Novel high-molecular surfactant as well as preparation method and application thereof

Abstract

The invention discloses a novel polymer surfactant as well as a preparation method and application thereof. The novel high-molecular surfactant is a polymer with a polymerization unit shown as a formula I. The invention further discloses a preparation method of the novel high-molecular surfactant. The surfactant avoids the defect of high price caused by introduction of fluorosilicone, has good surface activity, and has a good application prospect as a novel surfactant with low cost.

Description

Technical Field

[0001] This invention relates to the field of surfactants, and more particularly to a novel polymeric surfactant, its preparation method, and its application. Background Technology

[0002] Surfactants are amphiphilic molecules with a hydrophilic group at one end and a hydrophobic group at the other end, and they have important applications in many fields.

[0003] Surfactant molecules are typically composed of long-chain lipophilic groups and polar hydrophilic groups distributed at both ends of the molecule. This unique amphiphilic property of surfactants gives them properties such as foaming, emulsification, dispersion, antibacterial, wetting, solubilization, and detergency. The hydrophobic end of a surfactant is usually composed of hydrocarbon chains, sometimes containing elements such as nitrogen, oxygen, sulfur, chlorine, bromine, and iodine. These common surfactants are conventionally called hydrocarbon surfactants. Common hydrocarbon surfactants can reduce the surface tension of aqueous solutions to as low as 30 mN / m. For example, sodium dodecylbenzenesulfonate (SDBS) at a concentration of 1.5 wt% has a surface tension of 31.83 mN / m, and alkyl glycoside (APG0810) at a concentration of 1.5 wt% has a surface tension of 33.41 mN / m. [1] [1] Yan Min; Yang Ting; Lin Haifei; Yan Dongjie; Li Yong; Huo Shihao. Experimental study on the effect of surfactant foaming properties on the slow release of gas in coal [J]. Coal Science and Technology, 2023, (10): 129-139.

[0004] When a surfactant contains elements such as fluorine, silicon, boron, and phosphorus, it is called a specialty surfactant. Due to the presence of these special elements, fluorine and silicon, the intermolecular attraction between the alkyl chains at the hydrophobic ends is reduced, allowing molecules to migrate more easily from the interior of the solution to the surface. This results in a large amount of adsorption on the surface, lowering the surface free energy of the solution and thus enhancing its ability to reduce the surface tension of aqueous solutions. The surface tension of aqueous solutions containing silicon surfactants can typically be reduced to below 30 mN / m. For example, fluorocarbon surfactants can reduce the surface tension of their aqueous solutions to below 20 mN / m, and even to around 15 mN / m. For instance, OFX-5211 has a surface tension of 21.13 mN / m at its critical micelle concentration, and FC-134 has a surface tension of 14.46 mN / m at its critical micelle concentration. [2]. [2] Sheng Y, Jiang N, Lu S, et al. Molecular interaction and foaming property of the mixtures of hydrocarbon, fluorocarbon and siliconesurfactants[J]. Journal of Molecular Liquids, 2019, 296: 111836.

[0005] Due to the superior surface activity of fluorinated and silicon-containing surfactants, they have been widely used in fire extinguishing agents, surface treatment agents for photosensitive materials, textile finishing agents, cleaning and surface treatment fluids in the semiconductor industry, inert liquids in the aerospace industry, chromium plating mist suppressants, industrial and daily cleaning agent additives, coating and paint additives, pesticide additives, cosmetic additives, oil extraction additives, and high-efficiency emulsifiers in fluorochemicals. Because the synthesis methods and production processes of fluorocarbon and silicon-carbon chains require advanced technology, the mainstream market still relies on foreign companies such as Chemco, BASF, and Evonik, resulting in high prices. Summary of the Invention

[0006] The purpose of this invention is to overcome the high cost of existing high-surface-active materials such as fluorosilicone. To this end, a novel polymeric surfactant, its preparation method, and its applications are provided. This type of surfactant avoids the high cost associated with the introduction of fluorosilicone while possessing excellent surface activity. Some novel polymeric surfactants even achieve surface activity comparable to fluorocarbon surfactants. Furthermore, the high-surface-active polymeric structure synthesis method of this invention is simple, has high yield, and possesses significant practical application value and broad market prospects.

[0007] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0008] This invention provides a polymer having polymeric units as shown in Formula I:

[0009] ,

[0010] Where R1 and R2 are independently C 1-6 Alkyl group, R3 is a substituted or unsubstituted C. 1-20 Alkyl or substituted or unsubstituted C 2-20 alkenyl groups;

[0011] The substituted C 1-20 Alkyl and substituted C 2-20 The substituents in the alkenyl group are selected from the following groups: halogen, nitro and hydroxyl.

[0012] In one embodiment, the degree of polymerization of the polymer is preferably any natural integer from 100 to 5000, more preferably any natural integer from 100 to 2000, and even more preferably any natural integer from 100 to 500.

[0013] In one scheme, R1 and R2 are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl; for example, methyl.

[0014] In a given scheme, R1 and R2 can be the same or different, for example, the same.

[0015] In one scheme, R1 and R2 are both methyl or ethyl, for example, methyl.

[0016] In one embodiment, R3, the substituted or unsubstituted C 1-20 The alkyl group is either substituted or unsubstituted C. 4-18 Alkyl groups, preferably substituted or unsubstituted C4 groups. 12-14 Alkyl groups.

[0017] In one embodiment, R3, the substituted or unsubstituted C 2-20 The alkenyl group is either substituted or unsubstituted C. 4-18 The alkenyl group, preferably substituted or unsubstituted C, is preferred. 12-14 The alkenyl group.

[0018] In one particular scheme, R3 represents unsubstituted C. 4-18 Alkyl groups, preferably unsubstituted C4 groups. 12-14 Alkyl groups.

[0019] In one embodiment, R3 is n-butyl, straight-chain dodecyl, or straight-chain tetradecyl, preferably straight-chain dodecyl or straight-chain tetradecyl.

[0020] In one embodiment, the polymer is a polymer having polymeric units as shown in any of the following formulas:

[0021] , or .

[0022] In one embodiment, the polymer is any of the following compounds:

[0023] , or ;

[0024] n is any natural integer from 100 to 5000, preferably any natural integer from 100 to 2000, and more preferably any natural integer from 100 to 500.

[0025] In one embodiment, the polymer is prepared by the following method: the preparation method of the polymer includes the following steps: in a solvent, a polymer having polymeric units as shown in Formula A and a compound as shown in Formula B are reacted to prepare the polymer.

[0026] ,

[0027] R1, R2, and R3 are as described above.

[0028] In one embodiment, the solvent is one or more of water, alcohol solvents, and ketone solvents, such as water.

[0029] In one embodiment, the alcohol solvent is methanol, ethanol, or propanol.

[0030] In one embodiment, the ketone solvent is acetone.

[0031] In one embodiment, the solvent is one or more of water, methanol, ethanol, propanol, and acetone, such as water.

[0032] In one embodiment, the degree of polymerization of the polymer having polymeric units as shown in Formula A is preferably any natural integer from 100 to 5000, more preferably any natural integer from 100 to 2000, and even more preferably any natural integer from 100 to 500.

[0033] In one embodiment, the molar ratio of the polymer having polymeric units as shown in Formula A to the compound shown in Formula B is 1:(0.95~1.2), for example 1:1.1.

[0034] In one embodiment, the mass ratio of the polymer having polymerization units as shown in Formula A to the solvent is 1:(10~20), for example 1:15.

[0035] In one embodiment, the reaction is carried out at a pH of 7 to 10, for example, at pH 8.

[0036] In one embodiment, the reaction temperature in the polymer preparation method is 0~80°C, preferably 40~60°C, for example 40~50°C.

[0037] In one embodiment, the method for preparing the polymer of the polymerization unit shown in Formula I preferably includes the following post-processing steps: concentration (e.g., vacuum concentration), dissolution with a solvent (e.g., dichloromethane), and further concentration (e.g., vacuum concentration).

[0038] The method for preparing the polymer may further include a method for preparing a polymer having polymeric units as shown in Formula A, which includes the following steps: reacting a polymer having polymeric units as shown in Formula Aa with sulfuric acid to prepare a polymer having polymeric units as shown in Formula A.

[0039] .

[0040] In one embodiment, the sulfuric acid mass concentration is 70% to 98%, preferably 98%.

[0041] In one embodiment, the degree of polymerization of the polymer having polymeric units as shown in Formula Aa is preferably any natural integer from 100 to 5000, more preferably any natural integer from 100 to 2000, and even more preferably any natural integer from 100 to 500.

[0042] The polymer having polymer units as shown in Formula Aa is preferably polyetheretherketone (PEEK) purchased from Zhongyan (e.g., model 330) or polyetheretherketone purchased from Weigesi.

[0043] In one embodiment, the polymer having polymer units as shown in Formula Aa has a mass ratio of sulfuric acid of 1:(5~15), for example 1:10.

[0044] In one embodiment, in the method for preparing a polymer having polymeric units as shown in Formula A, the reaction temperature is 0~100℃, preferably 70~80℃.

[0045] In one embodiment, in the method for preparing a polymer having polymeric units as shown in Formula A, the reaction time is 2 to 10 hours, preferably 4 to 8 hours.

[0046] After the reaction is completed, the post-processing of the reaction preferably includes the following steps: mixing the reaction solution and ice, letting it stand, precipitating, filtering and drying to obtain a solid, then stirring the solid in water, filtering and drying to obtain a polymer having polymeric units as shown in Formula A.

[0047] In one embodiment, the mass ratio of the reaction solution to ice is 1:(1~5), preferably 1:(1~3), for example 1:2.

[0048] In one embodiment, the mass ratio of the solid to water is 1:(1~5), preferably 1:(1~3), for example 1:2.

[0049] In one embodiment, the stirring temperature is 0~50℃, preferably 0~30℃.

[0050] In one embodiment, the stirring time is 1 to 5 hours, preferably 2 to 4 hours.

[0051] The present invention also provides a method for preparing the above-mentioned polymer, wherein the conditions and operations in the preparation method are as described above.

[0052] The present invention also provides an application of the polymer described above as a surfactant.

[0053] "alkyl" refers to an alkyl group having a specified number of carbon atoms (e.g., C1~C1). 20 Alkyl groups are straight-chain or branched, saturated monovalent hydrocarbon groups. Alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, dodecyl or tetradecyl, etc.

[0054] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0055] All reagents and raw materials used in this invention are commercially available. Specifically, compound Aa1 was purchased from Zhongyan (model 330), or from Weigesi.

[0056] The degree of polymerization n is 100~500.

[0057] The positive and progressive effects of this invention are as follows: 1. The polymeric surfactant prepared by this invention has a novel chemical structure and belongs to a completely new series of polymeric substances.

[0058] 2. The polymeric surfactant prepared by this invention is an aqueous solution, which is convenient to use. It can greatly reduce the surface tension of water and has strong compatibility; it is an ideal substitute for special surfactants.

[0059] 3. The preparation process of the polymeric surfactant of the present invention is simple, with high synthesis yield and low production cost. Attached Figure Description

[0060] Figure 1 The curves show the surface tension of the aqueous solutions of the compounds obtained in Examples 2-3 as a function of concentration. Detailed Implementation

[0061] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0062] Unless otherwise specified, room temperature in the following examples refers to 20~25°C.

[0063] Example 1 Preparation of compound A1

[0064] ,

[0065] 400g of sulfuric acid (98% by mass) was added to a dry reaction flask and magnetically stirred. 40g of compound Aa1 was added all at once, and the mixture was heated to 80°C and maintained at this temperature for 5 hours until the system was completely dissolved. The mixture was then maintained at this temperature for another 3 hours, cooled to room temperature, and 800g of ice was added. After the ice dissolved, the mixture was filtered and dried. The solid was pulverized using a grinder, and twice the mass of the solid was added to it. The mixture was stirred at room temperature for 2 hours, filtered, and freeze-dried to obtain 35g of solid A1, with a yield of 68%.

[0066] The degree of polymerization n is 100~500.

[0067] 1 H NMR (400 MHz, DMSO) δ 7.79 (dt, J = 28.2, 8.3 Hz, 4H), 7.50 (d, J= 2.8 Hz, 1H), 7.18 (ddd, J = 29.8, 15.2, 5.7 Hz, 4H), 7.02 (d, J = 8.4 Hz,2H).

[0068] Example 2 Preparation of Compound I1

[0069] ,

[0070] Add 20g of dried compound A1 to a reaction flask, add 300g of water, heat to 40-50°C and stir to dissolve. After the system is dissolved, slowly add N,N-dimethyldodecylamine dropwise until the pH of the system reaches 8. After the reaction is complete, concentrate under reduced pressure to obtain a viscous substance. Then add dichloromethane to dissolve and concentrate under reduced pressure again to obtain a white viscous solid I1.

[0071] The degree of polymerization n is 100~500.

[0072] 1 H NMR (500 MHz, DMSO) δ 7.79 (dt, J = 34.8, 9.3 Hz, 4H), 7.52 (d, J= 1.9 Hz, 1H), 7.33 – 7.09 (m, 4H), 7.03 (d, J = 8.3 Hz, 2H), 2.91 – 2.81 (m,3H), 2.64 (s, 10H), 1.22 (s, 33H), 0.84 (t, J = 6.5 Hz, 5H).

[0073] Example 3 Preparation of Compound I2

[0074] ,

[0075] Add 20g of dried compound A1 to a reaction flask, add 300g of water, heat to 40-50 °C and stir to dissolve. After the system is dissolved, slowly add N,N-dimethyltetradecylamine dropwise until the pH of the system reaches 8. After the reaction is complete, concentrate under reduced pressure to obtain a viscous substance. Then add dichloromethane to dissolve and concentrate under reduced pressure again to obtain a white viscous solid I2.

[0076] The degree of polymerization n is 100~500.

[0077] 1 H NMR (500 MHz, DMSO) δ 7.79 (dt, J = 34.4, 8.8 Hz, 4H), 7.53 (s,1H), 7.33 – 7.08 (m, 4H), 7.03 (d, J = 7.9 Hz, 2H), 2.97 – 2.88 (m, 3H), 2.69 (s, 10H), 1.21 (s, 38H), 0.83 (t, J = 6.2 Hz, 5H).

[0078] Example 4 Preparation of compound I3

[0079] ,

[0080] Add 20g of dried compound A1 to a reaction flask, add 300g of water, heat to 40~50 °C and stir to dissolve. After the system is dissolved, slowly add N,N-dimethylbutylamine dropwise until the pH of the system reaches 8. After the reaction is complete, concentrate under reduced pressure to obtain a viscous substance. Then add dichloromethane to dissolve and concentrate under reduced pressure again to obtain a white viscous solid I3.

[0081] The degree of polymerization n is 100~500.

[0082] Example 1: Surface tension test of aqueous solutions of compounds I1-I3

[0083] The surface tension of aqueous solutions of each compound at different concentrations was measured at 25℃ using the Kruss K100 fully automatic surface tension meter (Germany) plate method, and the data are shown in Table 1.

[0084] Table 1. Surface tension values ​​of aqueous solutions of the compounds at different concentrations

[0085]

[0086] The surface tension of aqueous solutions of compounds I1 and I2 obtained in Examples 2 and 3 as a function of concentration is shown in the following curves. Figure 1As shown, surface tension represents the surface tension, expressed as log C / g*mL. -1 This is the logarithm of the concentration.

[0087] Among them, compound I1: CMC (g / mL) is 3.13 × 10⁻⁶. -4 ;γ cmc The concentration (mN / m) is 19.93. The CMC (g / mL) of compound I2 is 6.25 × 10⁻⁶. -4 ;γ cmc The concentration (mN / m) is 19.79. The CMC (g / mL) of compound I3 is 1.56 × 10⁻⁶. -4 ;γ cmc The value (mN / m) is 40.86.

[0088] Note: γ cmc The surface tension at the critical micelle concentration;

[0089] CMC stands for Critical Micelle Concentration, which is the minimum concentration at which a surfactant associates and forms micelles in a solvent. Once this concentration is reached, the surface tension of the solvent no longer decreases with increasing concentration.

[0090] In comparison, this invention is similar to the commercially available product DuPont. TM 1157, 3M TM The relevant numerical values ​​of the compounds in FC 4430 and invention patent CN109851529B are shown in Table 2 below:

[0091] Compound 4a in CN109851529B: .

[0092] Table 2 Comparison of surface tension values ​​of aqueous solutions

[0093]

[0094] As can be seen from the table, compounds I1 and I2 exhibit superior surface activity compared to commercially available fluorocarbon surfactants from 3M. TM FC 4430, and its activity is comparable to that of the fluorocarbon surfactant in compound 4a of invention patent CN109851529B, and in low-concentration applications, it is comparable to the commercially available fluorocarbon surfactant product DuPont. TM The surface activity of 1157 is comparable.

Claims

1. A polymer, which is a polymer having a polymer unit as shown in Formula I: ， wherein, R1and R2are independently C 1-6 alkyl, R3is substituted or unsubstituted C 1-20 alkyl or substituted or unsubstituted C 2-20 alkenyl; The substituents in the substituted C 1-20 The substituents in the substituted C 2-20 The substituents in the substituted C alkenyl are selected from the group consisting of halogen, nitro and hydroxy.

2. The polymer of claim 1, wherein which satisfies one or more of the following conditions: (1) the polymer has a degree of polymerization of any natural integer from 100 to 5000, preferably any natural integer from 100 to 2000, further preferably any natural integer from 100 to 500; (2) R1 and R2 are independently methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl; for example, methyl; (3) R1 and R2 are the same or different, for example, the same; (4) in R3, the substituted or unsubstituted C 1-20 substituted or unsubstituted C 4-18 substituted or unsubstituted C 12-14 substituted or unsubstituted C and, (5) in R3, the substituted or unsubstituted C 2-20 alkenyl is substituted or unsubstituted C 4-18 alkenyl, preferably substituted or unsubstituted C 12-14 alkenyl.

3. The polymer of claim 2, wherein which satisfies one or more of the following conditions: (1) R1 and R2 are both methyl or ethyl, for example, methyl; and, (2) R3 is n-butyl, straight-chain dodecyl or straight-chain tetradecyl, preferably straight-chain dodecyl or straight-chain tetradecyl.

4. The polymer according to any one of claims 1 to 3, wherein which is a polymer having a polymer unit as shown in any of the following formulas: , or ; the polymer is preferably any of the following compounds: , or ; n is any natural integer from 100 to 5000, preferably any natural integer from 100 to 2000, further preferably any natural integer from 100 to 500.

5. The polymer according to any one of claims 1 to 4, wherein the polymer is prepared by a method comprising the following steps: reacting a polymer having a polymer unit as shown in Formula A and a compound as shown in Formula B in a solvent to obtain the polymer; , wherein R1, R2 and R3 are as described in any of claims 1-4.

6. The polymer of claim 5, wherein which satisfies one or more of the following conditions: (1) the solvent is one or more of water, an alcohol solvent and a ketone solvent, for example, water; (2) the polymer having a polymer unit as shown in Formula A has a degree of polymerization of any natural integer from 100 to 5000, preferably any natural integer from 100 to 2000, further preferably any natural integer from 100 to 500; (3) the molar ratio of the polymer having a polymer unit as shown in Formula A to the compound as shown in Formula B is 1:(0.95-1.2), for example, 1:1.1; (4) the mass ratio of the polymer having a polymer unit as shown in Formula A to the solvent is 1:(10-20), for example, 1:15; (5) the reaction is carried out at a pH of 7-10, for example, pH 8; (6) the reaction temperature is 0-80°C, preferably 40-60°C, for example, 40-50°C; and, (7) the preparation method of the polymer of Formula I includes the following post-treatment steps: concentration, dissolution with a solvent and re-concentration.

7. The polymer of claim 5, wherein the preparation method of the polymer can further include a preparation method of a polymer having a polymer unit as shown in Formula A, which comprises the following steps: reacting a polymer having a polymer unit as shown in Formula Aa and sulfuric acid to obtain a polymer having a polymer unit as shown in Formula A; 。 8. The polymer of claim 7, wherein which satisfies one or more of the following conditions: (1) the mass concentration of the sulfuric acid is 70%-98%, preferably 98%. (2) the polymer having the polymerization unit as shown in Formula Aa has any natural integer from 100 to 5000, preferably any natural integer from 100 to 2000, and further preferably any natural integer from 100 to 500; (3) the mass ratio of the compound having the polymerization unit as shown in Formula Aa to sulfuric acid is 1:(5-15), for example 1:10; (4) in the preparation method of the polymer having the polymerization unit as shown in Formula A, the temperature of the reaction is 0-100℃, preferably 70-80℃; (5) in the preparation method of the polymer having the polymerization unit as shown in Formula A, the time of the reaction is 2-10h, preferably 4-8h; and (6) after the reaction, the post-treatment of the reaction comprises the following steps: mixing the reaction solution with ice, standing, precipitating, filtering and air-drying to obtain a solid, then stirring the solid in water, filtering and drying to obtain the polymer having the polymerization unit as shown in Formula A.

9. A process for the preparation of a polymer as claimed in any one of claims 1 to 8, characterized in that, which comprises the following steps: reacting the polymer having the polymerization unit as shown in Formula A with the compound as shown in Formula B in a solvent, to obtain the polymer; , wherein R1, R2 and R3 are as defined in any one of claims 1-8; the conditions and operations in the preparation method can be as defined in any one of claims 6-8.

10. Use of the polymer as defined in any one of claims 1-8 as a surfactant.

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