Alkyl tetrahydronaphthalene sulfonate and its preparation process and application

Abstract

The present invention discloses an alkyl tetrahydronaphthalene sulfonate and its preparation process and application. The alkyl tetrahydronaphthalene sulfonate has any of the following structural formulas. The alkyl tetrahydronaphthalene sulfonate of the embodiment of the present invention has novel structure, can effectively reduce surface tension, has good surface activity, strong foaming ability, high detergency, low cost, wide application field, and is easy to be compounded with various additives into a surfactant, or used alone as a surfactant.

Description

Technical Field

[0001] The invention relates to the field of fine chemical surfactants, in particular to an alkyl tetrahydronaphthalene sulfonate and its preparation process and application. Background Art

[0002] Surfactant refers to a substance that can significantly reduce the surface tension of the target solution. It has fixed hydrophilic and lipophilic groups and can be arranged in a directional manner on the surface of the solution. The molecular structure of the surfactant is amphiphilic: one end is a hydrophilic group and the other end is a hydrophobic group; the hydrophilic group is often a polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amine group and its salt, hydroxyl, amide, ether bond, etc. can also be used as a polar hydrophilic group; while the hydrophobic group is often a non-polar hydrocarbon chain, such as a hydrocarbon chain with more than 8 carbon atoms. Surfactants are divided into ionic surfactants (including cationic surfactants, anionic surfactants and zwitterionic surfactants), non-ionic surfactants, compound surfactants, other surfactants, etc. Surfactants are widely needed in the fields of civil and industrial cleaning agents.

[0003] Therefore, the present invention provides a new surfactant. Summary of the invention

[0004] The object of the present invention is to provide an alkyl tetrahydronaphthalene sulfonate, which has a novel structure, good surface activity, effectively reduces surface tension, has strong foaming ability, high detergency, is easy to be compounded with various additives, and has low cost.

[0005] The present invention also aims to provide a preparation process and application of alkyl tetrahydronaphthalene sulfonate.

[0006] To achieve the above object, an embodiment of the present invention provides an alkyl tetrahydronaphthalene sulfonate having any of the following structural formulas:

[0007]

[0008] Among them, C n is an alkyl group with n carbon atoms, C m It is an alkyl group with m carbon atoms, and the relationship between m and n satisfies: m+n=3-15, and M is a monovalent cation.

[0009] The embodiment of the present invention provides a preparation process of the above-mentioned alkyl tetrahydronaphthalene sulfonate, which can be used to prepare the above-mentioned alkyl tetrahydronaphthalene sulfonate, comprising the following steps:

[0010] A mixed reaction system comprising a catalyst, tetralin and an α-olefin is subjected to an alkylation reaction to obtain an alkyltetralin, wherein the α-olefin has a structural formula of: The relationship between m and n satisfies: m+n=3-15;

[0011] The alkyltetralin is subjected to a sulfonation reaction with sulfur trioxide as a sulfonating agent, and the product after the sulfonation reaction is neutralized with an alkaline neutralizing agent containing sodium or potassium to obtain the above-mentioned alkyltetralin sulfonate.

[0012] In one or more embodiments of the present invention, when the molar ratio of the catalyst to tetralin is 1:(2-16), and the molar ratio of the tetralin to the α-olefin is (3-10):1, an alkyltetralin shown in the following structural formula is obtained:

[0013]

[0014] Among them, C n is an alkyl group with n carbon atoms, C m It is an alkyl group with m carbon atoms, m+n=3-15.

[0015] In one or more embodiments of the present invention, when the molar ratio of the catalyst to tetralin is 1:(2-16), and the molar ratio of the tetralin to the α-olefin is 1:(2-10), an alkyltetralin shown in the following structural formula is obtained:

[0016]

[0017] Among them, C n is an alkyl group with n carbon atoms, C m It is an alkyl group with m carbon atoms, m+n=3-15.

[0018] The process for preparing alkyl tetrahydronaphthalene sulfonate according to claim 2, characterized in that the catalyst is a chloroaluminate type acidic ionic liquid catalyst.

[0019] In one or more embodiments of the present invention, the α-olefin is any one of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, and 1-hexadecene;

[0020] The alkaline neutralizer containing sodium or potassium is any one of NaOH, Na2CO3, KOH, and K2CO3.

[0021] In one or more embodiments of the present invention, the sulfonation reaction is carried out in a capillary microchannel reactor.

[0022] In one or more embodiments of the present invention, in the sulfonation reaction, the molar ratio of the alkyltetralin to sulfur trioxide is 1:(1.0-1.8), the reaction temperature of the sulfonation reaction is 20-80° C., and the reaction time is 0.5-3.0 h; and / or,

[0023] The reaction temperature of the alkylation reaction is 0 to 100° C., and the reaction time is 3 to 80 minutes.

[0024] An embodiment of the present invention provides a use of the above-mentioned alkyltetrahydronaphthalene sulfonate in the preparation of a surfactant.

[0025] An embodiment of the present invention provides a surfactant, including the above-mentioned alkyltetrahydronaphthalene sulfonate.

[0026] Compared with the prior art, the alkyl tetrahydronaphthalene sulfonate according to the embodiment of the present invention has novel structure, good surface activity, effectively reduces surface tension, has strong foaming ability, high detergency, is easy to compound with various additives, has low cost, and has the advantages of wide application fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is an infrared spectrum of monohexyltetralinonesulfonate and monohexyltetralinone according to one embodiment of the present invention;

[0028] Figure 2 is an ESI-MS graph of a monohexyltetrahydronaphthalenesulfonate anionic surfactant according to one embodiment of the present invention;

[0029] Figure 3 is a surface tension diagram of a monohexyltetrahydronaphthalenesulfonate anionic surfactant according to one embodiment of the present invention;

[0030] Figure 4 is a foam diagram of a monohexyltetrahydronaphthalenesulfonate anionic surfactant according to one embodiment of the present invention. DETAILED DESCRIPTION

[0031] The specific implementation modes of the present invention are described in detail below in conjunction with the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific implementation modes.

[0032] The alkyl tetrahydronaphthalene sulfonate according to the preferred embodiment of the present invention has any of the following structural formulas:

[0033]

[0034] Among them, C n is an alkyl group with n carbon atoms, C m is an alkyl group with m carbon atoms, m+n=3 to 15, and M is a monovalent cation. Specifically, M is Na +or K + .

[0035] The present invention also provides a process for preparing the above-mentioned alkyl tetrahydronaphthalene sulfonate, comprising the following steps:

[0036] S1. subjecting a mixed reaction system comprising a catalyst, tetralin and α-olefin to an alkylation reaction to obtain alkyltetralin.

[0037] S2. The alkyltetralin is subjected to a sulfonation reaction with sulfur trioxide, and the product after the sulfonation reaction is neutralized with an alkaline neutralizer containing sodium or potassium to obtain the above-mentioned alkyltetralin sulfonate.

[0038] It should be noted that the advantages of sulfur trioxide as a sulfonating agent are: strong sulfonating ability, equimolar reaction with the substrate, high quality of the product generated by the reaction, less impurities, no waste acid, less corrosion to equipment, fast sulfonation reaction speed, high production efficiency, and high technical level. Microchannel reactors can accurately control the raw material feed ratio and reaction temperature, can achieve continuous and efficient synthesis reactions, shorten reaction time, save production costs, and have the advantages of simple process, continuous control, few side reactions, and high product purity.

[0039] In step S1, when the molar ratio of the catalyst to tetralin is 1:(2-16), and the molar ratio of tetralin to α-olefin is (3-10):1, after the alkylation reaction, an alkyltetralin shown in the following structural formula is obtained:

[0040]

[0041] Among them, C n is an alkyl group with n carbon atoms, C m It is an alkyl group with m carbon atoms, m+n=3 to 15. The reaction mode is:

[0042]

[0043] In step S1, when the molar ratio of the catalyst to tetralin is 1:(2-16), and the molar ratio of tetralin to α-olefin is 1:(2-10), after the alkylation reaction, an alkyltetralin shown in the following structural formula is obtained:

[0044]

[0045] Among them, C n is an alkyl group with n carbon atoms, C m It is an alkyl group with m carbon atoms, m+n=3 to 15. The reaction mode is:

[0046]

[0047] Specifically, in step S1, the conditions for the alkylation reaction are: stirring the reaction at 0-100° C. for 3-80 min; after the reaction is completed, the mixture obtained by the alkylation reaction is allowed to stand for stratification, washed with water, and subjected to reduced pressure distillation to obtain alkyltetralin.

[0048] In a specific embodiment, the catalyst is a chloroaluminate type acidic ionic liquid catalyst. Specifically, the chloroaluminate type acidic ionic liquid catalyst is obtained by reacting anhydrous aluminum chloride and triethylamine hydrochloride in a solvent n-decane. Further, under a dry high-purity argon atmosphere, anhydrous aluminum chloride, triethylamine hydrochloride and n-decane are added to a three-necked round-bottom flask in sequence, and stirred continuously for 1 hour in a constant temperature oil bath at 60°C to obtain a chloroaluminate type acidic ionic liquid catalyst, wherein the molar ratio of anhydrous aluminum chloride to triethylamine hydrochloride is 2:1, and the molar ratio of n-decane to anhydrous aluminum chloride is 10:1.

[0049] In a specific embodiment, the α-olefin is any one of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene and 1-hexadecene.

[0050] In step S2, the reactor for the sulfonation reaction is a capillary microchannel reactor.

[0051] Specifically, in the sulfonation reaction, the molar ratio of alkyltetralin to sulfur trioxide is 1:(1.0-1.8).

[0052] Specifically, the reaction temperature of the sulfonation reaction is 20 to 80° C., and the reaction time is 0.5 to 3.0 h.

[0053] Specifically, the alkaline neutralizer containing sodium or potassium is any one of NaOH, Na2CO3, KOH, and K2CO3.

[0054] Specifically, in the sulfonation reaction, the SO3 concentration is 3% to 5% (the concentration of the mixed gas of SO3 and dry air can be considered as the volume fraction of the mixed gas occupied by SO3).

[0055] The equation for the sulfonation reaction in step S2 is:

[0056]

[0057] A capillary microchannel reactor is used, sulfur trioxide is used as a sulfonating agent, and the alkyltetralin compound obtained in step S1 undergoes a sulfonation reaction. The gaseous sulfur trioxide is measured by a gas flow meter, and the alkyltetralin liquid is measured by a constant flow pump. The mixed materials are introduced into a capillary microchannel reactor for sulfonation reaction, and the reaction temperature is controlled by a constant temperature water bath at 20 to 80° C. The reaction time is 0.5 to 3.0 hours. After the reaction is completed, impurities are removed by neutralization, extraction, desalination, reduced pressure distillation, drying and dehydration to obtain alkyltetralin sulfonate.

[0058] The present invention also provides a use of the above-mentioned alkyltetrahydronaphthalene sulfonate in the preparation of a surfactant.

[0059] The present invention also provides a surfactant, which may include the above-mentioned alkyltetrahydronaphthalene sulfonate. It is understood that the alkyltetrahydronaphthalene sulfonate can be used directly as a surfactant, or can be compounded with other substances to obtain a surfactant.

[0060] The alkyltetrahydronaphthalene sulfonate and its preparation process of the present invention will be described in detail below in conjunction with specific examples.

[0061] Example 1

[0062] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in sequence, and stir continuously in a constant temperature oil bath at 60°C for 1h. According to the molar ratio of tetralin to 1-hexene of 6:1 and the molar ratio of catalyst to tetralin of 1:8, first add tetralin to the catalyst, then slowly drip 1-hexene into the mixture, and stir the reaction at 40°C for 60min. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, the mixture is allowed to stand for stratification. Take the upper liquid product, wash with water to remove a small amount of liquid catalyst, and then distill under reduced pressure to remove the inert organic solvent and residual tetralin. The selectivity of the monohexyltetralin product is 96.60% as measured by gas chromatography.

[0063] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyltetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 3%, the alkyltetralin liquid is measured by a constant flow pump, the molar ratio of alkyltetralin to sulfur trioxide is 1:1.2, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 40°C, the reaction time is 3.0h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, anhydrous ethanol is added to precipitate salt, and then deionized water and petroleum ether are added to extract and remove unreacted alkyltetralin, and secondary desalination is performed again, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then it is placed in an oven for drying and dehydration. The product alkyltetralin sulfonate is obtained. The product yield is 93.4%.

[0064] Figure 1 The infrared spectrum of the alkyl tetrahydronaphthalene sulfonate obtained in Example 1 of the present invention is shown. It can be seen from the figure that the wave number is 2926cm -1 and 2852cm -1 The stretching vibration peaks of -CH3 and -CH2- are at 3003cm -1 , 700cm -1 , 650cm -1 The characteristic peak of the benzene ring is at 1175 cm -1 and 1055cm -1 The characteristic stretching vibration peak of sulfonate appeared at . Therefore, it can be known that the synthesized product is alkyl tetrahydronaphthalene sulfonate.

[0065] Figure 2 The results of the determination of the alkyl tetrahydronaphthalene sulfonate obtained in Example 1 of the present invention by ESI-MS in negative ion mode are shown. ESI-MS [M-Na + ]=295.2(calcd 295.13).

[0066] Figure 3The surface tension diagram of the alkyl tetrahydronaphthalene sulfonate obtained in Example 1 of the present invention at different concentrations is shown. 1.0g of the alkyl tetrahydronaphthalene sulfonate sample synthesized in Example 1 was weighed, and an alkyl tetrahydronaphthalene sulfonate aqueous solution with a concentration of 1g / L was prepared. The instrument used for the test was a German Krüss K100C surface tension tester. The surface tension was tested based on the Wilhelmy Plate method by using a platinum plate to contact the surface of an aqueous solution containing a certain concentration of alkyl tetrahydronaphthalene sulfonate. The test temperature was controlled to 25±0.5°C using a circulating water bath of Ulabo Technology. When the instrument starts the test, it first measures the surface tension of pure water, and continuously injects an equal volume of alkyl tetrahydronaphthalene sulfonate solution into the test container while keeping the volume of the measured solution constant, and accurately draws out the corresponding volume of solution, so that the concentration of the alkyl tetrahydronaphthalene sulfonate solution continuously changes from dilute to concentrated, and the surface tension of the solution at different concentrations can be obtained accordingly. At the end of the test, the relationship curve between the surface tension and the concentration can be obtained (such as Figure 3 ). Figure 3 It can be determined that the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.531 mmol / L and the corresponding surface tension (γ CMC ) is 33.453 mN / m, which shows that the alkyltetrahydronaphthalene sulfonate synthesized in Example 1 has typical surfactant properties and can effectively reduce the surface tension of the aqueous solution.

[0067] Weigh the alkyl tetrahydronaphthalene sulfonate sample synthesized in Example 1, prepare alkyl tetrahydronaphthalene sulfonate aqueous solutions of different concentrations, and use DFA 100 dynamic foam analyzer (Krüss, Germany) to measure the foaming properties of alkyl tetrahydronaphthalene sulfonate aqueous solutions of different concentrations. The specific test steps are as follows: 50 mL of sample solution is placed in a cylindrical glass column with a length of 250 mL, and run at a speed of 6000 r / min for 30 seconds by mechanical stirring to generate foam, and the total running time is 1200 seconds. All experiments were repeated three times at room temperature, and the average of the three results was taken as the final calculation result. The results are as follows: Figure 4 As shown. In addition, the foaming properties of aqueous solutions of alkyl tetrahydronaphthalene sulfonate salts of different concentrations were tested by the improved Ross-Miles method. The foam volume of the aqueous solution of alkyl tetrahydronaphthalene sulfonate salts was measured from 0s to 20min at 25±0.2°C, and the foam instability data were expressed by foam stability (foam volume ratio at 5min and 30s) and the reduction of foam volume (FV) at 20min. It can be seen from Table 1 that the alkyl tetrahydronaphthalene sulfonate salt synthesized in Example 1 has a large initial foaming volume and a fast defoaming speed.

[0068] Table 1 Foaming of Example 1 (1.5 g / L) Alkyl Tetrahydronaphthalene Sulfonate

[0069]

[0070] Weigh the alkyl tetrahydronaphthalene sulfonate sample synthesized in Example 1 to prepare an alkyl tetrahydronaphthalene sulfonate aqueous solution with a concentration of 0.25-2.0 g / L, measure 40 mL of the alkyl tetrahydronaphthalene sulfonate aqueous solution and 40 mL of liquid paraffin liquid respectively and add them to a stoppered measuring cylinder. Under a constant temperature of 25±1°C, shake the stoppered measuring cylinder up and down violently 5 times, let it stand for 1 minute, and repeat this operation 5 times. Record the time required to separate 10 mL of aqueous phase in the measuring cylinder. This time is used to describe the emulsifying ability of alkyl tetrahydronaphthalene sulfonate aqueous solutions of different concentrations. The longer the time required to separate 10 mL of aqueous phase, the better the emulsifying ability of the alkyl tetrahydronaphthalene sulfonate. As can be seen from Table 2, the alkyl tetrahydronaphthalene sulfonate obtained by the present invention has good emulsifying ability (the corresponding emulsifying time is 220s when the concentration of alkyl tetrahydronaphthalene sulfonate is 1 g / L).

[0071] Table 2 Emulsification ability of alkyl tetrahydronaphthalene sulfonate at different concentrations (25°C)

[0072]

[0073] Example 2

[0074] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in sequence, and stir continuously in a constant temperature oil bath at 60°C for 1h. According to the molar ratio of tetralin to 1-octene of 3:1 and the molar ratio of catalyst to tetralin of 1:6, first add tetralin to the catalyst, then slowly drip 1-octene into the mixture, and stir and react at 60°C for 30min. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, the mixture is allowed to stand for stratification. Take the upper liquid product, wash it with water to remove a small amount of liquid catalyst, and then distill it under reduced pressure to remove the inert organic solvent and residual tetralin to obtain a mixed alkyl tetralin product. According to gas chromatograph analysis: the selectivity of monooctyl tetralin is 95.65%.

[0075] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyltetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 3%, the alkyltetralin liquid is measured by a constant flow pump, the molar ratio of alkyltetralin to sulfur trioxide is 1:1.4, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 20°C, the reaction time is 2.0h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, anhydrous ethanol is added to precipitate salt, deionized water and petroleum ether are added to extract and remove unreacted alkyltetralin, and then secondary desalination is performed, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then placed in an oven for drying and dehydration. The product alkyltetralin sulfonate is obtained. The product yield is 96.7%.

[0076] Using the detection method described in Example 1, the IR (KBr) of the alkyl tetrahydronaphthalene sulfonate obtained in this example was obtained: ν = 3003, 2931, 2850, 1173, 1055, 700, 650 cm -1 ; ESI-MS[M-Na + ]=323.3(calcd323.16); the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.678mmol / L and the surface tension (γ CMC ) is 33.628mN / m; the alkyl tetrahydronaphthalene sulfonate synthesized in this embodiment has an initial foaming of 150mL at 25°C, a fast defoaming speed, and a foam stability of 91.5%; it has good emulsifying ability at 25°C, and the corresponding emulsifying time is 347s.

[0077] Example 3

[0078] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in sequence, and stir continuously in a constant temperature oil bath at 50℃ for 1h. According to the molar ratio of tetralin to 1-decene of 8:1 and the molar ratio of catalyst to tetralin of 1:2, first add tetralin to the catalyst, then slowly drip 1-decene into the mixture, and stir and react for 60min at 0℃. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, let it stand for stratification. Take the upper liquid product, wash it with water to remove a small amount of liquid catalyst, and then distill the residual tetralin under reduced pressure to obtain a mixed alkyl tetralin product. The product is quantitatively analyzed by gas chromatograph, and the results show that the selectivity of monodecyl tetralin is 97.34%.

[0079] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyltetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 4%, the alkyltetralin liquid is measured by a constant flow pump, the molar ratio of alkyltetralin to sulfur trioxide is 1:1.0, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 60°C, the reaction time is 0.5h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, ethanol is added to precipitate salt, and then deionized water and petroleum ether are added to extract and remove unreacted alkyltetralin, secondary desalination is performed, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then placed in an oven for drying and dehydration. The product alkyltetralin sulfonate is obtained. The product yield is 96.3%.

[0080] Using the detection method described in Example 1, the IR (KBr) of the alkyl tetrahydronaphthalene sulfonate obtained in this example was obtained: ν = 3003, 2926, 2854, 1175, 1052, 700, 650 cm -1 ; ESI-MS[M-Na + ]=351(calcd351.19); the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.732mmol / L and the corresponding surface tension (γ CMC ) is 33.643mN / m; the alkyl tetrahydronaphthalene sulfonate synthesized in this embodiment has an initial foaming of 150.3mL at 25°C, a fast defoaming speed, and a foam stability of 94.8%; it has good emulsifying ability at 25°C, and the corresponding emulsifying time is 333s.

[0081] Example 4

[0082] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in sequence, and stir continuously in a constant temperature oil bath at 60℃ for 1h. According to the molar ratio of tetralin to 1-dodecene of 5:1 and the molar ratio of catalyst to tetralin of 1:10, first add tetralin to the catalyst, then slowly drip 1-dodecene into the mixture, and stir and react at 50℃ for 80min. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, the mixture is allowed to stand and separate. Take the upper liquid product, wash it with water to remove a small amount of liquid catalyst, and then remove the residual tetralin by reduced pressure distillation to obtain a mixed alkyltetralin product. The product is quantitatively analyzed by gas chromatograph, and the results show that the selectivity of monododecyltetralin is 97.63%.

[0083] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyltetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 4%, the alkyltetralin liquid is measured by a constant flow pump, the molar ratio of alkyltetralin to sulfur trioxide is 1:1.8, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 40°C, the reaction time is 1.0h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, ethanol is added to precipitate salt, and then deionized water and petroleum ether are added to extract and remove unreacted alkyltetralin, and secondary desalination is performed, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then placed in an oven for drying and dehydration. The product alkyltetralin sulfonate is obtained. The product yield is 95.8%.

[0084] Using the detection method described in Example 1, the IR (KBr) of the alkyl tetrahydronaphthalene sulfonate obtained in this example was obtained: ν = 3003, 2930, 2852, 1173, 1052, 700, 650 cm -1 ; ESI-MS[M-Na + ]=379.2(calcd379.22); the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.833mmol / L and the corresponding surface tension (γ CMC ) is 33.885mN / m; the alkyl tetrahydronaphthalene sulfonate synthesized in this embodiment has an initial foaming of 136.1mL at 25°C, a fast defoaming speed, and a foam stability of 71.1%; it has good emulsifying ability at 25°C, and the corresponding emulsifying time is 270s.

[0085] Example 5

[0086] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in sequence, and stir continuously in a constant temperature oil bath at 60℃ for 1h. According to the molar ratio of tetralin to 1-tetradecene of 10:1 and the molar ratio of catalyst to tetralin of 1:16, first add tetralin to the catalyst, then slowly drip 1-tetradecene into the mixture, and stir and react at 80℃ for 20min. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, the mixture is allowed to stand and separate. Take the upper liquid product, wash it with water to remove a small amount of liquid catalyst, and then remove the residual tetralin by reduced pressure distillation to obtain a mixed alkyltetralin product. The product is quantitatively analyzed by gas chromatograph, and the results show that the selectivity of monotetradecene is 96.26%.

[0087] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyltetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 4%, the alkyltetralin liquid is measured by a constant flow pump, the molar ratio of alkyltetralin to sulfur trioxide is 1:1.4, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 50°C, the reaction time is 1.5h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, ethanol is added to precipitate salt, and then deionized water and petroleum ether are added to extract and remove unreacted alkyltetralin, and secondary desalination is performed, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then placed in an oven for drying and water removal. The product alkyltetralin sulfonate is obtained. The product yield is 94.7%.

[0088] Using the detection method described in Example 1, the IR (KBr) of the alkyl tetrahydronaphthalene sulfonate obtained in this example was obtained: ν = 3003, 2930, 2852, 1173, 1052, 700, 650 cm -1 ; ESI-MS[M-Na + ]=407.6(calcd407.63); the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.854mmol / L and the corresponding surface tension (γ CMC ) is 33.435mN / m; the alkyl tetrahydronaphthalene sulfonate synthesized in this embodiment has an initial foaming of 143.5mL at 25°C, a fast defoaming speed, and a foam stability of 78.8%; it has good emulsifying ability at 25°C, and the corresponding emulsifying time is 321s.

[0089] Example 6

[0090] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in turn, and stir continuously in a constant temperature oil bath at 60℃ for 1h. According to the molar ratio of tetralin to 1-hexadecene of 8:1 and the molar ratio of catalyst to tetralin of 1:12, first add tetralin to the catalyst, then slowly drip 1-hexadecene into the mixture, and stir and react at 100℃ for 40min. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, the mixture is allowed to stand and separate. Take the upper liquid product, wash it with water to remove a small amount of liquid catalyst, and then remove the residual tetralin by reduced pressure distillation to obtain a mixed alkyltetralin product. The product is quantitatively analyzed by gas chromatograph, and the results show that the selectivity of monohexadecyltetralin is 96.83%.

[0091] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyl tetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 5%, the alkyl tetralin liquid is measured by a constant flow pump, the molar ratio of alkyl tetralin to sulfur trioxide is 1:1.6, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 80°C, the reaction time is 3.0h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, ethanol is added to precipitate salt, and then deionized water and petroleum ether are added to extract and remove unreacted alkyl tetralin, and secondary desalination is performed, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then it is placed in an oven for drying and dehydration. The product alkyl tetralin sulfonate is obtained. The product yield is 95.38%.

[0092] Using the detection method described in Example 1, the IR (KBr) of the alkyl tetrahydronaphthalene sulfonate obtained in this example was obtained: ν = 3003, 2930, 2852, 1173, 1052, 700, 650 cm -1 ; ESI-MS[M-Na + ]=435.6(calcd435.69); the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.898mmol / L and the surface tension (γ CMC ) is 33.685mN / m; the alkyl tetrahydronaphthalene sulfonate synthesized in this embodiment has an initial foaming of 138.7mL at 25°C, a fast defoaming speed, and a foam stability of 84.5%; it has good emulsifying ability at 25°C, and the corresponding emulsifying time is 356s.

[0093] Example 7

[0094] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in turn, and stir continuously in a constant temperature oil bath at 60°C for 1h. According to the molar ratio of tetralin to 1-hexene of 1:2; the molar ratio of catalyst to tetralin of 1:2, first add tetralin to the catalyst, then slowly drip 1-hexene into the mixture, and stir the reaction at 50°C for 40min. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, the mixture is allowed to stand for stratification. Take the upper liquid product, wash with water to remove a small amount of liquid catalyst, and then distill under reduced pressure to remove the inert organic solvent and residual tetralin. The selectivity of dihexyltetralin is 96.89% as measured by gas chromatography.

[0095] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyltetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 4%, the alkyltetralin liquid is measured by a constant flow pump, the molar ratio of alkyltetralin to sulfur trioxide is 1:1.4, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 50°C, the reaction time is 2.0h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, anhydrous ethanol is added to precipitate salt, and then deionized water and petroleum ether are added to extract and remove unreacted alkyltetralin, and then secondary desalination is performed again, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then it is placed in an oven for drying and dehydration. The product alkyltetralin sulfonate is obtained. The product yield is 95.4%.

[0096] Using the detection method described in Example 1, the IR (KBr) of the alkyl tetrahydronaphthalene sulfonate obtained in this example was obtained: ν = 3003, 2930, 2852, 1173, 1052, 700, 650 cm -1 ; ESI-MS[M-Na + ]=402.6(calcd402.57); the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.887mmol / L and the corresponding surface tension (γ CMC ) is 32.745mN / m; the alkyl tetrahydronaphthalene sulfonate synthesized in this embodiment has an initial foaming of 141.8mL at 25°C, a fast defoaming speed, and a foam stability of 78.5%; it has good emulsifying ability at 25°C, and the corresponding emulsifying time is 421s.

[0097] Example 8

[0098] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in sequence, and stir continuously in a constant temperature oil bath at 60°C for 1h. According to the molar ratio of tetralin to 1-decene of 1:6 and the molar ratio of catalyst to tetralin of 1:10, first add tetralin to the catalyst, then slowly drip 1-decene into the mixture, and stir and react for 80min at 0°C. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, the mixture is allowed to stand for stratification. Take the upper liquid product, wash with water to remove a small amount of liquid catalyst, and then distill under reduced pressure to remove the inert organic solvent and residual tetralin. The selectivity of didecyltetralin product measured by gas chromatography is 95.86%.

[0099] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyl tetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 4%, the alkyl tetralin liquid is measured by a constant flow pump, the molar ratio of alkyl tetralin to sulfur trioxide is 1:1.0, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 20°C, the reaction time is 3.0h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, anhydrous ethanol is added to precipitate salt, and then deionized water and petroleum ether are added to extract and remove unreacted alkyl tetralin, and then secondary desalination is performed again, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then it is placed in an oven for drying and dehydration. The product alkyl tetralin sulfonate is obtained. The product yield is 95.7%.

[0100] Using the detection method described in Example 1, the IR (KBr) of the alkyl tetrahydronaphthalene sulfonate obtained in this example was obtained: ν = 3003, 2930, 2852, 1173, 1052, 700, 650 cm -1 ; ESI-MS[M-Na + ]=514.8(calcd514.78); the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.878mmol / L and the surface tension (γ CMC ) is 32.756mN / m; the alkyl tetrahydronaphthalene sulfonate synthesized in this embodiment has an initial foaming of 140.3mL at 25°C, a fast defoaming speed, and a foam stability of 76.5%; it has good emulsifying ability at 25°C, and the corresponding emulsifying time is 435s.

[0101] Example 9

[0102] 1) Alkylation reaction: Prepare the catalyst, add anhydrous aluminum chloride (3.0mmol), triethylamine hydrochloride (1.5mmol) and inert organic solvent n-decane (6.0mL) into a three-necked round-bottom flask in sequence, and stir continuously in a constant temperature oil bath at 60℃ for 1h. According to the molar ratio of tetralin to 1-hexadecene of 1:10 and the molar ratio of catalyst to tetralin of 1:16, first add tetralin to the catalyst, then slowly drip 1-hexadecene into the mixture, and stir and react at 100℃ for 20min. The whole process is carried out in a dry high-purity argon atmosphere. After the reaction is completed, the mixture is allowed to stand and separate. Take the upper liquid product, wash it with water to remove a small amount of liquid catalyst, and then remove the residual tetralin by reduced pressure distillation to obtain a mixed alkyltetralin product. The product is quantitatively analyzed by gas chromatograph, and the results show that the selectivity of hexadecyltetralin is 95.73%.

[0103] 2) Sulfonation reaction: using a capillary microchannel reactor, sulfur trioxide is used as a sulfonation reagent to react with the alkyltetralin obtained by the above reaction 1), the gaseous sulfur trioxide is measured by a gas flow meter, the SO3 concentration is 5%, the alkyltetralin liquid is measured by a constant flow pump, the molar ratio of alkyltetralin to sulfur trioxide is 1:1.8, the mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction, the reaction temperature is controlled by a constant temperature water bath, the reaction temperature is controlled at 80°C, the reaction time is 0.5h, after the reaction is completed, sodium hydroxide is added to neutralize to neutrality, ethanol is added to precipitate salt, and then deionized water and petroleum ether are added to extract and remove unreacted alkyltetralin, and secondary desalination is performed, and then suction filtration and rotary evaporation are performed to remove most of the ethanol, and then it is placed in an oven for drying and dehydration. The product alkyltetralin sulfonate is obtained. The product yield is 96.7%.

[0104] Using the detection method described in Example 1, the IR (KBr) of the alkyl tetrahydronaphthalene sulfonate obtained in this example was obtained: ν = 3003, 2930, 2852, 1173, 1052, 700, 650 cm -1 ; ESI-MS[M-Na + ]=661.1(calcd661.12); the critical micelle concentration (CMC) of the alkyl tetrahydronaphthalene sulfonate is 0.873mmol / L and the corresponding surface tension (γ CMC ) is 32.368mN / m; the alkyl tetrahydronaphthalene sulfonate synthesized in this embodiment has an initial foaming of 143.6mL at 25°C, a fast defoaming speed, and a foam stability of 76.7%; it has good emulsifying ability at 25°C, and the corresponding emulsifying time is 489s.

[0105] In summary, the alkyl tetrahydronaphthalene sulfonate of the present invention has the advantages of good surface activity, effective reduction of surface tension, strong foaming ability, high detergency, low cost and wide application field. In addition, the alkyl tetrahydronaphthalene sulfonate of the present invention can be used as a surfactant, or can be easily compounded with various additives to form a surfactant for use.

[0106] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. A surfactant, characterized in that It includes alkyl tetrahydronaphthalene sulfonate, wherein the alkyl tetrahydronaphthalene sulfonate has any of the following structural formulas: Among them, C n is an alkyl group with n carbon atoms, C m is an alkyl group of m carbon atoms, and the relationship between m and n satisfies: m+n=5 or 7 or 9, and M is a sodium ion or a potassium ion; The preparation process of the alkyl tetrahydronaphthalene sulfonate comprises the following steps: A mixed reaction system comprising a catalyst, tetralin and an α-olefin is subjected to an alkylation reaction to obtain an alkyltetralin, wherein the α-olefin has a structural formula of: , wherein the relationship between m and n satisfies: m+n=5 or 7 or 9; the catalyst is a chloroaluminate type acidic ionic liquid catalyst; The alkyltetralin is subjected to a sulfonation reaction with sulfur trioxide as a sulfonating agent, and the product after the sulfonation reaction is neutralized with an alkaline neutralizing agent containing sodium or potassium to obtain the alkyltetralin sulfonate.

2. The surfactant according to claim 1, characterized in that When the molar ratio of the catalyst to tetralin is 1:(2-16), and the molar ratio of the tetralin to the α-olefin is (3-10):1, an alkyltetralin shown in the following structural formula is obtained: Among them, C n is an alkyl group with n carbon atoms, C m It is an alkyl group with m carbon atoms, m+n=5 or 7 or 9.

3. The surfactant according to claim 1, characterized in that When the molar ratio of the catalyst to tetralin is 1:(2-16), and the molar ratio of the tetralin to the α-olefin is 1:(2-10), the alkyltetralin shown in the following structural formula is obtained: Among them, C n is an alkyl group with n carbon atoms, C m It is an alkyl group with m carbon atoms, m+n=5 or 7 or 9.

4. The surfactant according to claim 1, characterized in that The α-olefin is any one of 1-hexene, 1-octene and 1-decene; The alkaline neutralizer containing sodium or potassium is any one of NaOH, Na2CO3, KOH, and K2CO3.

5. The surfactant according to claim 1, characterized in that The sulfonation reaction is carried out in a capillary microchannel reactor.

6. The surfactant according to claim 1, characterized in that In the sulfonation reaction, the molar ratio of the alkyltetralin to sulfur trioxide is 1:(1.0-1.8), the SO3 concentration is 3%-5%, the reaction temperature of the sulfonation reaction is 20-80°C, and the reaction time is 0.5-3.0 h; and / or, The reaction temperature of the alkylation reaction is 0-100°C, and the reaction time is 3-80 min.

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