Anionic organosilicon surfactant and preparation method thereof

Abstract

The invention relates to an anionic organic silicon surfactant which is prepared by taking D4, diethyldiethoxysilane, polyethylene glycol trimethoxysilylpropyl ether, dibutyl ether, succinic anhydride, 7-amino-1, 3-naphthalene disulfonic acid, sodium carbonate and the like as raw materials through polymerization and other reactions. The surfactant is used as a fabric detergent, has triple functions of washing, static resistance and softening, does not need to be additionally added with an antistatic agent, a softener and the like, and is relatively good in stability and application effect and relatively wide in application market; besides, the surfactant has the functions of wetting, dispersing and cleaning, meanwhile, the excellent functions of low surface tension and softening are achieved, silicone oil and other softener components do not need to be additionally added like a conventional detergent, and an emulsification process does not need to be adopted; the obtained product can be directly used as a main surfactant component to be dissolved in water to prepare a high-end detergent product, and has the advantages of short preparation flow, simple process and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of surfactants, and specifically relates to an anionic organosilicon surfactant and a preparation method thereof, as well as application of the anionic organosilicon surfactant in fabric detergents. Background Art

[0002] Silicone oil has a small surface tension. When used in the washing process of clothes, hair and fabrics, its molecular chain can make these hair and fabrics extremely soft. Therefore, silicone oil is often used as a formula component in shampoos and high-end laundry detergents to enhance their softness. However, due to the poor compatibility of silicone oil alone with water, the preparation of the above products requires a special emulsification method, which requires the additional use of emulsifiers. The stability of the emulsified products is often poor, and stratification often occurs after long-term storage, affecting the application effect. Moreover, since the silicone oil molecules and the surfactant molecules used are in a separated state, it will also affect the balance between washing and softening, resulting in uneven softness in some areas of the washed fabric or hair, which affects the application experience to a certain extent.

[0003] In view of the above problems, the present invention adopts D4, diethyldiethoxysilane, polyethylene glycol trimethoxysilyl propyl ether, dibutyl ether, succinic anhydride, 7-amino-1,3-naphthalene disulfonic acid, sodium carbonate and other raw materials, and prepares an anionic silicone surfactant through polymerization and other reactions. The surfactant is used as a fabric detergent, and has the triple functions of washing, antistatic and softening; at the same time, the anionic silicone surfactant molecules introduce silicone oil segment structure and sodium sulfonate and amide structure, which has the wetting, dispersing and cleaning functions, and realizes excellent low surface tension and soft functions, and can be dissolved in water, and can be directly dissolved in water without special emulsification process for the preparation of high-end detergent products, etc., and has good effects. Summary of the invention

[0004] The present invention relates to an anionic organosilicon surfactant, which comprises the following raw materials in molar proportions:

[0005]

[0006]

[0007] The components also include Catalyst 1 and Catalyst 2.

[0008] Preferably, the catalyst 1 is stannous chloride, and the amount used is 0.2-0.3% of the mass of succinic anhydride; the catalyst 2 is concentrated hydrochloric acid, and the concentration is 32-35%, and the amount used is 1-1.5% of the mass of D4.

[0009] The method for preparing an anionic silicone surfactant as described above comprises the following steps:

[0010] A. Add the formulated amount of 7-amino-1,3-naphthalene disulfonic acid, succinic anhydride, catalyst 1, and one-half the formulated amount of dibutyl ether into a reaction kettle 1, start stirring and heat to perform an amidation reaction;

[0011] B. Take a sample to test the total amine value. When the total amine value drops to 1 mgKOH / g, it means that the amino group has basically reacted and the amidation reaction is completed. The reaction intermediate solution is obtained and set aside.

[0012] C. Add the formula amount of D4, diethyldiethoxysilane and catalyst 2, and the remaining formula amount of dibutyl ether into the reaction kettle 2, then start stirring, and heat up to carry out polymerization reaction;

[0013] D. Sampling and detecting the content of diethyldiethoxysilane by gas chromatography. When the conversion rate of diethyldiethoxysilane reaches 97% or more, adding a formulated amount of polyethylene glycol trimethoxysilyl propyl ether, and heating to carry out chain extension polymerization reaction;

[0014] E. Sampling and testing the room temperature viscosity (25° C.) of the polymer, when the room temperature viscosity of the polymer reaches 370-410 mPa·s, then adding the reaction intermediate solution obtained in step B to continue the carboxyl grafting and capping reaction;

[0015] F. Take samples to test the acid value of the polymer. When the acid value of the polymer reaches 90-105 mgKOH / g, it indicates that the carboxyl end-capping reaction is completed; cool to 80-85°C, add the formula amount of sodium carbonate for neutralization and salt formation reaction, take samples for testing, and when the acid value of the polymer drops to 1 mgKOH / g, it indicates that the neutralization reaction is completed;

[0016] After cooling and post-treatment, an anionic silicone surfactant is obtained.

[0017] Preferably, in step A, stirring is started and the temperature is raised to 130-135° C. to carry out the amidation reaction.

[0018] Preferably, in step C, the temperature is raised to 110-115° C. for polymerization reaction; in step D, the temperature is raised to 130-135° C. for chain extension polymerization reaction.

[0019] Preferably, in step E, the carboxyl grafting and capping reaction is carried out at 130-135°C.

[0020] Preferably, in step F, the cooling post-treatment includes: cooling to 30-40°C, then filtering to remove excess unreacted sodium carbonate particles to obtain a filtrate; pumping the filtrate into a distillation kettle, heating to 110-115°C, and then starting a vacuum system to perform reduced pressure distillation to remove the solvent; when the volatile matter is less than 1%, releasing the vacuum system and discharging at high temperature to obtain an anionic silicone surfactant.

[0021] Preferably, in step F, the neutralization and salt-forming reaction time is 1-2 h.

[0022] For example, the preparation method of the anionic silicone surfactant comprises the following steps:

[0023] A. Add the formulated amount of 7-amino-1,3-naphthalene disulfonic acid, succinic anhydride, catalyst 1, and one-half the formulated amount of dibutyl ether into reactor 1, start stirring and heat to 130-135° C. to carry out amidation reaction;

[0024] B. Take a sample to test the total amine value. When the total amine value drops to 1 mgKOH / g, it means that the amino group has basically reacted and the amidation reaction is completed. The reaction intermediate solution is obtained and set aside.

[0025] C. Add the formula amount of D4, diethyldiethoxysilane and catalyst 2, and the remaining formula amount of dibutyl ether into the reaction kettle 2, then start stirring, and heat to 110-115° C. to carry out polymerization reaction;

[0026] D. Take a sample and detect the content of diethyldiethoxysilane by gas chromatography. When the conversion rate of diethyldiethoxysilane reaches more than 97%, add the formulated amount of polyethylene glycol trimethoxysilyl propyl ether and raise the temperature to 130-135° C. to carry out chain extension polymerization reaction;

[0027] E. Sampling and testing the room temperature viscosity (25° C.) of the polymer, when the room temperature viscosity of the polymer reaches 370-410 mPa·s, then adding the reaction intermediate solution obtained in step B, and continuing the carboxyl grafting and capping reaction at 130-135° C.;

[0028] F. Take samples to detect the acid value of the polymer. When the acid value of the polymer reaches 90-105 mgKOH / g, it indicates that the carboxyl end-capping reaction is completed; cool to 80-85°C, add the formula amount of sodium carbonate for neutralization and salt-forming reaction for 1-2 hours, take samples for detection, and when the acid value of the polymer is reduced to 1 mgKOH / g, it indicates that the neutralization reaction is completed; cool to 30-40°C, and then filter to remove excess unreacted sodium carbonate particles to obtain a filtrate; pump the filtrate into a distillation kettle, heat to 110-115°C, and then start the vacuum system for reduced pressure distillation to remove the solvent; when the volatile matter is less than 1%, release the vacuum system and discharge the material at high temperature to obtain an anionic silicone surfactant.

[0029] The obtained product has an appearance of a milky white paste, a viscosity (50°C) of 3500-3800 mPa·s, and a pH of 8-9.

[0030] The present invention also relates to the use of the anionic organosilicon surfactant as described above or the anionic organosilicon surfactant obtained by the preparation method in fabric detergents.

[0031] Beneficial Effects

[0032] The present invention adopts D4, diethyldiethoxysilane, polyethylene glycol trimethoxysilyl propyl ether, dibutyl ether, succinic anhydride, 7-amino-1,3-naphthalene disulfonic acid, sodium carbonate and other raw materials, and prepares an anionic silicone surfactant through polymerization and other reactions. The surfactant is used as a fabric detergent, and has the triple functions of washing, antistatic and softening, and does not need to be added with antistatic agents and softeners. It has good stability and application effect, and has a wide application market. At the same time, the anionic silicone surfactant molecules introduce silicone oil segment structure and sodium sulfonate and amide structure, and have wetting, dispersing and cleaning functions, while achieving excellent low surface tension and soft functions. It does not need to add softener ingredients such as silicone oil like conventional detergents, and does not need to adopt emulsification process. The obtained product can be directly stirred and dissolved with water for the preparation of high-end detergent products, and has the advantages of short preparation process and simple process.

[0033] The present invention has been described in detail above, but the above embodiments are only illustrative in nature and are not intended to limit the present invention. In addition, this article is not limited by any theory described in the above prior art or invention content or the following examples. DETAILED DESCRIPTION

[0034] The present invention is further described below in conjunction with examples. It should be noted that the following examples are provided for illustrative purposes only and do not constitute a limitation on the scope of protection claimed for the present invention.

[0035] Unless otherwise specified, the raw materials, reagents, methods, etc. used in the examples are conventional raw materials, reagents, methods in the art.

[0036] Example 1

[0037] An anionic silicone surfactant comprises the following raw materials in molar proportions:

[0038]

[0039] The catalyst 1 is stannous chloride, and the dosage is 0.25% of the mass of succinic anhydride; the catalyst 2 is concentrated hydrochloric acid, and the concentration is 35%, and the dosage is 1% of the mass of D4.

[0040] The preparation method of the anionic silicone surfactant comprises the following steps:

[0041] A. Add the formulated amount of 7-amino-1,3-naphthalene disulfonic acid, succinic anhydride, catalyst 1, and one-half the formulated amount of dibutyl ether into reactor 1, start stirring and heat to 130-135° C. to carry out amidation reaction;

[0042] B. Take a sample to test the total amine value. When the total amine value drops to 1 mgKOH / g, it means that the amino group has basically reacted and the amidation reaction is completed. The reaction intermediate solution is obtained and set aside.

[0043] C. Add the formula amount of D4, diethyldiethoxysilane and catalyst 2, and the remaining formula amount of dibutyl ether into the reaction kettle 2, then start stirring, and heat to 110-115° C. to carry out polymerization reaction;

[0044] D. Take a sample and detect the content of diethyldiethoxysilane by gas chromatography. When the conversion rate of diethyldiethoxysilane reaches 97%, add the formulated amount of polyethylene glycol trimethoxysilyl propyl ether and raise the temperature to 130-135° C. to carry out chain extension polymerization reaction;

[0045] E. Sampling and testing the room temperature viscosity of the polymer, when the viscosity of the polymer reaches 370-410 mPa·s, then adding the reaction intermediate solution obtained in step B, and continuing the carboxyl grafting and capping reaction at 130-135° C.;

[0046] F. Take samples to detect the acid value of the polymer. When the acid value of the polymer reaches 90-105 mgKOH / g, it indicates that the carboxyl end-capping reaction is completed; cool to 85°C, add the formula amount of sodium carbonate for neutralization and salt-forming reaction for 2 hours, take samples for detection, and when the acid value of the polymer is reduced to 1 mgKOH / g, it indicates that the neutralization reaction is completed; cool to 40°C, and then filter to remove excess unreacted sodium carbonate particles to obtain a filtrate; pump the filtrate into a distillation kettle, heat to 115°C, and then start the vacuum system for reduced pressure distillation to remove the solvent; when the volatile matter is less than 1%, release the vacuum system and discharge the material at high temperature to obtain an anionic silicone surfactant.

[0047] Appearance: milky white paste, viscosity (50°C) is 3688mPa·s, pH is 8.1.

[0048] Example 2

[0049] An anionic silicone surfactant comprises the following raw materials in molar proportions:

[0050]

[0051] Catalyst 1 is stannous chloride, and the amount used is 0.3% of the mass of succinic anhydride; Catalyst 2 is concentrated hydrochloric acid, with a concentration of 32%, and the amount used is 1.5% of the mass of D4.

[0052] The preparation method is the same as Example 1.

[0053] Appearance: milky white paste, viscosity (50°C) is 3512mPa·s, pH is 8.3.

[0054] Example 3

[0055] An anionic silicone surfactant comprises the following raw materials in molar proportions:

[0056]

[0057] Catalyst 1 is stannous chloride, and the amount used is 0.3% of the mass of succinic anhydride; Catalyst 2 is concentrated hydrochloric acid, with a concentration of 35%, and the amount used is 1% of the mass of D4.

[0058] The preparation method is the same as Example 1.

[0059] Appearance: milky white paste, viscosity (50°C) is 3742mPa·s, pH is 8.6.

[0060] Example 4

[0061] An anionic silicone surfactant comprises the following raw materials in molar proportions:

[0062]

[0063] Catalyst 1 is stannous chloride, and the amount used is 0.2% of the mass of succinic anhydride; catalyst 2 is concentrated hydrochloric acid, with a concentration of 35%, and the amount used is 1% of the mass of D4.

[0064] The preparation method is the same as Example 1.

[0065] Appearance: milky white paste, viscosity (50°C) is 3614mPa·s, pH is 8.4.

[0066] Comparative Example 1

[0067] The commercially available common anionic surfactant sodium dodecylbenzene sulfonate was used as comparative example 1.

[0068] Performance Testing:

[0069] (1) Detergency test: The test was conducted in accordance with the method specified in GB / T 13174-2021 "Determination of Detergency and Cycle Washing Performance of Detergents for Clothing Materials"; the sample concentration was 0.3 wt%; the detergent solution in the washing test was prepared with 250 mg / kg hard water;

[0070] (2) Foaming power was measured according to GB / T7462-1994 "Determination of foaming power of surfactants - Improved Ross-Miles method". A test solution with an active substance content of 2 g / L was prepared with hard water and measured at 50.0±1.0°C. The higher the foam height in the same time, the better the foaming power.

[0071] (3) Antistatic performance and softness test: First, the products of Examples 1-4 and Comparative Example 1 were prepared into a 7% aqueous solution, and the woven twill pure cotton bleached fabric used in the experiment was soaked in the aqueous solution for 20 minutes, then rolled dry with a rolling dryer, and repeatedly dried at 40°C. The fabric was taken out for antistatic performance and softness tests.

[0072] The antistatic performance test was conducted according to the method in GB / T14342-1993 "Test Method for Specific Resistance of Synthetic Staple Fibers". The smaller the resistance value, the better the antistatic effect. The softness test was conducted by five masters who have been engaged in hand finishing for a long time. The test was divided into 1 to 5 levels. The larger the value, the softer it is. The test results are shown in Table 1.

[0073] Table 1 Comparison of product performance between the embodiment and the comparative example

[0074]

[0075]

[0076] As can be seen from Table 1, the anionic silicone surfactant prepared by the present invention using a specific formula and process not only has good decontamination ability and foaming power, but also has antistatic properties. The softness level of the fabric surface after washing is high, basically above level 4, with good comprehensive performance, and can be used as the main surfactant in high-end detergents. In addition, high-end detergents often need to add small molecule silicone oil components to improve the softness of the fabric, and the added silicone oil itself is difficult to dissolve in water, so the process of preparing high-end detergents requires the use of a special emulsification process to prevent it from stratification, and the preparation process is complicated, and the product of the present invention is an anionic silicone surfactant, which can be dissolved in water by itself, and at the same time contains silicone oil segments by itself, has a soft function, and can prepare high-end detergent products without using a special emulsification process, with the advantage of a simple preparation process. And Comparative Example 1 uses sodium dodecylbenzene sulfonate, a component of ordinary detergent, which is the most commonly used anionic surfactant. The results show that its decontamination ability and foaming power are slightly lower than the product of the present invention, but the antistatic performance and softness are poor, and it is impossible to meet the use of high-end detergents in the field of fabric washing.

[0077] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions described in the above embodiments may be modified, or some or all of the technical features thereof may be replaced by equivalents, without departing from the spirit and essence of the claims of the present invention; and these modifications or replacements are still within the scope defined by the claims of the present invention.

Claims

1. An anionic silicone surfactant, characterized in that: The raw materials comprising the following molar compositions: The components also include Catalyst 1 and Catalyst 2.

2. An anionic organosilicon surfactant as claimed in claim 1, further characterized in that the catalyst 1 is stannous chloride, and the amount used is 0.2-0.3% of the mass of succinic anhydride.

3. An anionic organosilicon surfactant as claimed in claim 1, further characterized in that the catalyst 2 is concentrated hydrochloric acid with a concentration of 32-35% and an amount of 1-1.5% of the mass of D4.

4. A method for preparing an anionic organosilicon surfactant according to any one of claims 1 to 3, characterized in that: The following steps are involved: A. Add the formulated amount of 7-amino-1,3-naphthalene disulfonic acid, succinic anhydride, catalyst 1, and one-half the formulated amount of dibutyl ether into a reaction kettle 1, start stirring and heat to perform an amidation reaction; B. Take a sample to test the total amine value. When the total amine value is reduced to 1 mgKOH / g, the amidation reaction is completed, and a reaction intermediate solution is obtained for standby use; C. Add the formula amount of D4, diethyldiethoxysilane and catalyst 2, and the remaining formula amount of dibutyl ether into the reaction kettle 2, then start stirring, and heat up to carry out polymerization reaction; D. Sampling and detecting the content of diethyldiethoxysilane by gas chromatography. When the conversion rate of diethyldiethoxysilane reaches 97% or more, adding a formulated amount of polyethylene glycol trimethoxysilyl propyl ether, and heating to carry out chain extension polymerization reaction; E. Sampling and testing the room temperature viscosity of the polymer, when the room temperature viscosity of the polymer reaches 370-410 mPa·s, then adding the reaction intermediate solution obtained in step B to continue the carboxyl grafting and capping reaction; F. Take samples to test the acid value of the polymer. When the acid value of the polymer reaches 90-105 mgKOH / g, it indicates that the carboxyl end-capping reaction is completed; cool to 80-85°C, add the formula amount of sodium carbonate for neutralization and salt formation reaction, take samples for testing, and when the acid value of the polymer drops to 1 mgKOH / g, it indicates that the neutralization reaction is completed; After cooling and post-treatment, an anionic organic silicon surfactant is obtained.

5. A method for preparing an anionic organosilicon surfactant as claimed in claim 4, further characterized in that, in step A, stirring is started and the temperature is raised to 130-135°C for amidation reaction.

6. A method for preparing an anionic organosilicon surfactant as claimed in claim 4, further characterized in that in step C, the temperature is raised to 110-115°C for polymerization reaction; in step D, the temperature is raised to 130-135°C for chain extension polymerization reaction.

7. The method for preparing an anionic organosilicon surfactant according to claim 4, further characterized in that in step E, the carboxyl grafting and capping reaction is carried out at 130-135°C.

8. The method for preparing an anionic organosilicon surfactant according to claim 4, further characterized in that in step F, the cooling post-treatment comprises: The temperature is lowered to 30-40°C, and then the excess unreacted sodium carbonate particles are removed by suction to obtain a filtrate; the filtrate is pumped into a distillation kettle, the temperature is raised to 110-115°C, and then the vacuum system is started to perform reduced pressure distillation to remove the solvent; when the volatile matter is less than 1%, the vacuum system is released, and the material is discharged at a high temperature to obtain an anionic silicone surfactant.

9. A method for preparing an anionic organosilicon surfactant as claimed in claim 4, further characterized in that in step F, the neutralization and salt-forming reaction time is 1-2 hours.

10. Use of the anionic organosilicon surfactant according to any one of claims 1 to 3 or the anionic organosilicon surfactant obtained by the preparation method according to any one of claims 4 to 9 in a fabric detergent.

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