Fluorine-modified acetylene glycol surfactant, and preparation method and application thereof

Abstract

The application belongs to the technical field of surfactants, and particularly relates to a fluorine-modified alkyne diol surfactant, which has a structure as shown in general formula (I). In the general formula (I), R1 and R3 are each independently H or CH3, R2 and R4 are each independently a linear or branched C1-C10 alkyl group, R5 is one of H, a linear or branched C1-C8 alkyl group, and a benzyl group, R f and R f ' are one of fluorinated C1-C10 linear or branched alkyl sulfonyl groups, p is an integer of 0-40, y is an integer of 0-40, and p and y are not 0 at the same time. The application also relates to a preparation method of the fluorine-modified alkyne diol surfactant. The fluorine-modified alkyne diol surfactant has low static surface tension and low foamability, and can be applied as a defoaming agent in paints, inks, and cleaning agents.

Description

Technical Field

[0001] This invention belongs to the field of surfactant technology, specifically relating to a fluorinated modified acetylenic diol surfactant, its preparation method, and its application. Background Technology

[0002] Additives are essential in the preparation of coatings, inks, and cleaning agents. Among them, wetting agents, as the main additives for wetting the substrates of coatings, inks, and cleaning agents, play a crucial role in reducing the surface tension of the product and increasing its wetting, spreading, and penetration ability on substrates such as steel and plastic films. When the surface tension of the product decreases, the system produces more foam, and the application defects caused by foam will greatly affect the product quality. Traditionally, adding defoamers is one of the important measures to deal with this problem, but it will lead to increased costs. Therefore, developing additives with both wetting and defoaming / foam-suppressing capabilities is one of the research topics of many experts and scholars at home and abroad.

[0003] Alkyne glycol compounds and their derivatives, such as alkynyl glycol polyoxyethylene ethers, are widely used as wetting and defoaming agents. However, studies have shown that alkynyl glycol polyoxyethylene ethers have high surface tension and slightly insufficient wetting ability. Research indicates that tetramethyl-5-decyn-4,7-diol polyoxyethylene ether has a surface tension as high as 40 dyn / cm at a concentration of 0.1 g / L, while tetramethyl-6-decyn-5,8-diol polyoxyethylene ether has a minimum surface tension of 26 dyn / cm at the same concentration. Therefore, developing alkynyl glycol polyoxyethylene ethers with lower surface tension and lower foaming properties is particularly important. Summary of the Invention

[0004] The present invention aims to provide a fluorinated modified acetylenic diol surfactant to solve the problem of insufficient wetting ability caused by the high surface tension of acetylenic diol polyoxyethylene ether.

[0005] To achieve the above objectives, the present invention provides a fluorinated alkynyldiol surfactant, wherein the structure of the fluorinated alkynyldiol surfactant is shown in the following general formula (Ⅰ):

[0006]

[0007] In general formula (Ⅰ), R1 and R3 are each independently H or CH3; R2 and R4 are each independently straight-chain or branched C1-C10 alkyl groups; R5 is one of H, straight-chain or branched C1-C8 alkyl groups, or benzyl; R f R f Each is independently a fluorinated C1-C10 straight-chain or branched alkyl sulfonyl group; p is an integer from 0 to 40, y is an integer from 0 to 40, and p and y are not both 0.

[0008] Optionally, in general formula (Ⅰ), p+y=1-30.

[0009] The present invention also provides a method for preparing the above-mentioned fluorinated modified acetylenic diol surfactant, comprising the following steps:

[0010] S1. In an oxygen-free environment, at 70-100℃, the catalyst and amino acids are added to acetylenol polyoxyethylene ether, stirred and reacted for 8-12 hours until anhydrous substances are removed, to obtain acetylenol polyoxyethylene ether amino acid ester; the structure of the amino acid is shown in the following general formula (II), and the structure of the acetylenol polyoxyethylene ether is shown in the following general formula (III):

[0011]

[0012] In general formula (II), R5 is one of H, straight-chain or branched C1-C8 alkyl, or benzyl;

[0013] In general formula (Ⅲ), R1 and R3 are each independently H or CH3, R2 and R4 are each independently straight-chain or branched C1-C10 alkyl, and p is an integer from 0 to 40, y is an integer from 0 to 40, and p and y are not both 0.

[0014] S2. In an oxygen-free environment at 0-15°C, a fluorine compound is added dropwise to the acetylenol polyoxyethylene ether amino acid ester obtained in step S1, and the reaction is carried out for 4-5 hours to obtain fluorinated modified acetylenol polyoxyethylene ether; the fluorine compound is one or both of fluorinated C1-C10 straight-chain or branched alkyl sulfonyl fluoride.

[0015] Optionally, in step S1, the catalyst is one or two of p-benzenesulfonic acid, concentrated sulfuric acid, and dodecylbenzenesulfonic acid.

[0016] Optionally, the molar ratio between the acetylenol polyoxyethylene ether, the catalyst, the amino acid and the fluorine compound is 1:(0.001-0.05):(2-2.5):(2-2.5).

[0017] The working principle and beneficial effects of this solution are as follows: Acetylene glycol polyoxyethylene ether with the structure shown in general formula (III) has excellent defoaming ability and can reduce the foaming properties of the system when applied in coatings, inks, and cleaning agents. However, acetylene glycol polyoxyethylene ether with this structure has a high surface tension, resulting in insufficient wetting ability. Therefore, in this solution, acetylene glycol polyoxyethylene ether with the structure shown in general formula (III) is modified to obtain a fluorinated acetylene glycol surfactant, which has low surface tension, excellent substrate wetting, and excellent defoaming / foam suppression ability, and can be widely used in the fields of coatings, inks, and cleaning agents. Detailed Implementation

[0018] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0019] This invention provides a fluorinated acetylinyl diol surfactant, the structure of which is shown in the following general formula (Ⅰ):

[0020]

[0021] In general formula (Ⅰ), R1 and R3 are each independently H or CH3; R2 and R4 are each independently straight-chain or branched C1-C10 alkyl groups; R5 is one of H, straight-chain or branched C1-C8 alkyl groups, or benzyl; R f R f Each is independently a fluorinated C1-C10 straight-chain or branched alkyl sulfonyl group; p is an integer from 0 to 40, y is an integer from 0 to 40, and p and y are not both 0, preferably p+y=1-30.

[0022] This invention also provides a method for preparing a fluorinated acetylene diol surfactant, comprising the following steps:

[0023] S1. In an oxygen-free environment, at 70-100℃, the catalyst and amino acids are added to acetylenol polyoxyethylene ether, stirred and reacted for 8-12 hours until anhydrous substances are removed, to obtain acetylenol polyoxyethylene ether amino acid ester; the structure of the amino acid is shown in the following general formula (II), and the structure of the acetylenol polyoxyethylene ether is shown in the following general formula (III):

[0024]

[0025] In general formula (II), R5 is one of H, straight-chain or branched C1-C8 alkyl, or benzyl;

[0026] In general formula (Ⅲ), R1 and R3 are each independently H or CH3, R2 and R4 are each independently straight-chain or branched C1-C10 alkyl, and p is an integer from 0 to 40, y is an integer from 0 to 40, and p and y are not both 0.

[0027] S2. In an oxygen-free environment at 0-15°C, a fluorine compound is added dropwise to the acetylenol polyoxyethylene ether amino acid ester obtained in step S1, and the reaction is carried out for 4-5 hours to obtain fluorinated modified acetylenol polyoxyethylene ether; the fluorine compound is one or both of fluorinated C1-C10 straight-chain or branched alkyl sulfonyl fluoride.

[0028] In step S1, the catalyst is one or two of p-benzenesulfonic acid, concentrated sulfuric acid, and dodecylbenzenesulfonic acid; the molar ratio between acetylenic glycol polyoxyethylene ether, the catalyst, the amino acid, and the fluorine compound is 1:(0.001-0.05):(2-2.5):(2-2.5), and preferably 1:0.03:(2-2.05):(2-2.05). Furthermore, the amino acid is preferably leucine or phenylalanine.

[0029] The following specific examples illustrate the present invention in detail. It should also be understood that the following examples are only for specific illustrative purposes and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0030] Example 1

[0031] This embodiment provides a fluorinated acetylenol surfactant having a structure as shown in formula (I):

[0032]

[0033] In formula (Ⅰ), R1 and R3 are both CH3; R2 and R4 are both isopropyl; R5 is H; R f R f ' are all trifluoromethylsulfonyl groups; p+y=2.

[0034] This embodiment also provides a method for preparing the above-mentioned fluorinated modified acetylenic diol surfactant, which includes the following steps:

[0035] S1. In a nitrogen atmosphere at 70-75°C, concentrated sulfuric acid and glycine are added to 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether, stirred and reacted for 8-12 hours until anhydrous substances are removed, to obtain 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether amino acid ester.

[0036] S2. In a nitrogen atmosphere at 0-10°C, trifluoromethanesulfonyl fluoride is added dropwise to the 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether amino acid ester obtained in step S1. The reaction is carried out for 4-5 hours. After neutralization and desalting, the fluorinated modified acetylenol polyoxyethylene ether (i.e., fluorinated modified acetylenol surfactant) is obtained by filtration.

[0037] The molar ratio of 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether, concentrated sulfuric acid, glycine, and trifluoromethylsulfonyl fluoride is 1:0.03:2.05:2.05.

[0038] Example 2

[0039] This embodiment provides a fluorinated acetylenol surfactant having a structure as shown in formula (I):

[0040]

[0041] In formula (Ⅰ), R1 and R3 are both CH3; R2 and R4 are both isobutyl; R5 is methyl; R f R f ' are all heptadecafluoro-1-octanesulfonyl; p+y=4.

[0042] This embodiment also provides a method for preparing the above-mentioned fluorinated modified acetylenic diol surfactant, which includes the following steps:

[0043] S1. In a nitrogen atmosphere at 70-75°C, p-benzenesulfonic acid and alanine are added to 2,5,8,11-tetramethyldodecane-6-yne-5,8-diol polyoxyethylene ether, stirred and reacted for 8-12 hours until anhydrous substances are removed, to obtain 2,5,8,11-tetramethyldodecane-6-yne-5,8-diol polyoxyethylene ether amino acid ester.

[0044] S2. In a nitrogen atmosphere at 0-10°C, add heptadecafluoro-1-octanesulfonyl fluoride dropwise to the 2,5,8,11-tetramethyldodecane-6-yne-5,8-diol polyoxyethylene ether amino acid ester obtained in step S1. React for 4-5 hours, neutralize and desalt, and filter to obtain fluorinated modified ynediol polyoxyethylene ether (i.e., fluorinated modified ynediol surfactant).

[0045] The molar ratio of 2,5,8,11-tetramethyldodecane-6-yne-5,8-diol polyoxyethylene ether, p-benzenesulfonic acid, alanine, and heptadecafluoro-1-octanesulfonyl fluoride is 1:0.03:2:2.

[0046] Example 3

[0047] This embodiment provides a fluorinated acetylenol surfactant having a structure as shown in formula (I):

[0048]

[0049] In formula (Ⅰ), R1 and R3 are both CH3; R2 and R4 are both isobutyl; R5 is isopropyl; R f R f' are all heptadecafluoro-1-octanesulfonyl; p+y=4.

[0050] This embodiment also provides a method for preparing the above-mentioned fluorinated modified acetylenic diol surfactant, which includes the following steps:

[0051] S1. In a nitrogen atmosphere at 70-75°C, p-benzenesulfonic acid and leucine are added to 2,5,8,11-tetramethyldodecane-6-yne-5,8-diol polyoxyethylene ether, stirred and reacted for 8-12 hours until anhydrous substances are removed, to obtain 2,5,8,11-tetramethyldodecane-6-yne-5,8-diol polyoxyethylene ether amino acid ester.

[0052] S2. In a nitrogen atmosphere at 0-10°C, add heptadecafluoro-1-octanesulfonyl fluoride dropwise to the 2,5,8,11-tetramethyldodecane-6-yne-5,8-diol polyoxyethylene ether amino acid ester obtained in step S1. React for 4-5 hours, neutralize and desalt, and filter to obtain fluorinated modified ynediol polyoxyethylene ether (i.e., fluorinated modified ynediol surfactant).

[0053] The molar ratio of 2,5,8,11-tetramethyldodecane-6-yne-5,8-diol polyoxyethylene ether, p-benzenesulfonic acid, leucine and heptadecano-1-octanesulfonyl fluoride is 1:0.03:2:2.05.

[0054] Example 4

[0055] This embodiment provides a fluorinated acetylenol surfactant having a structure as shown in formula (I):

[0056]

[0057] In formula (Ⅰ), R1 and R3 are both CH3; R2 and R4 are both isopropyl; R5 is benzyl; R f R f All of them are heptadecafluoro-1-octanesulfonyl; p+y=10.

[0058] This embodiment also provides a method for preparing the above-mentioned fluorinated modified acetylenic diol surfactant, which includes the following steps:

[0059] S1. In a nitrogen atmosphere at 70-75°C, p-benzenesulfonic acid and phenylalanine are added to 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether, stirred and reacted for 8-12 hours until anhydrous substances are removed, to obtain 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether amino acid ester.

[0060] S2. In a nitrogen atmosphere at 0-10°C, undecylenyl cyclohexane sulfonyl fluoride is added dropwise to the 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether amino acid ester obtained in step S1. The reaction is carried out for 4-5 hours. After neutralization and desalting, the fluorinated modified acetylenol polyoxyethylene ether (i.e., fluorinated modified acetylenol surfactant) is obtained by filtration.

[0061] The molar ratio of 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether, p-benzenesulfonic acid, phenylalanine, and undecylfluorocyclohexanesulfonyl fluoride is 1:0.03:2:2.

[0062] Example 5

[0063] This embodiment provides a fluorinated acetylenol surfactant having a structure as shown in formula (I):

[0064]

[0065] In formula (Ⅰ), R1 and R3 are both CH3; R2 and R4 are both isopropyl; R5 is isopropyl; R f It is undecylfluorocyclohexanesulfonyl, R f ' is heptadecafluoro-1-octanesulfonyl; p+y=30.

[0066] This embodiment also provides a method for preparing the above-mentioned fluorinated modified acetylenic diol surfactant, which includes the following steps:

[0067] S1. In a nitrogen atmosphere at 70-75°C, p-benzenesulfonic acid and leucine are added to 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether, stirred and reacted for 8-12 hours until anhydrous substances are removed, to obtain 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether amino acid ester.

[0068] S2. In a nitrogen atmosphere at 0-10°C, a fluorinated compound (a mixture of undecyloncyclohexanesulfonyl fluoride and heptadecano-1-octanesulfonyl fluoride) is added dropwise to the 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether amino acid ester obtained in step S1. The reaction is carried out for 4-5 hours. After neutralization and desalting, the fluorinated modified ynediol polyoxyethylene ether (i.e., fluorinated modified ynediol surfactant) is obtained by filtration.

[0069] The molar ratio of 2,4,7,9-tetramethyl-5-decynediol polyoxyethylene ether, p-benzenesulfonic acid, leucine, undecylfluorocyclohexanesulfonyl fluoride and heptadecafluoro-1-octanesulfonyl fluoride is 1:0.03:2:1:1.

[0070] Experimental Example

[0071] The fluorinated modified acetylenic diol polyoxyethylene ethers obtained in Examples 1-5 above were compared with unmodified 2,4,7,9-tetramethyl-5-decynyl diol polyoxyethylene ether (Comparative Example 1) and unmodified 2,5,8,11-tetramethyldodec-6-acetylen-5,8-diol polyoxyethylene ether (Comparative Example 2). The comparison results are shown in Table 1. Static surface tension was tested using a JYW-200C static surface tension meter (ring pull method) with a sample concentration of 0.1% aqueous solution. The foaming force was determined as follows: at 25°C, 20 mL of a 0.1% mass concentration sample was added to a 100 mL stoppered graduated cylinder, and the cylinder was vigorously shaken 10 times (one round trip counted as one cycle). The foam volume was immediately recorded, and the average foam volume of three parallel experiments was taken as the foaming force. The smaller the foam volume, the worse the foaming force and the better the low-foaming characteristics of the sample.

[0072] Table 1. Static surface tension and foaming force data for each embodiment and comparative example.

[0073] Example 1 23.5 4 Example 2 24.3 6 Example 3 21.7 2 Example 4 20.9 4 Example 5 26.3 5 Comparative Example 1 43.2 6 Comparative Example 2 32.5 5

[0074] As shown in Table 1, the static surface tension of Examples 1-5 is significantly lower than that of the comparative example, and their foaming power is slightly lower. Therefore, the fluorinated modified acetylenol polyoxyethylene ether (i.e., the fluorinated modified acetylenol surfactant) of this invention reduces surface tension, improves wettability, and reduces foaming. The fluorinated modified acetylenol surfactant prepared by this invention can be used in coatings, inks, and cleaning agents.

[0075] The above are merely embodiments of the present invention. The invention is not limited to the fields covered by these embodiments. Commonly known structures and characteristics are not described in detail here. Those skilled in the art are aware of all common technical knowledge in the field prior to the application date or priority date, are aware of all existing technologies in that field, and have the ability to apply conventional experimental methods prior to that date. Those skilled in the art can improve and implement this solution based on the guidance provided in this application and their own capabilities. Some typical known structures or methods should not be obstacles for those skilled in the art to implement this application. It should be noted that those skilled in the art can make several modifications and improvements without departing from the structure of the present invention. These should also be considered within the scope of protection of the present invention, and will not affect the effectiveness or practicality of the invention. The scope of protection claimed in this application should be determined by the content of its claims. The specific embodiments described in the specification can be used to interpret the content of the claims.

Claims

1. A fluorinated modified alkynyldiol surfactant, characterized in that: The structure of the fluorinated modified alkynyldiol surfactant is shown in the following general formula (Ⅰ): In general formula (Ⅰ), R1 and R3 are each independently H or CH3; R2 and R4 are each independently a straight-chain or branched C1-C10 alkyl group; R5 is one of H, straight-chain or branched C1-C8 alkyl, or benzyl; R f R f Each is independently a fluorinated C1-C10 straight-chain or branched alkyl sulfonyl group; p is an integer between 0 and 40, y is an integer between 0 and 40, and p and y are not both 0.

2. The fluorinated modified alkynyldiol surfactant according to claim 1, characterized in that: In general formula (Ⅰ), p+y=1-30.

3. A method for preparing a fluorinated acetylenic diol surfactant, characterized in that: Includes the following steps: S1. In an oxygen-free environment, at 70-100℃, the catalyst and amino acids are added to acetylenol polyoxyethylene ether, stirred and reacted for 8-12 hours until anhydrous substances are removed, to obtain acetylenol polyoxyethylene ether amino acid ester; the structure of the amino acid is shown in the following general formula (II), and the structure of the acetylenol polyoxyethylene ether is shown in the following general formula (III): In general formula (II), R5 is one of H, straight-chain or branched C1-C8 alkyl, or benzyl; In general formula (Ⅲ), R1 and R3 are each independently H or CH3, R2 and R4 are each independently straight-chain or branched C1-C10 alkyl, and p is an integer from 0 to 40, y is an integer from 0 to 40, and p and y are not both 0. S2. In an oxygen-free environment at 0-15°C, a fluorine compound is added dropwise to the acetylenol polyoxyethylene ether amino acid ester obtained in step S1, and the reaction is carried out for 4-5 hours to obtain fluorinated modified acetylenol polyoxyethylene ether; the fluorine compound is one or both of fluorinated C1-C10 straight-chain or branched alkyl sulfonyl fluoride.

4. The preparation method according to claim 3, characterized in that: In step S1, the catalyst is one or two of p-benzenesulfonic acid, concentrated sulfuric acid, and dodecylbenzenesulfonic acid.

5. The preparation method according to claim 3, characterized in that: The molar ratio between the acetylenol polyoxyethylene ether, the catalyst, the amino acid, and the fluorine compound is 1:(0.001-0.05):(2-2.5):(2-2.5).

6. The application of the fluorinated modified acetylenic diol surfactant as described in claim 1 or 2 as an antifoaming agent in the fields of coatings, inks and cleaning agents.

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