction temperature and reaction time in the presence of the reaction temperature are controlled to the reflux temperature of the solvent, and the reaction time is controlled to be 3-50h.

In yet another specific technical solution of the present invention, the sugar in step (3) refers to sugar lactone or sugar acid.

In yet another specific technical solution of the present invention, the sugar lactone in the step (3) refers to gluconolactone, and the sugar acid is lactobionic acid.

In yet another specific technical solution of the present invention, the low-carbon alcohol solvent in the step (3) is methanol, ethanol, propanol or isopropanol.

In a further specific technical solution of the present invention, a method for preparing cyclosiloxane surfactant, the reaction steps are as follows:

where R is:

As a new cyclosiloxane surfactant, the cyclosiloxane surfactant provided by the invention can enrich the types of cyclosiloxane surfactants and expand the scope of use. Because the preparation process is simple and not troublesome, and the preparation cost is low, it can meet the requirements of industrial scale-up production and can make the obtained cyclosiloxane surfactant have excellent surface activity, so it can be used in oil extraction, textile, leather, in the field of biotechnology.

detailed description

The following examples are further illustrations of the present invention, but the content of the present invention is not limited thereto. The embodiments in the description of the present invention are only used to illustrate the present invention, and they do not limit the protection scope of the present invention. The protection scope of the present invention is limited only by the claims, and any omission, replacement or modification made by those skilled in the art on the basis of the disclosed embodiments of the present invention will fall within the protection scope of the present invention.

The preparation of cyclosiloxane surfactants of the general structure shown below is illustrated by eight examples respectively.

where R is:

Example 1

Preparation of Tetraepoxy Terminated Cyclosiloxane

Add 24.0Kg (100mol) of tetramethyltetrahydrocyclotetrasiloxane, 45.61Kg (400mol) of allyl glycidyl ether, and 2.05Kg (5mol) of chloroplatinic acid as a catalyst in the reaction kettle, and react at 60°C for 50h Afterwards, 69.6 Kg of tetraepoxy-terminated cyclosiloxane was obtained by distillation under reduced pressure.

Preparation of Tetraamino-terminated Cyclosiloxane

Add 69.6Kg (100mol) of the above-mentioned tetraepoxy-terminated cyclosiloxane and 48.08Kg (800mol) of ethylenediamine into the reaction kettle, and react at 25°C for 50 hours. Terminated ring siloxane 96.6Kg.

Preparation of sugar-modified cyclosiloxane surfactant

Add 96.6 Kg (100 mol) of the above-mentioned tetraamino-terminated cyclosiloxane and 71.2 Kg (400 mol) of gluconolactone into the reaction kettle, use methanol as a solvent, and react at reflux temperature for 3 hours. The solvent methanol was evaporated, and 160.6 Kg of the product tetraglucamide modified cyclosiloxane surfactant was obtained after vacuum drying. The minimum surface tension of its aqueous solution measured with a K12 surface tensiometer is 23mN/m, and the critical micelle concentration is 55mg/L.

Example 2

The preparation of tetraepoxy-terminated cyclosiloxane and tetraamino-terminated cyclosiloxane is the same as in Example 1.

Preparation of sugar-modified cyclosiloxane surfactant

Add 96.6 Kg (100 mol) of the above-mentioned tetraamino-terminated cyclosiloxane and 143.3 Kg (400 mol) of lactobionic acid into the reaction kettle, use methanol as a solvent, and react at reflux temperature for 3 hours. The solvent methanol was evaporated, and 232.8 Kg of the product tetralactosamide-modified cyclosiloxane surfactant was obtained after vacuum drying. The minimum surface tension of its aqueous solution measured with a K12 surface tensiometer is 32mN/m, and the critical micelle concentration is 160mg/L.

Example 3

Preparation of tetraepoxy-terminated cyclosiloxane

Add 24.0Kg (100mol) of tetramethyltetrahydrocyclotetrasiloxane, 228Kg (2000mol) of allyl glycidyl ether, and 20.5Kg (50mol) of chloroplatinic acid as a catalyst in the reaction kettle, and react at 150°C for 5 hours 69.6Kg of tetraepoxy-terminated cyclosiloxane was obtained by distillation under reduced pressure.

Preparation of Tetraamino-terminated Cyclosiloxane

Add 69.6Kg (100mol) of the above-mentioned tetraepoxy-terminated cyclosiloxane and 360.6Kg (6000mol) of ethylenediamine into the reaction kettle, and react at 100°C for 2 hours. Terminated ring siloxane 96.6Kg.

Preparation of sugar-modified cyclosiloxane surfactant

Add 96.6 Kg (100 mol) of the above-mentioned tetraamino-terminated cyclosiloxane and 213.7 Kg (1200 mol) of gluconolactone into the reaction kettle, use ethanol as a solvent, and react at reflux temperature for 50 hours. The solvent ethanol was evaporated, and 160.6 Kg of the product tetraglucamide modified cyclosiloxane surfactant was obtained after vacuum drying. The minimum surface tension of its aqueous solution measured with a K12 surface tensiometer is 23mN/m, and the critical micelle concentration is 55mg/L.

Example 4

The preparation of tetraepoxy-terminated cyclosiloxane and tetraamino-terminated cyclosiloxane is the same as in Example 3.

Preparation of sugar-modified cyclosiloxane surfactant

Add 96.6 Kg (100 mol) of the above-mentioned tetraamino-terminated cyclosiloxane and 429.9 Kg (1200 mol) of lactobionic acid into the reaction kettle, use ethanol as a solvent, and react at reflux temperature for 50 hours. The solvent ethanol was evaporated, and 232.8 Kg of the product tetralactosamide-modified cyclosiloxane surfactant was obtained after vacuum drying. The minimum surface tension of its aqueous solution measured with a K12 surface tensiometer is 32mN/m, and the critical micelle concentration is 160mg/L.

Example 5

Preparation of Tetraepoxy Terminated Cyclosiloxane

Add 24.0Kg (100mol) of tetramethyltetrahydrocyclotetrasiloxane, 114Kg (1000mol) of allyl glycidyl ether, and 4.1Kg (10mol) of chloroplatinic acid as a catalyst in the reaction kettle, and react at 100°C for 20 hours 69.6Kg of tetraepoxy-terminated cyclosiloxane was obtained by distillation under reduced pressure.

Preparation of Tetraamino-terminated Cyclosiloxane

Add 69.6Kg (100mol) of the above-mentioned tetraepoxy-terminated cyclosiloxane and 120.2Kg (2000mol) of ethylenediamine into the reaction kettle, and react at 50°C for 25 hours. Terminated ring siloxane 96.6Kg.

Preparation of sugar-modified cyclosiloxane surfactant

Add 96.6 Kg (100 mol) of the above-mentioned tetraamino-terminated cyclosiloxane and 106.9 Kg (600 mol) of gluconolactone into the reaction kettle, use propanol as solvent, and react at reflux temperature for 10 hours. The solvent propanol was evaporated, and 160.6 Kg of the product tetraglucamide modified cyclosiloxane surfactant was obtained after vacuum drying. The minimum surface tension of its aqueous solution measured with a K12 surface tensiometer is 23mN/m, and the critical micelle concentration is 55mg/L.

Example 6

The preparation of tetraepoxy-terminated cyclosiloxane and tetraamino-terminated cyclosiloxane is the same as in Example 5.

Preparation of sugar-modified cyclosiloxane surfactant

Add 96.6 Kg (100 mol) of the above-mentioned tetraamino-terminated cyclosiloxane and 215.0 Kg (600 mol) of lactobionic acid into the reaction kettle, use propanol as solvent, and react at reflux temperature for 10 hours. The solvent propanol was evaporated, and 232.8 Kg of the product tetralactosamide-modified cyclosiloxane surfactant was obtained after vacuum drying. The minimum surface tension of its aqueous solution measured with a K12 surface tensiometer is 32mN/m, and the critical micelle concentration is 160mg/L.

Example 7

Preparation of tetraepoxy-terminated cyclosiloxane

Add 24.0Kg (100mol) of tetramethyltetrahydrocyclotetrasiloxane, 171.1Kg (1500mol) of allyl glycidyl ether, and 8.2Kg (20mol) of chloroplatinic acid as a catalyst in the reaction kettle, and react at 80°C for 30h Afterwards, 69.6 Kg of tetraepoxy-terminated cyclosiloxane was obtained by distillation under reduced pressure.

Preparation of Tetraamino-terminated Cyclosiloxane

Add 69.6Kg (100mol) of the above-mentioned tetraepoxy-terminated cyclosiloxane and 240.4Kg (4000mol) of ethylenediamine into the reaction kettle, and react at 70°C for 35h. Terminated ring siloxane 96.6Kg.

Preparation of sugar-modified cyclosiloxane surfactant

Add 96.6 Kg (100 mol) of the above-mentioned tetraamino-terminated cyclosiloxane and 142.5 Kg (800 mol) of gluconolactone into the reaction kettle, use isopropanol as a solvent, and react at reflux temperature for 30 hours. The solvent isopropanol was evaporated, and 160.6 Kg of the product tetraglucamide-modified cyclosiloxane surfactant was obtained after vacuum drying. The minimum surface tension of its aqueous solution measured with a K12 surface tensiometer is 23mN/m, and the critical micelle concentration is 55mg/L.

Example 8

The preparation of tetraepoxy-terminated cyclosiloxane and tetraamino-terminated cyclosiloxane is the same as in Example 7.

Preparation of sugar-modified cyclosiloxane surfactant

Add 96.6 Kg (100 mol) of the above-mentioned tetraamino-terminated cyclosiloxane and 286.6 Kg (800 mol) of lactobionic acid into the reaction kettle, use isopropanol as solvent, and react at reflux temperature for 30 hours. The solvent isopropanol was evaporated, and 232.8 Kg of the product tetralactosamide-modified cyclosiloxane surfactant was obtained after vacuum drying. The minimum surface tension of its aqueous solution measured with a K12 surface tensiometer is 32mN/m, and the critical micelle concentration is 160mg/L.

The above examples are only to illustrate the technical conception and characteristics of the present invention, and its purpose is to allow people familiar with this technology to understand the content of the present invention and implement it accordingly, and cannot limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (8)

1. a cyclosiloxane surfactant, its general structural formula is as follows: where R is: 2. a preparation method of cyclosiloxane surfactant, it may further comprise the steps: (1) Preparation of tetraepoxy-terminated cyclosiloxane Using tetramethyltetrahydrocyclotetrasiloxane and allyl glycidyl ether as raw materials, under the action of platinum catalyst, after reacting at a certain temperature for a certain period of time, tetraepoxy-terminated cyclosiloxane is obtained through treatment; (2) Preparation of tetraamino-terminated cyclosiloxane After reacting ethylenediamine and the tetraepoxy-terminated cyclosiloxane raw material obtained in step (1) for a certain period of time at a certain temperature, the tetraamino-terminated cyclosiloxane is obtained through treatment; (3) Preparation of glycosyl-modified cyclosiloxane surfactant The saccharides and the step (2) to obtain the tetraamino-terminated cyclosiloxane are reacted in the presence of a low-carbon alcohol solvent, and the reaction temperature and the reaction time in the presence of a low-carbon alcohol solvent are controlled. After the reaction is completed, the low-carbon alcohol is evaporated Solvent, obtain glycosyl modified cyclosiloxane surfactant, where R is: 3. the preparation method of cyclosiloxane surfactant according to claim 2, is characterized in that, in described step (1), the mixture of tetramethyltetrahydrocyclotetrasiloxane and allyl glycidyl ether and catalyzer The molar ratio is 1:4-20:0.05-0.5; the reaction temperature is controlled at 60-150°C; the reaction time is controlled at 5-50h. 4. the cyclosiloxane surfactant preparation method according to claim 2, is characterized in that, the platinum catalyst in described step (1) is chloroplatinic acid. 5. the preparation method of cyclosiloxane surfactant according to claim 2, is characterized in that, in described step (2), the mol ratio of tetraepoxy-terminated cyclosiloxane and ethylenediamine is 1:8- 60; control the reaction temperature to 25-100°C, and control the reaction time to 2-50h. 6. the preparation method of cyclosiloxane surfactant according to claim 2, is characterized in that, the mol ratio of tetraamino-terminated cyclosiloxane of described step (3) and described carbohydrate is 1:4 -12; the control of the reaction temperature and reaction time in the presence of a low-carbon alcohol solvent is to control the reaction temperature to the reflux temperature of the solvent, and control the reaction time to 3-50h. 7. The preparation method of cyclosiloxane surfactant according to claim 2 or 6, characterized in that, the carbohydrate in the step (3) refers to sugar lactone or sugar acid. 8. the preparation method of cyclosiloxane surfactant according to claim 2, is characterized in that, the low carbon alcohol solvent of described step (3) is methyl alcohol, ethanol, propanol or Virahol.