Polymethyl branched anionic surfactants, methods of making, compositions, uses

Abstract

The application discloses a multi-methyl branched anionic surfactant, a preparation method, a composition and application, wherein the surfactant has a hydrophobic group R and a hydrophilic group M, wherein the hydrophobic group R is selected from a first oligomer with a polymerization degree of not more than 4 obtained by oligomerization of at least two isobutylene monomers, a second oligomer obtained by selective dimerization of the first oligomer and derivatives of the second oligomer. The application provides a new efficient preparation technology of the surfactant, and has the characteristics of high reaction efficiency, low cost and good surfactant performance.

Description

TECHNICAL FIELD

[0001] The present application relates to fine chemical surfactants, in particular to a multi-methyl branched anionic surfactant and a preparation method, composition and application thereof. BACKGROUND

[0002] Isobutene is a common chemical raw material, mainly used for producing gasoline additive methyl tert-butyl ether (MTBE). With the popularization of ethanol gasoline and the restriction of MTBE due to environmental health problems, the resource utilization of isobutene has become an important problem. The oligomerization of isobutene is an effective way to solve the problem of MTBE. The reaction is a typical acid catalysis process, which can synthesize diisobutene, triisobutene, tetraisobutene and even higher carbon number oligomers. These oligomers have carbon-carbon double bonds and multi-methyl branched chains in their molecular structures, which are potential high-quality hydrophobic end materials. By grafting hydrophilic groups through carbon-carbon double bond functionalization reaction, it is expected to obtain multi-methyl branched surfactants suitable for industrial hard surface cleaning, expand the utilization way of isobutene, and realize the resource utilization of low-value raw material isobutene.

[0003] At present, many teams have reported research on isobutene oligomerization. The main products obtained under various catalytic systems are diisobutene and triisobutene. High-purity diisobutene and triisobutene can be obtained after vacuum distillation, but the selectivity of tetraisobutene is very low, and it is difficult to obtain high-yield tetraisobutene through isobutene oligomerization.

[0004] The information disclosed in this BACKGROUND section is only for the purpose of increasing the understanding of the background of the present application and should not be taken as an acknowledgement or any form of suggestion that this information forms prior art that is publicly known. SUMMARY

[0005] The present application provides a multi-methyl branched anionic surfactant and a preparation method, composition and application thereof, and provides a new efficient preparation technology of surfactants, which has the characteristics of high reaction efficiency, low cost and good surfactant performance.

[0006] To achieve the above-mentioned purpose, the embodiments of the present application provide an anionic surfactant having a hydrophobic group R and a hydrophilic group M, wherein: the hydrophobic group R is selected from a first oligomer obtained by oligomerization of at least 2 isobutene monomers, a second oligomer obtained by selective dimerization of the first oligomer, and derivatives thereof.

[0007] In one or more embodiments of the present application, the hydrophobic group R is selected from oligomers diisobutene and triisobutene obtained by oligomerization of 2-3 isobutene monomers, tetraisobutene obtained by selective dimerization of diisobutene, hexaisobutene obtained by selective dimerization of triisobutene, and derivatives thereof.

[0008] In one or more embodiments of the present application, the hydrophobic group R is at least selected from

[0009] wherein denotes the position of bonding of the group.

[0010] In one or more embodiments of the present application, the hydrophilic group M is selected from SO3Na.

[0011] In one or more embodiments of the present application, the preparation method of the anionic surfactant comprises the following steps: A, using isobutene monomer as raw material, obtaining oligomers by catalytic reaction, wherein the oligomers are obtained by polymerization of at least two isobutene monomers; B, after the oligomers are sulfonated with a sulfonating agent, separating and purifying to obtain the target product.

[0012] In one or more embodiments of the present application, the catalyst of the catalytic condition in step A is selected from the following catalytic systems: protonic acid catalyst, heteropoly acid catalyst, metallocene catalyst, zeolite catalyst and acidic ion exchange resin catalyst.

[0013] In one or more embodiments of the present application, the protonic acid catalyst in step A is selected from: trifluoromethane sulfonic acid, concentrated sulfuric acid, methane sulfonic acid, sulfamic acid, perchloric acid, phosphoric acid, dodecyl benzene sulfonic acid, p-toluene sulfonic acid.

[0014] In one or more embodiments of the present application, the heteropoly acid catalyst in step A is selected from: phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid.

[0015] In one or more embodiments of the present application, the metallocene catalyst in step A is selected from: dichromiumocene, dibromodiferrocene, dichlorobis-titanocene, dichlorobis-zirconocene and cocatalyst methylaluminoxane.

[0016] In one or more embodiments of the present application, the zeolite catalyst in step A is selected from: H-Y zeolite, H-β zeolite, H-ZSM-5 zeolite.

[0017] In one or more embodiments of the present application, the acidic ion exchange resin catalyst in step A is selected from: Amberlyst 35, Amberlyst 15, Aquivion PW98, Aquivion PW87S, NKC-9.

[0018] In one or more embodiments of the present application, the sulfonating agent in step B is selected from: concentrated sulfuric acid (concentration preferably 98%), chlorosulfonic acid, sulfamic acid, sodium sulfite, sodium bisulfite, sulfur trioxide.

[0019] In one or more embodiments of the present application, the conditions of the sulfonation reaction in step B: the reaction temperature is 10-80℃, and the reaction time is 6-100h.

[0020] In one or more embodiments of the present application, the composition comprises the anionic surfactant as described above.

[0021] In one or more embodiments of the present application, the use of the anionic surfactant as described above or the composition as described above in interfacial wetting. The relevant applications of interfacial wetting here include but are not limited to cleaning, flotation, emulsification, disinfection, etc.

[0022] Compared with the prior art, the multi-methyl branched anionic surfactant, the preparation method, the composition and the application according to the embodiments of the present application realize the preparation of high-yield and high-activity surfactants by adopting isobutene monomers for oligomerization and selectively dimerizing the oligomerization products under different catalytic conditions. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The infrared spectrum of the tetraisobutene in Example 7 of the present application is shown in the figure;

[0024] Figure 2 The infrared spectrum of the multi-methyl branched sulfonate anionic surfactant in Example 11 of the present application is shown in the figure;

[0025] Figure 3 The surface tension diagram of the multi-methyl branched sulfonate anionic surfactant in Example 11 of the present application under different concentrations is shown in the figure;

[0026] Figure 4 The dynamic surface tension diagram of the multi-methyl branched sulfonate anionic surfactant in Example 11 of the present application is shown in the figure. DETAILED DESCRIPTION

[0027] The specific embodiments of the present application are described in detail below, but it should be understood that the protection scope of the present application is not limited by the specific embodiments.

[0028] Unless otherwise clearly indicated otherwise, throughout the specification and claims, the term "comprise" or its variants such as "comprises" or "comprising" and the like will be understood to encompass the stated elements or components, without excluding the presence of other elements or components.

[0029] (1) Isobutene oligomerization reaction

[0030] (a): monomer primary oligomerization reaction

[0031] The isobutene oligomer mixture with multi-methyl structure is obtained by using isobutene as the starting material, under the action of a catalyst, and controlling the reaction temperature at -10-40℃ and the reaction time at 10-24h. The main components of the mixture are diisobutene and triisobutene. After the reaction, high-purity diisobutene and triisobutene are obtained by vacuum distillation.

[0032] The isobutene oligomerization reaction equation is as follows:

[0033]

[0034] The starting material used in the isobutene oligomerization reaction is low-temperature liquefied isobutene, and the catalyst is selected from the following acidic ion exchange resin catalysts: Amberlyst 15, Aquivion PW98, and NKC-9. The mass ratio of isobutene to catalyst is 1:0.01-0.25.

[0035] Example 1

[0036] In a 25mL high-pressure reaction kettle equipped with a magnetic stirrer, 0.7g of Amberlyst 15 catalyst was added. The mass ratio of isobutene to catalyst was 1:0.1. Low-temperature liquefied isobutene 15g was added to the reaction kettle by a laminar flow pump, and then 0.5MPa of nitrogen was introduced to ensure that the isobutene was in a liquid state. The reaction was stirred at room temperature 25℃ for 20h. After the reaction was completed, the nitrogen in the reaction kettle was slowly released, and the catalyst was separated by filtration to obtain an isobutene oligomer mixture 14.8g. Gas chromatography showed that the diisobutene accounted for 59.92%, the triisobutene accounted for 36.54%, and other polymers accounted for 3.54%. Finally, high-purity diisobutene (98.48%) and triisobutene (98.20%) were obtained by vacuum distillation.

[0037] (b) Diisobutene selective dimerization reaction:

[0038] In the presence of a catalyst, diisobutene obtained in step (1) was used as the raw material, the reaction temperature was controlled at -60-150℃, and the reaction time was 0.1-36h. The tetramer of isobutene, tetraisobutene, was generated with high selectivity. After the reaction was completed, the catalyst was treated, and high-purity tetraisobutene was obtained by vacuum distillation.

[0039] The diisobutene selective dimerization reaction equation is as follows:

[0040]

[0041] In the diisobutene selective dimerization reaction, the mass ratio of diisobutene to catalyst is 1:0.015-0.200. The catalyst is selected from the following catalyst systems: a protonic acid catalyst, a heteropoly acid catalyst, a metallocene catalyst, a zeolite catalyst, and an acidic ion exchange resin catalyst.

[0042] First group of examples

[0043] The protic acid catalyst is selected from trifluoromethanesulfonic acid, concentrated sulfuric acid, methane sulfonic acid, sulfamic acid, perchloric acid, phosphoric acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid.

[0044] Example 2:

[0045] Take the diisobutene 8g obtained in example 1 into 50mL constant pressure dropping funnel, according to the mass ratio of diisobutene and petroleum ether 1:1.25, add 10g of solvent petroleum ether into 250mL jacketed three-necked flask equipped with magnetic stirrer, then according to the mass ratio of diisobutene and trifluoromethanesulfonic acid 1:0.02, add 0.16g of trifluoromethanesulfonic acid into the jacketed three-necked flask, fully stir to make it dispersed in petroleum ether. With ethanol as cooling medium, through low temperature constant temperature bath access to the jacketed three-necked flask to cool to -40℃, after the temperature is stable, the diisobutene is added into the flask through the constant pressure dropping funnel to start the reaction, stirring at -40℃ for 10min. After the reaction is completed, add saturated sodium bicarbonate solution to quench the reaction, after water washing, petroleum ether extraction, anhydrous sodium sulfate drying, reduced pressure distillation to obtain the product tetraisobutene 7.78g, the purity of tetraisobutene is 98.78% measured by gas chromatography.

[0046] Example 3:

[0047] Take the diisobutene 8g obtained in example 1 into 50mL constant pressure dropping funnel, according to the mass ratio of diisobutene and petroleum ether 1:1.25, add 10g of solvent petroleum ether into 250mL jacketed three-necked flask equipped with magnetic stirrer, then according to the mass ratio of diisobutene and trifluoromethanesulfonic acid 1:0.02, add 0.16g of trifluoromethanesulfonic acid into the jacketed three-necked flask, fully stir to make it dispersed in petroleum ether. With ethanol as cooling medium, through low temperature constant temperature bath access to the jacketed three-necked flask to cool to -40℃, after the temperature is stable, the diisobutene is added into the flask through the constant pressure dropping funnel to start the reaction, stirring at -40℃ for 10min. After the reaction is completed, add saturated sodium bicarbonate solution to quench the reaction, after water washing, petroleum ether extraction, anhydrous sodium sulfate drying, reduced pressure distillation to obtain the product tetraisobutene 7.78g, the purity of tetraisobutene is 98.78% measured by gas chromatography.

[0048] Second group of examples

[0049] The heteropoly acid catalyst is selected from phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid.

[0050] Example 4:

[0051] The diisobutene obtained in Example 1 was taken 8 g into a 25 mL autoclave reactor with magnetic stirring, and phosphomolybdic acid 0.8 g was added into the reactor according to the mass ratio of diisobutene to catalyst of 1:0.1, then 0.8 MPa of nitrogen was introduced to reduce the volatilization of diisobutene as gas. The reaction was stirred at 60 °C for 24 h, and after the reaction was completed, the nitrogen in the reactor was slowly released, and the catalyst was separated by filtration to obtain the product 7.89 g. Gas chromatography analysis showed that the conversion rate of diisobutene was 22.80%, and the selectivity of tetraisobutene was 98.73%.

[0052] Third group of examples

[0053] The metallocene catalyst is selected from dichromiumocene, dibromodiferrocene, dichlorobis-titanocene, dichlorobis-zirconocene and the cocatalyst methylaluminoxane.

[0054] Example 5:

[0055] The diisobutene obtained in Example 1 was taken 5.61 g (0.05 mol) into a 25 mL reactor tube with magnetic stirring, and methylaluminoxane 0.295 g (1 mmol) and dichlorobis-zirconocene 0.029 g (0.5 mmol) were sequentially added in the glove box according to the molar ratio of diisobutene to catalyst of 1:0.03, and the molar ratio of methylaluminoxane to dichlorobis-zirconocene of 1:0.5. The reaction was stirred at 50 °C for 12 h, and after the reaction was completed, the reaction was quenched with water, washed with water, extracted with petroleum ether, dried with anhydrous sodium sulfate, and analyzed by gas chromatography. The conversion rate of diisobutene was 12.92%, and the selectivity of tetraisobutene was 98.12%.

[0056] Fourth group of examples

[0057] The zeolite catalyst is selected from H-Y zeolite, H-β zeolite, H-ZSM-5 zeolite.

[0058] Example 6:

[0059] The diisobutene obtained in Example 1 was taken 8 g into a 25 mL autoclave reactor with magnetic stirring, and H-β zeolite 1.6 g was added into the reactor according to the mass ratio of diisobutene to catalyst of 1:0.2, then 0.8 MPa of nitrogen was introduced to reduce the volatilization of diisobutene as gas. The reaction was stirred at 40 °C for 24 h, and after the reaction was completed, the nitrogen in the reactor was slowly released, and the catalyst was separated by filtration to obtain the product 7.92 g. Gas chromatography analysis showed that the conversion rate of diisobutene was 87.91%, and the selectivity of tetraisobutene was 95.19%.

[0060] Fifth group of examples

[0061] The acidic ion exchange resin catalysts were selected from: Amberlyst 35, Amberlyst 15, Aquivion PW98, Aquivion PW87S, and NKC-9.

[0062] Example 7:

[0063] 60g of diisobutylene obtained in Example 1 was added to a 100mL constant-pressure dropping funnel. 12g of Amberlyst 15 catalyst was added to a 250mL jacketed three-necked flask equipped with a magnetic stirrer, at a diisobutylene to Amberlyst 15 mass ratio of 1:0.2. Using ethanol as the cooling medium, the flask was cooled to -10°C via a cryostat. After the temperature stabilized, diisobutylene was added to the flask through the constant-pressure dropping funnel to initiate the reaction. The reaction was stirred at -10°C for 12 hours. After the reaction was complete, the catalyst was separated by filtration, yielding 58.84g of product. Gas chromatography analysis showed a diisobutylene conversion of 94.51% and a tetraisobutylene selectivity of 98.92%. High-purity tetraisobutylene with a purity of 99.41% was obtained after vacuum distillation.

[0064] Infrared spectroscopy analysis was performed on the tetraisobutylene compound obtained by selective dimerization of diisobutylene as described above. Figure 1 .

[0065] Please see Figure 1 , Figure 1 This is the infrared spectrum of the tetraisobutylene prepared in this embodiment. As shown in the figure, the infrared spectrum is obtained at wavenumbers of 3076, 1635, and 900 cm⁻¹. -1 The characteristic absorption peak of =CH2 appeared at wavenumbers 1394 and 1365 cm⁻¹. -1 A strong characteristic absorption peak of -C(CH3)3 appeared at 2952 cm⁻¹. -1 The peak at this point is the stretching vibration peak of -CH3, with the highest intensity, indicating that the molecular structure contains a large number of methyl (-CH3) groups. Therefore, the selective dimerization of diisobutylene synthesizes tetraisobutylene with a polymethyl branched structure.

[0066] (c) Selective dimerization of triisobutylene:

[0067] In the presence of a catalyst, using triisobutylene obtained in Example 1 as a raw material, the reaction temperature is controlled at 0–150°C and the reaction time is 0.1–36 h, which can selectively generate hexaisobutylene. After the reaction is completed, the catalyst is treated and high-purity hexaisobutylene can be obtained by vacuum distillation.

[0068] The equation for the selective dimerization of triisobutylene is:

[0069]

[0070] In the selective dimerization reaction of triisobutylene, the mass ratio of triisobutylene to catalyst is 1:0.015 to 0.100; the catalyst is selected from the following: trifluoromethanesulfonic acid, concentrated sulfuric acid, methanesulfonic acid, aminosulfonic acid, perchloric acid, and phosphoric acid.

[0071] Example 8:

[0072] 8g of the triisobutylene obtained in Example 1 was added to a 50mL constant-pressure dropping funnel. 9.6g of petroleum ether was added to a 250mL jacketed three-necked flask equipped with a magnetic stirrer, with a triisobutylene to petroleum ether mass ratio of 1:1.2. Then, 0.32g of trifluoromethanesulfonic acid was added to the jacketed three-necked flask with a triisobutylene to trifluoromethanesulfonic acid mass ratio of 1:0.04. The mixture was stirred thoroughly to disperse the triisobutylene in the petroleum ether. Using ethanol as the cooling medium, the temperature was lowered to -10°C by connecting a cryogenic bath to the jacketed three-necked flask. After the temperature stabilized, the diisobutylene was added to the flask through the constant-pressure dropping funnel to initiate the reaction. The reaction was stirred at -10°C for 30 minutes. After the reaction was completed, a saturated sodium bicarbonate solution was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and vacuum distillation, 5.78 g of the product hexaisobutylene was obtained. The purity of hexaisobutylene was determined to be 96.67% by gas chromatography.

[0073] (2) Sulfonation reaction:

[0074] The sulfonating agent is subjected to a sulfonation reaction with diisobutylene, triisobutylene, or tetraisobutylene. The reaction temperature is controlled at 10–80 °C, and the reaction time is 6–100 h. After the reaction is completed, the unreacted olefin compounds are removed by extraction with petroleum ether, dissolved in excess anhydrous ethanol, heated to boiling, filtered to remove insoluble inorganic salts, and the ethanol is removed by vacuum distillation to obtain the product polymethyl branched sulfonate.

[0075] The sulfonation reaction equation 1 is as follows:

[0076]

[0077] The sulfonating agent is any one of concentrated sulfuric acid (98%), chlorosulfonic acid, aminosulfonic acid, or sulfur trioxide.

[0078] Example 9:

[0079] 100 mL of diisobutylene obtained in Example 1 was subjected to a sulfonation reaction in a microchannel reactor. SO2 was generated into SO3 gas through a sulfur trioxide generator (vanadium pentoxide as catalyst, reaction temperature 480–520 °C), and the flow rate was adjusted to 200 SCCM by a flow meter. Diisobutylene was mixed with SO3 gas in a micro-mixer at a flow rate of 0.1 mL / min using a horizontal flow pump, and then both were introduced into the microchannel reactor for sulfonation. The reaction temperature was maintained at 40 °C by a constant temperature water bath, and the reaction time was 10 h. The product was collected from the reactor outlet using a receiving bottle. After the reaction, the pH of the product was adjusted to 7–8 with sodium hydroxide solution, and then extracted with petroleum ether and deionized water. The organic layer was separated and extracted three times with deionized water. The extracts were combined into the aqueous phase and then placed in an 80 °C oven for hydrolysis for 24 h. After hydrolysis, the product was dissolved in excess anhydrous ethanol, heated to boiling, filtered to remove insoluble inorganic salts, and the ethanol was removed by rotary evaporation to obtain the product polymethyl branched sulfonate.

[0080] Example 10:

[0081] 100 mL of triisobutylene obtained in Example 1 was subjected to a sulfonation reaction in a microchannel reactor. SO2 was generated into SO3 gas through a sulfur trioxide generator (vanadium pentoxide as catalyst, reaction temperature 480–520 °C), and the flow rate was adjusted to 200 SCCM by a flow meter. Triisobutylene was mixed with SO3 gas in a micro-mixer at a flow rate of 0.1 mL / min using a horizontal flow pump, and then both were introduced into the microchannel reactor for sulfonation. The reaction temperature was maintained at 40 °C by a constant temperature water bath, and the reaction time was 10 h. The product was collected from the reactor outlet using a receiving bottle. After the reaction, the pH of the product was adjusted to 7–8 with sodium hydroxide solution, and then extracted with petroleum ether and deionized water. The organic layer was separated and extracted three times with deionized water. The extracts were combined into the aqueous phase and then placed in an 80 °C oven for hydrolysis for 24 h. After hydrolysis, the product was dissolved in excess anhydrous ethanol, heated to boiling, filtered to remove insoluble inorganic salts, and the ethanol was removed by rotary evaporation to obtain the product polymethyl branched sulfonate.

[0082] Example 11:

[0083] 100 mL of tetraisobutylene obtained in Example 7 was subjected to a sulfonation reaction in a microchannel reactor. SO2 was generated into SO3 gas through a sulfur trioxide generator (vanadium pentoxide as catalyst, reaction temperature 480–520 °C), and the flow rate was adjusted to 200 SCCM by a flow meter. Tetraisobutylene was mixed with SO3 gas in a micro-mixer at a flow rate of 0.1 mL / min using a horizontal flow pump, and then both were introduced into the microchannel reactor for sulfonation. The reaction temperature was maintained at 40 °C by a constant temperature water bath, and the reaction time was 10 h. The product was collected from the reactor outlet using a receiving bottle. After the reaction, the pH of the product was adjusted to 7–8 with sodium hydroxide solution, and then extracted with petroleum ether and deionized water. The organic layer was separated and extracted three times with deionized water. The extracts were combined into the aqueous phase and then placed in an 80 °C oven for hydrolysis for 24 h. After hydrolysis, the product was dissolved in excess anhydrous ethanol, heated to boiling, filtered to remove insoluble inorganic salts, and the ethanol was removed by rotary evaporation to obtain the product polymethyl branched sulfonate.

[0084] The performance of this example sample is characterized as follows:

[0085] Infrared spectroscopy analysis was performed on the anionic surfactant polymethyl branched sulfonate prepared in this embodiment to obtain... Figure 2 . Figure 2 The infrared spectrum of the polymethyl branched sulfonate obtained in this invention is shown. The spectrum shows that at wavenumbers of 3087, 1620, and 913 cm⁻¹... -1 The characteristic absorption peak of =CH2 was still observed at the point, indicating that the product contains vinylidene; wavenumber 2952 cm⁻¹ -1 The peaks at these locations are the -CH3 stretching vibration peaks; and at wavenumbers of 1187 and 1048 cm⁻¹. -1 The characteristic stretching vibration peak of sulfonates appeared at the point. Therefore, it can be concluded that the synthesized product is the target product, polymethyl branched sulfonate.

[0086] Figure 3The surface tension diagrams of the polymethyl branched sulfonate obtained in this invention at different concentrations are shown. 1.0 g of the surfactant sample synthesized in Example 11 was weighed to prepare a surfactant aqueous solution with a concentration of 10 g / L. The instrument used for testing was a German KRUSS K100C surface tension meter. Based on the Wilhelmy Plate method, surface tension was tested by contacting a platinum plate with the surface of an aqueous solution containing a certain concentration of surfactant. A circulating water bath from Uribo Technology Co., Ltd. was used to control the test temperature at 25℃ ± 0.5℃. At the start of the test, the surface tension of pure water was measured first. While maintaining a constant volume of the solution being tested, an equal volume of surfactant solution was continuously injected into the test container, and a corresponding volume of solution was precisely withdrawn. In this way, the concentration of the surfactant solution continuously changed from dilute to concentrated, corresponding to the surface tension of the solution at different concentrations. After the test, the relationship curve between surface tension and concentration (e.g., ...) was obtained. Figure 3 (As shown). By Figure 3 The critical micelle concentration (CMC) of this surfactant can be determined to be 9.469 mmol / L, and the corresponding surface tension (γ) at this concentration can be determined. CMC The surface tension of water is 27.32 mN / m, which indicates that the polymethyl branched sulfonate surfactant synthesized in Example 11 has typical surfactant properties and can effectively reduce the surface tension of water.

[0087] Figure 4 The dynamic surface tension diagram of the polymethyl branched sulfonate obtained in this invention is shown. 1.0 g of the surfactant sample synthesized in Example 11 was weighed to prepare a surfactant aqueous solution with a concentration of 10 g / L. The instrument used for testing was a German KRUSS BP100C surface tension meter. Based on the bubble pressure method, the maximum pressure when an inert gas is slowly passed through a capillary inserted into the surface of the surfactant aqueous solution under pressure was measured. The surface tension of the liquid was calculated according to the Laplace formula. The test temperature was controlled at 25℃ ± 0.5℃ using a circulating water bath from Ulbo Technology Co., Ltd. At the start of the test, pure water was used to measure the capillary inner diameter. The test process involved creating a new interface in the surfactant solution system through continuous bubbling. The dynamic surface tension was studied by measuring the change in surface tension of the newly formed interface over time. After the test, the relationship curve between surface tension and bubble surface age (e.g., ...) was obtained. Figure 4 (As shown). By Figure 4 It can be seen that the polymethyl branched sulfonate surfactant prepared in this embodiment has the ability to rapidly reduce surface tension, and its dynamic surface tension effect is significantly better than that of commercial sodium dodecylbenzene sulfonate (LAS).

[0088] 1.0 g of the surfactant sample synthesized in Example 11 was weighed to prepare a surfactant aqueous solution with a concentration of 10 g / L. The foaming performance of the prepared surfactant aqueous solution was tested using a German KRUSSDFA100 fully automated foam analyzer. The specific test method was as follows: a circulating water bath from ULAB Technology Co., Ltd. was used to control the test temperature at 25℃±0.5℃. 50 mL of the surfactant aqueous solution was placed in a cylindrical glass column with a length of 250 mm and an inner diameter of 40 mm. Foaming was carried out by mechanical stirring at a rotor speed of 6000 r / min for 30 s, with a total running time of 1200 s. The foam of the surfactant was dynamically analyzed. The foam stability was calculated as follows: foam stability = (foam volume measured after 15 min / foam volume measured after 30 s) × 100%. The lower the foam stability, the easier it is to defoam. As shown in Table 1, compared with the commercial product LAS, the polymethyl branched sulfonate surfactant synthesized in Example 11 has excellent rapid defoaming ability.

[0089] Table 1. Foaming properties of the polymethyl branched sulfonate surfactant in Example 11 (25°C)

[0090]

[0091] 1.0 g of the surfactant sample synthesized in Example 11 was weighed to prepare a surfactant aqueous solution with a concentration of 10 g / L. The contact angle was tested using a German KRUSSDSA100 contact angle meter. A smaller contact angle indicates easier wetting of the interface, thus evaluating the wetting performance of the surfactant. The specific test method was as follows: a paraffin film was used as the hydrophobic interface for testing. A syringe with a needle outer diameter of 0.512 nm was used to draw the test solution, with a droplet volume of 3 μL each time. The test time was 30 s, and the temperature was 25 ± 0.5 °C. First, the contact angle of pure water was tested to ensure a clean and flat interface. Then, the contact angle of the surfactant was tested. As shown in Table 2, within 30 s, the contact angles of the polymethyl branched sulfonate surfactant synthesized in Example 11 were significantly lower than those of the commercial product LAS, indicating that it has good wetting performance.

[0092] Table 2 Wetting properties of polymethyl branched sulfonate surfactants in Example 11 (25°C)

[0093]

[0094]

[0095] Weigh 1.0 g of the surfactant sample synthesized in Example 11 to prepare a surfactant aqueous solution with a concentration of 10 g / L. Measure 40 mL of the surfactant aqueous solution and 40 mL of liquid paraffin solution and add them to a 100 mL beaker. Under constant temperature of 25 ± 1 °C, emulsify the liquid using a high-speed homogenizer at a speed of 10000 r / min for 12 s. Then, quickly transfer the emulsion to a stoppered graduated cylinder and record the time required to separate 10 mL of the aqueous phase. The longer the time required to separate 10 mL of the aqueous phase, the better the emulsifying ability of the surfactant. As shown in Table 3, the polymethyl branched sulfonate obtained in this invention has excellent emulsifying ability (the emulsification time corresponding to a surfactant concentration of 10 g / L is 29 h 39 min).

[0096] Table 3. Emulsifying properties of polymethyl branched sulfonate surfactants in Example 11 (25°C)

[0097] Surfactant Temperature (°C) Emulsification time Commercial product - LAS 25 10 min Sodium polymethyl branched sulfonate 25 29 h 39 min

[0098] Example 12:

[0099] 100 mL of the hexaisobutylene obtained in Example 8 was subjected to a sulfonation reaction in a microchannel reactor. SO2 was generated into SO3 gas through a sulfur trioxide generator (vanadium pentoxide as catalyst, reaction temperature 480–520 °C), and the flow rate was adjusted to 200 SCCM by a flow meter. The hexaisobutylene was mixed with the SO3 gas in a micro-mixer at a flow rate of 0.1 mL / min using a horizontal flow pump, and then both were introduced into the microchannel reactor for sulfonation. The reaction temperature was maintained at 40 °C by a constant temperature water bath, and the reaction time was 10 h. The product was collected from the reactor outlet using a receiving bottle. After the reaction, the pH of the product was adjusted to 7–8 with sodium hydroxide solution, and then extracted with petroleum ether and deionized water. The organic layer was separated and extracted three times with deionized water. The extracts were combined into the aqueous phase and then placed in an 80 °C oven for hydrolysis for 24 h. After hydrolysis, the product was dissolved in excess anhydrous ethanol, heated to boiling, filtered to remove insoluble inorganic salts, and the ethanol was removed by rotary evaporation to obtain the product polymethyl branched sulfonate.

[0100] The sulfonation reaction equation 2 is as follows:

[0101]

[0102] The sulfonating agent is either sodium sulfite or sodium bisulfite.

[0103] Example 13:

[0104] 8.416 g (0.05 mol) of triisobutylene obtained in Example 1 was added to a 50 mL beaker. 25.249 g of isopropanol was added at a triisobutylene to alcohol mass ratio of 1:3, and the mixture was stirred thoroughly until homogeneous. Separately, a 150 mL three-necked flask equipped with a magnetic stirrer was taken. 15.609 g (0.15 mol) of sodium bisulfite was added to the flask at a triisobutylene to sodium bisulfite molar ratio of 1:3. 25.249 g of deionized water was added at a deionized water to isopropanol mass ratio of 1:1 to fully dissolve the sodium bisulfite. Then, 0.589 g of tert-butyl peroxide (7% by mass of triisobutylene) and 0.035 g of triethylamine (6% by mass of tert-butyl peroxide) were added. The triisobutylene and alcohol mixture from the beaker was poured into the flask, and the mixture was stirred at 40 °C for 36 h. After the reaction was completed, water and isopropanol were first removed by vacuum distillation, then unreacted triisobutylene was removed by petroleum ether extraction, excess anhydrous ethanol was added to dissolve it, the ethanol was then heated to boiling, the insoluble inorganic salts were removed by filtration, and finally the ethanol was removed by vacuum distillation to obtain the product polymethyl branched sulfonate.

[0105] Example 14:

[0106] 11.222 g (0.05 mol) of tetraisobutylene obtained in Example 7 was added to a 50 mL beaker. 33.665 g of isopropanol was added at a tetraisobutylene to alcohol mass ratio of 1:3, and the mixture was stirred thoroughly until homogeneous. Separately, a 150 mL three-necked flask equipped with a magnetic stirrer was taken. 20.812 g (0.2 mol) of sodium bisulfite was added to the flask at a tetraisobutylene to sodium bisulfite molar ratio of 1:4. 33.665 g of deionized water was added at a deionized water to isopropanol mass ratio of 1:1 to fully dissolve the sodium bisulfite. Then, 0.898 g of tert-butyl peroxide (8% by mass of tetraisobutylene) and 0.063 g of triethylamine (7% by mass of tert-butyl peroxide) were added. The tetraisobutylene and alcohol mixture from the beaker was poured into the flask, and the mixture was stirred at 50 °C for 48 h. After the reaction was completed, water and isopropanol were removed by vacuum distillation, and unreacted tetraisobutylene was removed by extraction with petroleum ether. Excess anhydrous ethanol was added to dissolve the product, and then the ethanol was heated to boiling. The insoluble inorganic salts were removed by filtration, and finally the ethanol was removed by vacuum distillation to obtain the product polymethyl branched sulfonate.

[0107] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A polymethyl branched anionic surfactant, for .

2. The method for preparing anionic surfactant according to claim 1, characterized in that, Includes the following steps: A. Tetraisobutylene is obtained from isobutylene monomer as raw material through a catalytic reaction, wherein the catalyst in the catalytic reaction is Amberlyst 15; B. The target product is obtained by separating and purifying the tetraisobutylene after sulfonation reaction with a sulfonating agent. The sulfonating agent is selected from: concentrated sulfuric acid, chlorosulfonic acid, aminosulfonic acid, sodium sulfite, sodium bisulfite, and sulfur trioxide.

3. The method for preparing anionic surfactant as described in claim 2, characterized in that, The sulfonation reaction conditions described in step B are: a reaction temperature of 10 ~ 80 ℃ and a reaction time of 6 ~ 100 h.

4. A composition comprising the anionic surfactant as described in claim 1.

5. The use of the anionic surfactant as described in claim 1 or the composition as described in claim 4 in phase interface wetting.

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