Trialkylsilyl alcohol polyoxyethylene ether surfactant as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of surfactants, and particularly relates to a trialkylsilyl alcohol polyoxyethylene ether surfactant as well as a preparation method and application thereof. The preparation method comprises the following steps: by taking trialkylsilane and allyl polyoxyethylene ether as raw materials, reacting for 1-10 hours at the temperature of 20-150 DEG C under the action of a'platinum 'or'ruthenium' catalyst to obtain faint yellow to yellow transparent liquid after the reaction is finished, and filtering to obtain the trialkylsilyl alcohol polyoxyethylene ether surfactant. The mixture is the trialkyl silanol polyoxyethylene ether surfactant. The preparation process is simple in preparation and suitable for large-scale industrial production. The product has the advantages of high surface activity, good wettability, low foam and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of surfactants, and specifically relates to a trialkylsilyl propanol polyoxyethylene ether surfactant and a preparation method and application thereof. Background Art

[0002] Surfactant is an amphiphilic molecule, which contains both hydrophilic and hydrophobic groups in its molecular structure. Among them, non-ionic surfactants are widely used in textiles, coatings, daily chemicals, agricultural chemicals and other fields due to their good surface activity and good wetting and emulsifying properties. Polyoxyethylene ether surfactants are the most widely used non-ionic surfactants, and their hydrophobic groups are mostly straight-chain fatty alcohols. Later studies found that isomeric alcohol polyoxyethylene ethers with branched structures introduced into the hydrophobic groups showed better surface activity, excellent wetting properties and less gel phase, and were more suitable for industrial terminal uses [Chen Xue, Study on the Characteristics of Isomeric Alcohol Ether Nonionic Surfactants. Proceedings of the Fourth Annual Academic Conference of the "Runtu" Cup China Textile Printing and Dyeing Auxiliary Industry. 2010: 199-201].

[0003] In recent years, there have been a large number of reports on isomeric alcohol polyoxyethylene ethers and their derivatives. For example, patent CN101225161B reported a method for preparing isomeric tridecanol polyoxyethylene ether using isomeric tridecanol and ethylene oxide as raw materials. Patent CN116284736B reported the preparation of secondary alcohol polyoxyethylene ether surfactants by using secondary alcohol as an initiator to initiate ethylene oxide addition reaction. Patent CN118290720A uses isononanol as an initiator and ethylene oxide for ring-opening polymerization to obtain isononanol polyoxyethylene ether. Patent CN106750243B reported a method for synthesizing isomeric decanol polyoxyethylene ether. Recently, Dong Jinxiang et al. also reported a method for preparing narrow distribution Guerbet alcohol polyoxyethylene ether [Journal of Molecular Liquids (2024): 125102]. As can be seen from the above literature, isomeric alcohol polyoxyethylene ethers are mostly prepared by ethoxylation reaction using isomeric alcohol and ethylene oxide as raw materials. The current preparation process has two shortcomings;

[0004] On the one hand, the current isomeric alcohols are mainly straight-chain alcohols with a small amount of branches introduced, resulting in a low degree of branching of the isomeric alcohols, which affects the performance of the isomeric alcohol polyoxyethylene ethers;

[0005] On the other hand, the raw material ethylene oxide is flammable and explosive, and is not easy to transport over long distances, so it has a strong regional nature. In addition, the ethoxylation reaction is a high-pressure polymerization, which leads to high risks in the preparation process. Summary of the invention

[0006] In view of this, the purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a method for preparing a highly isomerized trialkylsilyl propanol polyoxyethylene ether surfactant. The preparation process of the present invention is simple and suitable for large-scale industrial production. The product of the present invention has the advantages of high surface activity, good product wettability, low foaming, etc.

[0007] To achieve the above object, the technical solution of the present invention is as follows:

[0008] In a first aspect, the present invention provides a trialkylsilyl propanol polyoxyethylene ether surfactant having the following structural formula:

[0009]

[0010] Among them, m=0-5, n=1-15.

[0011] In some embodiments of the present invention, the minimum surface tension of the aqueous solution is 27.00-32.00 mN / m; the critical micelle concentration is 10-200.00 mg / L; the minimum contact angle on paraffin film is 0-15°, and the 2.5 g / L foam height is 0-25 mm.

[0012] In a second aspect, the present invention provides a method for preparing the trialkylsilyl propanol polyoxyethylene ether surfactant described in the first aspect, comprising the following steps:

[0013] With trialkylsilane and allyl polyoxyethylene ether as raw materials, a hydrosilylation reaction occurs under the action of a platinum or ruthenium catalyst to obtain the trialkylsilyl propanol polyoxyethylene ether surfactant.

[0014] In some embodiments of the present invention, the temperature of the hydrosilylation reaction is 20-150° C. and the time is 1-10 h.

[0015] In some embodiments of the present invention, the trialkylsilane is trimethylsilane, triethylsilane, tripropylsilane or tributylsilane.

[0016] In some embodiments of the present invention, the number of polyoxyethylene n in the allyl polyoxyethylene ether is in the range of 1-15.

[0017] In some embodiments of the present invention, the "platinum" or "ruthenium" catalyst is one or more of chloroplatinic acid, ruthenium chloride, and Karstedt's catalyst.

[0018] In some embodiments of the present invention, the molar ratio of the trialkylsilane to the allyl polyoxyethylene ether is 1:1.0-1.2.

[0019] In a third aspect, the present invention provides the use of the trialkylsilyl propanol polyoxyethylene ether surfactant described in the first aspect in a drug carrier. When the concentration of the surfactant in the aqueous solution is higher than the critical micelle concentration, vesicle aggregates can be formed for use as a drug carrier.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1) The trialkylsilyl propanol polyoxyethylene ether surfactant prepared by the present invention has less foam, better wetting performance and no gel phase due to the high degree of isomerization of the hydrophobic group, and is easy to be formulated in daily chemicals, and has potential application value in the fields of daily chemicals.

[0022] 2) The preparation process of the present invention is a hydrosilylation method, the raw materials are not flammable and explosive, the reaction conditions are mild, there is no geographical restriction, it is more energy-saving, and it is more conducive to industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the sample in Example 1.

[0024] Figure 2 It is the hydrogen nuclear magnetic resonance spectrum of the sample in Example 2.

[0025] Figure 3 It is the surface tension curve of the samples in Example 1 and Example 2 in aqueous solution.

[0026] Figure 4 is the foam height of the sample solutions in Examples 1 and 2.

[0027] Figure 5 is the contact angle of the sample solution on the paraffin film in Example 1 and Example 2.

[0028] Figure 6 It is the aggregate morphology of the samples in Example 1 (left) and Example 2 (right) in aqueous solution.

[0029] Figure 7 This is a photograph of the sample of Example 2 at a concentration of 50%. DETAILED DESCRIPTION

[0030] In order to facilitate the understanding of the present invention, the present invention will be described more fully below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0031] The present invention uses highly isomerized trialkylsilane and allyl polyoxyethylene ether as raw materials to prepare highly isomerized trialkylsilyl alcohol allyl polyoxyethylene ether through a hydrosilylation reaction, and the reaction equation is as follows:

[0032]

[0033] Among them, m=0-5, n=1-15.

[0034] Embodiment 1:

[0035] 10.0kg tripropylsilane, 24.0kg allyl polyoxyethylene ether (n=8) and prepared chloroplatinic acid catalyst (wherein the total amount of platinum accounts for 30ppm of the total amount of raw materials) are put into a reactor, nitrogen is introduced, and the temperature is heated to 60°C for activation for half an hour under stirring, and then the temperature is raised to 150°C and reacted for 5h. The conversion rate of tripropylsilane is determined by measuring the hydrogen content. After reaching the requirement, the above reaction is stopped and cooled to room temperature to obtain 33.0kg amber transparent liquid, i.e. tripropylsilyl propanol polyoxyethylene ether surfactant. Its structure is characterized by nuclear magnetic resonance hydrogen spectrum and infrared spectrum, and the analysis based on the peak area shows that tripropylsilyl propanol polyoxyethylene ether is successfully synthesized.

[0036] The surface tension at the critical micelle concentration was measured by Krüss Tensíío surface tension meter to be 28.32 mN / m, the minimum contact angle on the paraffin film surface was measured by Krüss DSA25 contact angle meter to be 11°, and the foam height in aqueous solution was measured according to the national standard GBT13173-2021 to be 22 mm. The product aggregates in aqueous solution were determined to be vesicles by transmission electron microscopy.

[0037] Embodiment 2:

[0038] 15.0kg tributylsilane, 42.0kg allyl polyoxyethylene ether (n=10) and prepared Karstedt catalyst (wherein the total amount of platinum accounts for 20ppm of the total amount of raw materials) are put into a reactor, nitrogen is introduced, and the temperature is heated to 60°C for activation for half an hour under stirring, and then the temperature is raised to 90°C and reacted for 4 hours. The conversion rate of tributylsilane is determined by measuring the hydrogen content. After reaching the requirement, the above reaction is stopped and cooled to room temperature to obtain 56.0kg amber transparent liquid, i.e. tributylsilyl propanol polyoxyethylene ether surfactant. Its structure is characterized by nuclear magnetic resonance hydrogen spectrum and infrared spectrum, and analysis based on the peak area size shows that tributylsilyl propanol polyoxyethylene ether is successfully synthesized.

[0039] The surface tension at the critical micelle concentration was measured by Krüss Tensíío surface tension meter to be 27.27 mN / m, and the minimum contact angle on the paraffin film surface was measured by Krüss DSA25 contact angle meter to be 10.0°. The foam height in aqueous solution was measured according to the national standard GBT13173-2021 to be 5 mm. The aggregates of the product in aqueous solution were determined to be vesicles by transmission electron microscopy.

[0040] Embodiment 3:

[0041] 10kg triethylsilane, 26.5kg allyl polyoxyethylene ether (n=5) and prepared ruthenium chloride catalyst (wherein the total amount of ruthenium accounts for 20ppm of the total amount of raw materials) are put into a reactor, nitrogen is introduced, and the temperature is heated to 60°C for activation for half an hour under stirring, and then the temperature is raised to 100°C and reacted for 7h. The conversion rate of triethylsilane is determined by measuring the hydrogen content. After reaching the requirement, the above reaction is stopped and cooled to room temperature to obtain 36.0kg amber transparent liquid, i.e. triethylsilyl propanol polyoxyethylene ether surfactant. Its structure is characterized by nuclear magnetic resonance hydrogen spectrum and infrared spectrum, and the analysis based on the peak area shows that triethylsilyl propanol polyoxyethylene ether is successfully synthesized.

[0042] The surface tension at the critical micelle concentration was measured by Krüss Tensíío surface tension meter to be 28.50 mN / m, and the minimum contact angle on the paraffin film surface was measured by Krüss DSA25 contact angle meter to be 8°. The foam height in aqueous solution was measured according to the national standard GBT13173-2021 to be 10 mm. The aggregates of the product in aqueous solution were determined to be vesicles by transmission electron microscopy.

[0043] Embodiment 4:

[0044] 6.4kg trimethylsilane, 13.8kg allyl polyoxyethylene ether (n=2) and prepared chloroplatinic acid catalyst (wherein the total amount of platinum accounts for 20ppm of the total amount of raw materials) are put into a reactor, nitrogen is introduced, and the temperature is heated to 60°C for activation for half an hour under stirring, and then the temperature is raised to 130°C for reaction for 2h. The conversion rate of trimethylsilane is determined by measuring the hydrogen content. After reaching the requirement, the above reaction is stopped and cooled to room temperature to obtain 20kg of yellow transparent liquid, i.e. trimethylsilyl propanol polyoxyethylene ether surfactant. Its structure is characterized by nuclear magnetic resonance hydrogen spectrum and infrared spectrum, and the analysis based on the peak area shows that trimethylsilyl propanol polyoxyethylene ether is successfully synthesized.

[0045] The surface tension at the critical micelle concentration was measured by Krüss Tensíío surface tension meter to be 32.00 mN / m, the minimum contact angle on the paraffin film surface was measured by Krüss DSA25 contact angle meter to be 15°, and the foam height in aqueous solution was 0 mm according to the national standard GBT13173-2021. The aggregates of the product in aqueous solution were determined to be vesicles by transmission electron microscopy.

[0046] In short, from the attached Figure 1-7It can be seen that the surface tension of highly isomerized trialkylsilyl propanol polyoxyethylene ether is significantly lower than that of linear fatty alcohol polyoxyethylene ether (AEO-9), it has no gel phase and low foam, and is more suitable for the preparation of concentrated cleaning agents. In addition, trialkylsilyl propanol polyoxyethylene ether can spontaneously form vesicle aggregates in aqueous solution.

[0047] The above description is only for better explaining the embodiments of the present invention, and is not intended to limit the present invention. Any modification or equivalent substitution that does not depart from the spirit and scope of the present invention shall fall within the scope of the present invention.

Claims

1. A trialkylsilyl propanol polyoxyethylene ether surfactant, characterized in that: It has the following structural formula: Among them, m=0-5, n=1-15.

2. The trialkylsilyl propanol polyoxyethylene ether surfactant according to claim 1, characterized in that The minimum surface tension of its aqueous solution is 27.00-32.00 mN / m; the critical micelle concentration is 10-200.00 mg / L; the minimum contact angle on paraffin film is 0-15°, and the 2.5 g / L foam height is 0-25 mm.

3. The method for preparing the trialkylsilyl propanol polyoxyethylene ether surfactant according to claim 1 or 2, characterized in that: The steps include: With trialkylsilane and allyl polyoxyethylene ether as raw materials, a hydrosilylation reaction occurs under the action of a "platinum" or "ruthenium" catalyst to obtain the trialkylsilyl propanol polyoxyethylene ether surfactant.

4. The method for preparing the trialkylsilyl propanol polyoxyethylene ether surfactant according to claim 3, characterized in that: The temperature of the hydrosilylation reaction is 20-150° C. and the time is 1-10 h.

5. The method for preparing the trialkylsilyl propanol polyoxyethylene ether surfactant according to claim 3, characterized in that: The trialkylsilane is trimethylsilane, triethylsilane, tripropylsilane or tributylsilane.

6. The method for preparing the trialkylsilyl propanol polyoxyethylene ether surfactant according to claim 3, characterized in that: The number of polyoxyethylene n in the allyl polyoxyethylene ether is in the range of 1-15.

7. The method for preparing the trialkylsilyl propanol polyoxyethylene ether surfactant according to claim 3, characterized in that: The "platinum" or "ruthenium" catalyst is one or more of chloroplatinic acid, ruthenium chloride, and Karstedt catalyst.

8. The method for preparing the trialkylsilyl propanol polyoxyethylene ether surfactant according to claim 3, characterized in that: The molar ratio of the trialkylsilane to the allyl polyoxyethylene ether is 1:1.0-1.

2.

9. Use of the trialkylsilyl propanol polyoxyethylene ether surfactant according to claim 1 or 2 in a drug carrier.

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