Branched-chain fatty tertiary alcohol sulfate, branched-chain alkyl sulfonate and co-production method thereof

Abstract

The present application discloses a branched fatty tertiary alcohol sulfate, branched alkyl sulfonate and a co-production method thereof, wherein the co-production method comprises using a mixture of α-olefins and alkanes with the same carbon chain length as a raw material, and carrying out a dimerization reaction under the action of a catalyst to obtain a vinylidene olefin compound; in the presence of an acidic catalyst, using the vinylidene olefin compound and deionized water as reactants, carrying out a hydration reaction to obtain a branched fatty tertiary alcohol product and an α-olefin dimer isomerization product; using the branched fatty tertiary alcohol product as a raw material, carrying out a sulfation reaction to obtain a branched fatty tertiary alcohol sulfate; using the α-olefin dimer isomerization product as a raw material, carrying out a sulfonation reaction to obtain a branched alkyl sulfonate. The co-production method of the present application realizes the separation of straight-chain α-olefins and normal alkanes of the same carbon chain, and at the same time realizes the resource utilization of α-olefins, and the co-produced surfactant product has a clear composition and structure and high purity.

Description

Technical Field

[0001] The present application belongs to the technical field of surfactants, and specifically relates to a branched fatty tertiary alcohol sulfate, a branched alkyl sulfonate and a co-production method thereof. Background Art

[0002] Surfactants are an important class of fine chemicals, composed of hydrophilic groups and lipophilic groups, with the characteristics of reducing surface tension, wetting, emulsification, dispersion, solubilization, penetration, foaming, etc. According to the type of hydrophilic group, surfactants can be divided into nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Branched surfactants are a class of surfactants with branched hydrophobic end alkyl chains. The branched structure gives surfactants some excellent properties, such as lower surface tension, low foaming or fast defoaming properties, outstanding wetting, penetration and detergency, which makes branched surfactants show important research and application value in the field of industrial hard surface cleaning. Common branched surfactants are synthesized with petrochemical Gulbert alcohol as the hydrophobic end raw material, such as Gulbert alcohol sulfate, Gulbert alcohol polyoxyethylene ether, etc. However, due to the complex by-products in the synthesis process of Gulbert alcohol and the low selectivity of the target product, which is only 40-60%, the application and development of branched surfactants derived from Gulbert alcohol are limited. Summary of the invention

[0003] The purpose of the present application is to provide a branched fatty tertiary alcohol sulfate, a branched alkyl sulfonate and a co-production method thereof, so as to solve the technical problem in the prior art that the application and development of branched surfactants synthesized by deriving gulbert alcohol are limited due to the complex by-products and low selectivity of the target product in the synthesis process of gulbert alcohol.

[0004] To achieve the above purpose, a technical solution adopted in this application is:

[0005] Provided is a method for co-producing branched-chain fatty tertiary alcohol sulfate and branched-chain alkyl sulfonate, comprising:

[0006] A mixture of α-olefins and alkanes with the same carbon chain length is used as a raw material, and a dimerization reaction is carried out under the action of a catalyst. After the reaction is completed, water is added to quench the reaction, and then the alkanes are separated by washing, extraction, drying and distillation in sequence to obtain vinylidene olefin compounds.

[0007] In the presence of an acidic catalyst, the vinylidene olefin compound and deionized water are used as reactants and a low-carbon alcohol is used as a solvent to carry out a hydration reaction, and after the reaction is completed, extraction, water washing, drying and concentration are sequentially performed to obtain a mixture, and the mixture is separated by distillation to obtain a branched fatty tertiary alcohol product and an alpha-olefin dimer isomerization product;

[0008] The branched fatty tertiary alcohol product is used as a raw material, mixed with a mixture of sulfur trioxide and dry air, and subjected to a sulfation reaction. After the reaction is completed, impurities are removed and recrystallization is performed to obtain a branched fatty tertiary alcohol sulfate;

[0009] The α-olefin dimer isomerization product is used as a raw material, mixed with a mixed gas of sulfur trioxide and dry air, and subjected to a sulfonation reaction. After the reaction is completed, impurities are removed and recrystallization is performed to obtain a branched alkyl sulfonate.

[0010] In one or more embodiments, in the step of carrying out a dimerization reaction using a mixture of α-olefins and alkanes with the same carbon chain length as a raw material under the action of a catalyst, the catalyst comprises zirconocene dichloride and methylaluminoxane, the molar ratio of the zirconocene dichloride to methylaluminoxane is 1:(1-20), the molar ratio of the α-olefin to the catalyst is 1:(0.020-0.080), the reaction temperature of the dimerization reaction is 30-80°C, and the reaction time is 5-20h.

[0011] In one or more embodiments, in the step of carrying out a hydration reaction in the presence of an acidic catalyst, using the vinylidene olefin compound and deionized water as reactants and a low-carbon alcohol as a solvent, the molar ratio of the vinylidene olefin compound to the deionized water is 1:(1-20), the acidic catalyst is one or more combinations of a cation exchange resin catalyst, a zeolite catalyst and an organic acid catalyst, the mass ratio of the acidic catalyst to the vinylidene olefin compound is (5-50):100, the reaction temperature of the hydration reaction is 30-120°C, and the reaction time is 6-48h.

[0012] In one or more embodiments, the cation exchange resin catalyst is one or more combinations of Amberlyst 36, Amberlyst 35, Amberlyst 15, AquivionPW98, AquivionPW87S, and NKC-9; the zeolite catalyst is one or more combinations of H-ZSM-5, H-β, and mordenite; the organic acid catalyst is one or more combinations of trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid.

[0013] In one or more embodiments, in the step of using the branched fatty tertiary alcohol product as a raw material and mixing it with a mixed gas of sulfur trioxide and dry air to carry out a sulfation reaction, the volume fraction of sulfur trioxide in the mixed gas is 3.0-5.0%, the molar ratio of the branched fatty tertiary alcohol product to the sulfur trioxide is 1:(1.0-1.6), the reaction temperature of the sulfation reaction is 20-80°C, and the reaction time is 0.5-3.0h.

[0014] In one or more embodiments, the α-olefin dimer isomerization product is used as a raw material and mixed with a mixed gas of sulfur trioxide and dry air to carry out a sulfonation reaction, the molar ratio of the α-olefin dimer isomerization product to the sulfur trioxide is 1:(1.0-1.6), the volume fraction of sulfur trioxide in the mixed gas is 3.0-5.0%, the reaction temperature of the sulfonation reaction is 20-80°C, and the reaction time is 0.5-3.0h.

[0015] In one or more embodiments, the step of removing impurities after the reaction is completed is specifically to extract, desalt, filter, distill and dry the product after the reaction in sequence.

[0016] In one or more embodiments, the α-olefin is C4 to C 16 Any one of the olefins, the mixture of α-olefins and alkanes with the same carbon chain length is separated from coal-based synthetic oil.

[0017] To achieve the above purpose, another technical solution adopted by this application is:

[0018] Provided is a branched fatty tertiary alcohol sulfate prepared by the co-production method described in any one of the above embodiments, wherein the branched fatty tertiary alcohol sulfate has the following general chemical formula:

[0019]

[0020] In the formula, R is a C1-C13 saturated hydrocarbon group.

[0021] To achieve the above purpose, another technical solution adopted by this application is:

[0022] Provided is a branched alkyl sulfonate prepared by the co-production method described in any one of the above embodiments, wherein the branched alkyl sulfonate has the following general chemical formula:

[0023]

[0024] In the formula, R is a C1-C13 saturated hydrocarbon group.

[0025] Different from the prior art, the beneficial effects of this application are:

[0026] The co-production method of the present application uses α-olefins and alkanes with the same carbon chain length as raw materials, and realizes the separation of straight-chain α-olefins and normal alkanes with the same carbon chain through a reaction-separation-application integrated process to obtain alkanes, and at the same time realizes the resource utilization of α-olefins to co-produce branched fatty tertiary alcohol sulfate anionic surfactants and branched alkyl sulfonate anionic surfactants. The product composition and structure are clear, and the product purity is high, which solves the problems of complex by-products and low selectivity of target products in the synthesis process of branched surfactants derived from Gulbert alcohol.

[0027] The two branched anionic surfactant products co-produced in this application have clear composition and structure, high product purity, excellent performance, low foaming, excellent wetting performance, and typical branched surfactant characteristics;

[0028] The co-production method of the present application generates no waste during the reaction process, has a high raw material utilization rate, a low reaction temperature, good economy, and is easy to realize industrialized popularization and production. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic flow diagram of an embodiment of a method for co-producing a branched tertiary fatty alcohol sulfate anionic surfactant and a branched alkyl sulfonate anionic surfactant according to the present application;

[0030] Figure 2 is the infrared spectrum of the branched fatty tertiary alcohol product prepared in Example 1 of the present application;

[0031] Figure 3 is an infrared spectrum of the α-olefin dimer isomerization product prepared in Example 1 of the present application;

[0032] Figure 4 is the infrared spectrum of the branched fatty tertiary alcohol sulfate prepared in Example 1 of the present application;

[0033] Figure 5 is the infrared spectrum of the branched alkyl sulfonate prepared in Example 1 of the present application;

[0034] Figure 6 is a surface tension diagram of branched fatty tertiary alcohol sulfate prepared in Example 1 of the present application at different concentrations;

[0035] Figure 7 Surface tension diagram of branched alkyl sulfonate prepared in Example 1 of the present application at different concentrations. DETAILED DESCRIPTION

[0036] The present application will be described in detail below in conjunction with the accompanying drawings and various embodiments. However, these embodiments do not limit the present application, and any structural, methodological, or functional changes made by a person of ordinary skill in the art based on these embodiments are all within the scope of protection of the present application.

[0037] As the background art, the existing branched surfactants synthesized by deriving from Gulbert alcohol have limited application and development due to the complex by-products and low selectivity of the target product (40-60%) during the synthesis of Gulbert alcohol.

[0038] Alpha-olefins can be selectively dimerized by metallocene catalysts to synthesize structurally regular vinylidene olefin compounds. Alpha-olefin dimer vinylidene olefin compounds have similar molecular structures to Gulbert alcohols, and theoretically can be used as hydrophobic end raw materials for synthesizing branched surfactants. They can be grafted with hydrophilic groups through double bond functionalization reactions to synthesize branched surfactants, thereby replacing traditional Gulbert alcohols.

[0039] α-olefin is one of the important raw materials for the synthesis of fine chemicals. The content of α-olefin with carbon number of 5 to 25 in coal-based synthetic oil is as high as 60%. However, linear α-olefin and normal alkanes with the same carbon chain coexist in the liquid phase product of coal-based synthetic oil. Since the two have similar molecular structures and similar physical properties such as boiling point and melting point, it is very difficult to separate them by traditional distillation.

[0040] To this end, the applicant has developed a method for the co-production of branched tertiary fatty alcohol sulfate anionic surfactants and branched alkyl sulfonate anionic surfactants. The co-production method can use straight-chain α-olefins and normal alkanes with the same carbon chain as raw materials to co-produce branched tertiary fatty alcohol sulfate anionic surfactants and branched alkyl sulfonate anionic surfactants. On the one hand, it effectively solves the problems of existing branched surfactants synthesized by deriving Gulbert alcohol, and on the other hand, it also solves the problem of separating α-olefins from coal-based synthetic oils.

[0041] Specifically, see Figure 1 , Figure 1 It is a schematic flow chart of an implementation method of a method for co-producing a branched tertiary fatty alcohol sulfate anionic surfactant and a branched alkyl sulfonate anionic surfactant according to the present application.

[0042] The co-generation approach includes:

[0043] S100. A mixture of α-olefins and alkanes with the same carbon chain length is used as a raw material to carry out a dimerization reaction under the action of a catalyst. After the reaction is completed, water is added to quench the reaction. The alkanes are separated by washing, extraction, drying and distillation in sequence to obtain vinylidene olefin compounds.

[0044] Specifically, the reaction equation for the dimerization reaction is as follows:

[0045]

[0046] The catalyst may include a main catalyst zirconocene dichloride and a co-catalyst methylaluminoxane. In one embodiment, the molar ratio of zirconocene dichloride to methylaluminoxane may be 1:(1-20), and the molar ratio of α-olefin to catalyst may be 1:(0.020-0.080).

[0047] In one embodiment, the reaction temperature of the dimerization reaction may be 30 to 80° C., and the reaction time may be 5 to 20 hours.

[0048] It can be understood that under the action of the catalyst, α-olefins self-polymerize to synthesize α-olefin dimers, vinylidene olefin compounds. Due to the difference in boiling points between vinylidene olefin compounds and alkanes, the alkanes and vinylidene olefin compounds can be separated by sequential water washing, extraction, drying and distillation to obtain vinylidene olefin compounds, and alkanes are obtained simultaneously, thereby realizing the separation of α-olefins and alkanes with the same carbon chain length, and solving the problem of difficulty in separating straight-chain α-olefins and normal alkanes with the same carbon chain in coal-based synthetic oil.

[0049] It should be understood that in other embodiments, the raw materials for the dimerization reaction may also include only α-olefins, and the purpose of synthesizing vinylidene olefin compounds can also be achieved.

[0050] In one embodiment, drying after the reaction is completed may be performed using anhydrous sodium sulfate, and distillation may be performed under reduced pressure.

[0051] S200. In the presence of an acidic catalyst, a vinylidene olefin compound and deionized water are used as reactants and a low-carbon alcohol is used as a solvent to carry out a hydration reaction. After the reaction is completed, the mixture is extracted, washed with water, dried, and concentrated in sequence to obtain a mixture, and the mixture is separated by distillation to obtain a branched fatty tertiary alcohol product and an α-olefin dimer isomerization product.

[0052] Specifically, the reaction equation of the hydration reaction is as follows:

[0053]

[0054] Vinylidene olefin compounds can react with water under the action of an acidic catalyst to generate branched fatty tertiary alcohol products and α-olefin dimer isomerization products.

[0055] In one embodiment, the reaction temperature of the hydration reaction may be 30 to 120° C., and the reaction time may be 6 to 48 hours.

[0056] In one embodiment, the acidic catalyst may include one or more combinations of a cation exchange resin catalyst, a zeolite catalyst, and an organic acid catalyst.

[0057] Specifically, the cation exchange resin catalyst is one or more combinations of Amberlyst 36, Amberlyst 35, Amberlyst 15, Aquivion PW98, Aquivion PW87S, and NKC-9; the zeolite catalyst is one or more combinations of H-ZSM-5, H-β, and mordenite; and the organic acid catalyst is one or more combinations of trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid.

[0058] In order to ensure the reaction efficiency, the molar ratio of the vinylidene olefin compound to the deionized water may be 1:(1-20), and the mass ratio of the acid catalyst to the vinylidene olefin compound may be (5-50):100.

[0059] In one embodiment, the low-carbon alcohol may include ethylene glycol, tert-butyl alcohol, etc., all of which can achieve the effect of this embodiment.

[0060] In one embodiment, the concentration after the reaction is completed may be vacuum concentration, and the distillation of the mixture may be reduced pressure distillation.

[0061] S300, using the branched fatty tertiary alcohol product as a raw material, mixing it with a mixture of sulfur trioxide and dry air, and carrying out a sulfation reaction. After the reaction is completed, impurities are removed and recrystallization is performed to obtain branched fatty tertiary alcohol sulfate.

[0062] Specifically, the reaction equation of the sulfation reaction is as follows:

[0063]

[0064] A branched anionic surfactant, branched tertiary fatty alcohol sulfate, can be synthesized by using the branched tertiary fatty alcohol product, one of the products of step S200, as a raw material and reacting it with sulfur trioxide for sulfation.

[0065] In one embodiment, the reaction temperature of the sulfation reaction may be 20 to 80° C., and the reaction time may be 0.5 to 3.0 h.

[0066] In order to ensure the reaction efficiency, in one embodiment, the volume fraction of sulfur trioxide in the mixed gas can be 3.0-5.0%, and the molar ratio of the branched fatty tertiary alcohol product to sulfur trioxide can be 1:(1.0-1.6).

[0067] In one embodiment, in order to ensure sufficient contact between the branched fatty tertiary alcohol product and sulfur trioxide, a capillary microchannel reactor can be used for sulfation reaction. Specifically, the mixed gas of sulfur trioxide and dry air can be measured by a gas flow meter, and the branched fatty tertiary alcohol product can be measured by a constant flow pump. The mixed materials are introduced into the capillary microchannel reactor for sulfation reaction to ensure sufficient reaction; the reaction temperature can be controlled by a constant temperature water bath.

[0068] In one embodiment, the method of removing impurities after the reaction is completed may include extraction, desalination, suction filtration, distillation and drying in sequence, wherein the distillation may be vacuum distillation.

[0069] S400, using the isomerization product of α-olefin dimer as raw material, mixing it with a mixture of sulfur trioxide and dry air, and carrying out a sulfonation reaction. After the reaction is completed, impurities are removed and recrystallization is performed to obtain branched alkyl sulfonate.

[0070] Specifically, the reaction equation of the sulfonation reaction is as follows:

[0071]

[0072] One of the products of step S200, the isomerization product of α-olefin dimer, is used as a raw material and mixed with sulfur trioxide for sulfonation reaction to generate a branched anionic surfactant: branched alkyl sulfonate.

[0073] In one embodiment, the reaction temperature of the sulfonation reaction may be 20 to 80° C., and the reaction time may be 0.5 to 3.0 h.

[0074] To ensure the reaction efficiency, in one embodiment, the volume fraction of sulfur trioxide in the mixed gas may be 3.0-5.0%, and the molar ratio of the α-olefin dimer isomerization product to sulfur trioxide may be 1:(1.0-1.6).

[0075] In one embodiment, in order to ensure sufficient contact between the α-olefin dimer isomerization product and sulfur trioxide, a capillary microchannel reactor can be used for sulfation reaction. Specifically, the mixed gas of sulfur trioxide and dry air can be measured by a gas flow meter, and the α-olefin dimer isomerization product can be measured by a constant flow pump. The mixed materials are introduced into the capillary microchannel reactor for sulfonation reaction to ensure sufficient reaction; the reaction temperature can be controlled by a constant temperature water bath.

[0076] In one embodiment, the method of removing impurities after the reaction is completed may include extraction, desalination, suction filtration, distillation and drying in sequence, wherein the distillation may be vacuum distillation.

[0077] The two branched anionic surfactant products co-produced in the present application have clear composition and structure, high product purity, excellent performance, low foaming and excellent wetting properties, and typical branched surfactant characteristics. At the same time, no waste is generated during the reaction process, the raw material utilization rate is high, the reaction temperature is low, the economy is good, and it is easy to realize industrial popularization and production.

[0078] The technical solution of the present application is further explained in detail below in conjunction with specific embodiments.

[0079] Embodiment 1:

[0080] (1) Dimerization reaction

[0081] In a three-necked flask equipped with a magnetic stirrer, 15.150 g (0.180 mol) of n-hexene and 7.756 g (0.090 mol) of n-hexane were added. The molar ratio of olefin: alkane: catalyst was 2:1:0.08, and the molar ratio of methylaluminoxane: zirconocene dichloride was 10:1. In a glove box, 1.131 g (6.500 × 10 -3 mol), zirconocene dichloride 0.192 g (0.650 × 10 -3 mol). The mixture was stirred at 50°C for 10 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and vacuum distillation, 10.634 g of the dimerization product C6 dimer olefin compound was obtained. The purity of the product was 95.74% as measured by gas chromatography.

[0082] (2) Hydration reaction

[0083] 1.010 g (0.006 mol) of the C6 dimer olefin compound obtained by the dimerization reaction was added into a 25 mL reaction tube with a magnetic stirrer, followed by the addition of 2.162 g (0.120 mol) of deionized water, 4.448 g (0.060 mol) of tert-butanol and 360.505 g (50 wt.% of the C6 dimer olefin compound) of the acidic catalyst Amberlyst.

[0084] After sealing the reaction tube with a rubber stopper, the reaction was stirred at 50°C for 24 hours. After the reaction was completed, a mixture containing C6 branched fatty tertiary alcohol and C6 olefin dimer isomerization product was obtained through extraction, water washing, drying and vacuum concentration. After the obtained mixture was separated by vacuum distillation, branched fatty tertiary alcohol product and α-olefin dimer isomerization product were obtained respectively.

[0085] (3) Sulfation reaction

[0086] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent, with a SO3 volume fraction of 3.0%. The SO3 is metered into the capillary microchannel reactor by a gas flow meter, and a C6 branched fatty tertiary alcohol product is metered into the capillary microchannel reactor by a constant flow pump to mix with sulfur trioxide to ensure that the molar ratio of the C6 branched fatty tertiary alcohol product to sulfur trioxide is 1:1.0.

[0087] The reaction temperature was controlled at 25°C by a constant temperature water bath and the reaction was carried out for 0.5 h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C6 branched-chain fatty tertiary alcohol sulfate was obtained by ethanol recrystallization.

[0088] (4) Sulfonation reaction

[0089] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent, with a SO3 volume fraction of 3.0%. The SO3 is metered into the capillary microchannel reactor by a gas flow meter, and the C6 olefin dimer isomerization product is metered into the capillary microchannel reactor by a constant flow pump to mix with sulfur trioxide, ensuring that the molar ratio of the C6 olefin dimer isomerization product to sulfur trioxide is 1:1.1.

[0090] The reaction temperature was controlled at 40°C by a constant temperature water bath and the reaction was carried out for 0.8 h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C6 branched alkyl sulfonate was obtained by recrystallization with ethanol.

[0091] Embodiment 2:

[0092] (1) Dimerization reaction

[0093] In a three-necked flask equipped with a magnetic stirrer, 16.833 g (0.150 mol) of n-octene and 8.572 g (0.075 mol) of n-octane were added. The molar ratio of olefin: alkane: catalyst was 2:1:0.08, and the molar ratio of methylaluminoxane: zirconocene dichloride was 10:1. In a glove box, 0.949 g (5.450 × 10 -3 mol), zirconocene dichloride 0.158 g (0.540 × 10 -3 mol). The mixture was stirred at 40°C for 10 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 12.625 g of the dimerization product C8 dimer olefin compound was obtained. The purity of the product was 95.68% as measured by gas chromatography.

[0094] (2) Hydration reaction

[0095] 1.346 g (0.006 mol) of the C8 dimer olefin compound obtained by the dimerization reaction was added into a 25 mL reaction tube with a magnetic stirrer, followed by the addition of 1.08 g (0.060 mol) of deionized water, 4.448 g (0.060 mol) of tert-butanol and 0.067 g (50 wt.% of the C8 dimer olefin compound) of methanesulfonic acid.

[0096] After sealing the reaction tube with a rubber stopper, the reaction was stirred at 50°C for 48 hours. After the reaction was completed, a mixture containing C8 branched fatty tertiary alcohol and C8 olefin dimer isomerization product was obtained through extraction, water washing, drying and vacuum concentration. After the obtained mixture was separated by vacuum distillation, C8 branched fatty tertiary alcohol product and C8 olefin dimer isomerization product were obtained respectively.

[0097] (3) Sulfation reaction

[0098] A capillary microchannel reactor is used, and a mixture of sulfur trioxide and dry air is used as the sulfonating agent. The SO3 volume fraction is 3.5%, and it is measured by a gas flowmeter to enter the capillary microchannel reactor. The C8 branched fatty tertiary alcohol product is measured by a constant flow pump to enter the capillary microchannel reactor and mix with sulfur trioxide to ensure that the molar ratio of the C8 branched fatty tertiary alcohol product to sulfur trioxide is 1:1.1.

[0099] The reaction temperature was controlled at 30°C by a constant temperature water bath and the reaction was carried out for 0.7h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C8 branched-chain fatty tertiary alcohol sulfate was obtained by ethanol recrystallization.

[0100] (4) Sulfonation reaction

[0101] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent, with a SO3 volume fraction of 4.0%. The SO3 is metered into the capillary microchannel reactor by a gas flow meter, and the C8 olefin dimer isomerization product is metered into the capillary microchannel reactor by a constant flow pump to mix with sulfur trioxide, ensuring that the molar ratio of the C8 olefin dimer isomerization product to sulfur trioxide is 1:1.2.

[0102] The reaction temperature was controlled at 40°C by a constant temperature water bath and the reaction was carried out for 1.5 hours. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C8 branched alkyl sulfonate was obtained by recrystallization with ethanol.

[0103] Embodiment 3:

[0104] (1) Dimerization reaction

[0105] In a three-necked flask equipped with a magnetic stirrer, 15.430 g (0.110 mol) of n-decene and 7.826 g (0.055 mol) of n-decane were added. The molar ratio of olefin: alkane: catalyst was 2:1:0.02, and the molar ratio of methylaluminoxane: zirconocene dichloride was 20:1. In a glove box, 0.258 g (1.048 × 10 -3 mol), zirconocene dichloride 0.001 g (0.005 × 10 -3 mol). The mixture was stirred at 40°C for 10 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and vacuum distillation, 11.726 g of the dimerization product C10 dimer olefin compound was obtained. The purity of the product was 95.82% as measured by gas chromatography.

[0106] (2) Hydration reaction

[0107] 0.701 g (0.025 mol) of the C10 dimer olefin compound obtained by the dimerization reaction was added into a 25 mL reaction tube with a magnetic stirrer, followed by the addition of 0.452 g (0.025 mol) of deionized water, 1.853 g (0.025 mol) of tert-butanol and 0.245 g (40 wt.% of the C10 dimer olefin compound) of H-ZSM-5.

[0108] After sealing the reaction tube with a rubber stopper, the reaction was stirred at 90°C for 24 hours. After the reaction was completed, a mixture containing C10 branched fatty tertiary alcohol and C10 olefin dimer isomerization product was obtained through extraction, water washing, drying and vacuum concentration. After the obtained mixture was separated by vacuum distillation, branched fatty tertiary alcohol product and α-olefin dimer isomerization product were obtained respectively.

[0109] (3) Sulfation reaction

[0110] A capillary microchannel reactor is used, and a mixture of sulfur trioxide and dry air is used as a sulfonating agent. The SO3 volume fraction is 3.8%, and is measured by a gas flowmeter to enter the capillary microchannel reactor. The C10 branched fatty tertiary alcohol product is measured by a constant flow pump to enter the capillary microchannel reactor and mix with sulfur trioxide to ensure that the molar ratio of the C10 branched fatty tertiary alcohol product to sulfur trioxide is 1:1.6.

[0111] The reaction temperature was controlled at 80°C by a constant temperature water bath and the reaction was carried out for 0.9h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C10 branched-chain fatty tertiary alcohol sulfate was obtained by ethanol recrystallization.

[0112] (4) Sulfonation reaction

[0113] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent, with a SO3 volume fraction of 5.0%. The SO3 is metered into the capillary microchannel reactor by a gas flow meter, and a C10 olefin dimer isomerization product is metered into the capillary microchannel reactor by a constant flow pump to mix with sulfur trioxide, ensuring that the molar ratio of the C10 olefin dimer isomerization product to sulfur trioxide is 1:1.3.

[0114] The reaction temperature was controlled at 20°C by a constant temperature water bath and the reaction was carried out for 2.0 h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C10 branched alkyl sulfonate was obtained by recrystallization with ethanol.

[0115] Embodiment 4:

[0116] (1) Dimerization reaction

[0117] In a three-necked flask equipped with a magnetic stirrer, 19.637 g (0.100 mol) of n-tetradecene and 7.826 g (0.050 mol) of n-tetradecane were added. The molar ratio of olefin: alkane: catalyst was 2:1:0.04, and the molar ratio of methylaluminoxane: zirconocene dichloride was 5:1. In a glove box, 0.290 g (1.667 × 10 -3 mol), zirconocene dichloride 0.095 g (0.333 × 10 -3 mol). The mixture was stirred at 60°C for 5 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and vacuum distillation, 14.335 g of the dimerized product C14 dimerized olefin compound was obtained. The purity of the product was 95.71% as measured by gas chromatography.

[0118] (2) Hydration reaction

[0119] 0.785 g (0.002 mol) of the C14 dimer olefin compound obtained by the dimerization reaction was added into a 25 mL reaction tube with a magnetic stirrer, followed by the addition of 0.540 g (0.030 mol) of deionized water, 1.482 g (0.020 mol) of tert-butanol and 0.236 g (30 wt.% of the C14 dimer olefin compound) of Amberlyst 15.

[0120] After sealing the reaction tube with a rubber stopper, the reaction was stirred at 60°C for 48 hours. After the reaction was completed, a mixture containing C14 branched fatty tertiary alcohol and C14 olefin dimer isomerization product was obtained through extraction, water washing, drying and vacuum concentration. After the obtained mixture was separated by vacuum distillation, C14 branched fatty tertiary alcohol product and C14 olefin dimer isomerization product were obtained respectively.

[0121] (3) Sulfation reaction

[0122] A capillary microchannel reactor is used, and a mixture of sulfur trioxide and dry air is used as the sulfonating agent. The SO3 volume fraction is 4.2%, and is measured by a gas flowmeter to enter the capillary microchannel reactor. The C14 branched fatty tertiary alcohol product is measured by a constant flow pump to enter the capillary microchannel reactor and mix with sulfur trioxide to ensure that the molar ratio of the C14 branched fatty tertiary alcohol product to sulfur trioxide is 1:1.5.

[0123] The reaction temperature was controlled at 70°C by a constant temperature water bath and the reaction was carried out for 2.0 h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the C14 product branched fatty tertiary alcohol sulfate was obtained by ethanol recrystallization.

[0124] (4) Sulfonation reaction

[0125] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent. The SO3 volume fraction is 3.5%, and is measured by a gas flowmeter to enter the capillary microchannel reactor. The C14 olefin dimer isomerization product is measured by a constant flow pump to enter the capillary microchannel reactor and mix with sulfur trioxide to ensure that the molar ratio of the C14 olefin dimer isomerization product to sulfur trioxide is 1:1.4.

[0126] The reaction temperature was controlled at 20°C by a constant temperature water bath and the reaction was carried out for 0.8h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C14 branched alkyl sulfonate was obtained by recrystallization with ethanol.

[0127] Embodiment 5:

[0128] (1) Dimerization reaction

[0129] In a three-necked flask equipped with a magnetic stirrer, 22.443 g (0.100 mol) of n-hexadecene and 11.322 g (0.050 mol) of n-hexadecane were added, and the molar ratio of olefin: alkane: catalyst was 2:1:0.05, wherein the molar ratio of methylaluminoxane: zirconocene dichloride was 1:1. In a glove box, 0.218 g (1.250 × 10 -3 mol), zirconocene dichloride 0.355 g (1.250 × 10 -3 mol). The mixture was stirred at 70°C for 15 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and distillation under reduced pressure, 17.057 g of the dimerization product C16 dimer olefin compound was obtained. The purity of the product was 95.88% as measured by gas chromatography.

[0130] (2) Hydration reaction

[0131] Take 0.673 g (1.50 × 10 -3 mol) was added into a 25 mL reaction tube with a magnetic stirrer, followed by the addition of deionized water 0.540 g (0.030 mol), tert-butyl alcohol 1.112 g (0.015 mol) and trifluoromethanesulfonic acid 0.034 g (5 wt.% C16 dimer olefin compound).

[0132] After sealing the reaction tube with a rubber stopper, the reaction was stirred at 100°C for 24 hours. After the reaction was completed, a mixture containing C16 branched fatty tertiary alcohol and C16 olefin dimer isomerization product was obtained through extraction, water washing, drying and vacuum concentration. After the obtained mixture was separated by vacuum distillation, C16 branched fatty tertiary alcohol product and C16 olefin dimer isomerization product were obtained respectively.

[0133] (3) Sulfation reaction

[0134] A capillary microchannel reactor is used, and a mixture of sulfur trioxide and dry air is used as the sulfonating agent. The SO3 volume fraction is 4.3%, and is measured by a gas flowmeter to enter the capillary microchannel reactor. The C16 branched fatty tertiary alcohol product is measured by a constant flow pump to enter the capillary microchannel reactor and mix with sulfur trioxide to ensure that the molar ratio of the C16 branched fatty tertiary alcohol product to sulfur trioxide is 1:1.4.

[0135] The reaction temperature was controlled at 70°C by a constant temperature water bath and the reaction was carried out for 2.4 hours. After the reaction, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C16 branched-chain fatty tertiary alcohol sulfate was obtained by ethanol recrystallization.

[0136] (4) Sulfonation reaction

[0137] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent. The SO3 volume fraction is 4.5%, and is measured by a gas flowmeter to enter the capillary microchannel reactor. The C16 olefin dimer isomerization product is measured by a constant flow pump to enter the capillary microchannel reactor and mix with sulfur trioxide to ensure that the molar ratio of the C16 olefin dimer isomerization product to sulfur trioxide is 1:1.5.

[0138] The reaction temperature was controlled at 60°C by a constant temperature water bath and the reaction was carried out for 0.8h. After the reaction, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C16 branched alkyl sulfonate was obtained by recrystallization with ethanol.

[0139] Embodiment 6:

[0140] (1) Dimerization reaction

[0141] In a three-necked flask equipped with a magnetic stirrer, 23.706 g (0.130 mol) of n-tridecene and 13.827 g (0.075 mol) of n-tridecane were added. The molar ratio of olefin: alkane: catalyst was 2:1:0.07, and the molar ratio of methylaluminoxane: zirconocene dichloride was 14:1. In a glove box, 0.853 g (4.900 × 10 -3 mol), zirconocene dichloride 0.099 g (0.350 × 10 -3 mol). The mixture was stirred at 55°C for 7 h. After the reaction was completed, water was added to quench the reaction. The mixture was washed with water, extracted with petroleum ether, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain 17.068 g of the dimerized product C13 dimerized olefin compound. The purity of the product was 95.64% as measured by gas chromatography.

[0142] (2) Hydration reaction

[0143] 0.729 g (0.002 mol) of the C13 dimer olefin compound obtained by the dimerization reaction was added into a 25 mL reaction tube with a magnetic stirrer, followed by the addition of 0.360 g (0.020 mol) of deionized water, 1.482 g (0.020 mol) of tert-butanol and 0.073 g (10 wt.% of the C13 dimer olefin compound) of p-toluenesulfonic acid.

[0144] After sealing the reaction tube with a rubber stopper, the reaction was stirred at 120°C for 48 hours. After the reaction was completed, a mixture containing C13 branched fatty tertiary alcohol and C13 olefin dimer isomerization product was obtained through extraction, water washing, drying and vacuum concentration. After the obtained mixture was separated by vacuum distillation, C13 branched fatty tertiary alcohol product and C13 olefin dimer isomerization product were obtained respectively.

[0145] (3) Sulfation reaction

[0146] A capillary microchannel reactor is used, and a mixture of sulfur trioxide and dry air is used as the sulfonating agent. The SO3 volume fraction is 3.3%. It is measured by a gas flowmeter to enter the capillary microchannel reactor, and the C13 branched fatty tertiary alcohol product is measured by a constant flow pump to enter the capillary microchannel reactor and mix with sulfur trioxide to ensure that the molar ratio of the C13 branched fatty tertiary alcohol product to sulfur trioxide is 1:1.2.

[0147] The reaction temperature was controlled at 30°C by a constant temperature water bath and the reaction was carried out for 2.6 hours. After the reaction, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C13 branched-chain fatty tertiary alcohol sulfate was obtained by ethanol recrystallization.

[0148] (4) Sulfonation reaction

[0149] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent, with a SO3 volume fraction of 3.0%. The SO3 is metered into the capillary microchannel reactor by a gas flow meter, and the C13 olefin dimer isomerization product is metered into the capillary microchannel reactor by a constant flow pump to mix with sulfur trioxide, ensuring that the molar ratio of the C13 olefin dimer isomerization product to sulfur trioxide is 1:1.6.

[0150] The reaction temperature was controlled at 60°C by a constant temperature water bath and the reaction was carried out for 2.0 h. After the reaction was completed, impurities were removed by extraction, desalination, filtration, vacuum distillation, drying and dehydration, and the product C13 branched alkyl sulfonate was obtained by recrystallization with ethanol.

[0151] Embodiment 7:

[0152] (1) Dimerization reaction

[0153] In a three-necked flask equipped with a magnetic stirrer, 25.248 g (0.150 mol) of n-dodecene and 12.775 g (0.075 mol) of n-dodecane were added. The molar ratio of olefin: alkane: catalyst was 2:1:0.05, and the molar ratio of methylaluminoxane: zirconocene dichloride was 9:1. In a glove box, 0.587 g (3.375 × 10 -3 mol), zirconocene dichloride 0.107 g (0.375 × 10 -3 mol). The mixture was stirred at 35°C for 12 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and vacuum distillation, 18.431 g of the dimerized product C12 dimerized olefin compound was obtained. The purity of the product was 95.79% as measured by gas chromatography.

[0154] (2) Hydration reaction

[0155] 0.673 g (0.002 mol) of the C12 dimer olefin compound obtained by the dimerization reaction was added into a 25 mL reaction tube with a magnetic stirrer, followed by the addition of 0.180 g (0.010 mol) of deionized water, 1.482 g (0.020 mol) of tert-butanol and 0.202 g (30 wt.% of the C12 dimer olefin compound) of NKC-9.

[0156] After sealing the reaction tube with a rubber stopper, the reaction was stirred at 80°C for 24 hours. After the reaction was completed, a mixture containing C12 branched fatty tertiary alcohol and C12 olefin dimer isomerization product was obtained through extraction, water washing, drying and vacuum concentration. After the obtained mixture was separated by vacuum distillation, C12 branched fatty tertiary alcohol product and C12 olefin dimer isomerization product were obtained respectively.

[0157] (3) Sulfation reaction

[0158] A capillary microchannel reactor is used, and a mixture of sulfur trioxide and dry air is used as a sulfonating agent, with a SO3 volume fraction of 5.0%. The SO3 is metered into the capillary microchannel reactor by a gas flow meter, and the C12 branched fatty tertiary alcohol product is metered into the capillary microchannel reactor by a constant flow pump to mix with sulfur trioxide to ensure that the molar ratio of the C12 branched fatty tertiary alcohol product to sulfur trioxide is 1:1.5.

[0159] The reaction temperature was controlled at 45°C by a constant temperature water bath and the reaction was carried out for 1.8 hours. After the reaction, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C12 branched-chain fatty tertiary alcohol sulfate was obtained by ethanol recrystallization.

[0160] (4) Sulfonation reaction

[0161] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent, with a SO3 volume fraction of 4.0%. The SO3 is metered into the capillary microchannel reactor by a gas flow meter, and the C12 olefin dimer isomerization product is metered into the capillary microchannel reactor by a constant flow pump to mix with sulfur trioxide, ensuring that the molar ratio of the C12 olefin dimer isomerization product to sulfur trioxide is 1:1.0.

[0162] The reaction temperature was controlled at 80°C by a constant temperature water bath and the reaction was carried out for 1.0 h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C12 branched alkyl sulfonate was obtained by recrystallization with ethanol.

[0163] Embodiment 8:

[0164] (1) Dimerization reaction

[0165] In a three-necked flask equipped with a magnetic stirrer, 22.741 g (0.180 mol) of n-nonene and 11.543 g (0.090 mol) of n-nonane were added. The molar ratio of olefin: alkane: catalyst was 2:1:0.04, and the molar ratio of methylaluminoxane: zirconocene dichloride was 7:1. In a glove box, 0.548 g (3.150 × 10 -3 mol), zirconocene dichloride 0.128 g (0.450 × 10 -3 mol). The mixture was stirred at 65°C for 8 h. After the reaction was completed, water was added to quench the reaction. After washing with water, extraction with petroleum ether, drying with anhydrous sodium sulfate, and vacuum distillation, 16.828 g of the dimerization product C9 dimer olefin compound was obtained. The purity of the product was 95.92% as measured by gas chromatography.

[0166] (2) Hydration reaction

[0167] 0.632 g (2.500 × 10 -3 mol) was added into a 25 mL reaction tube with a magnetic stirrer, followed by the addition of 0.450 g (0.025 mol) of deionized water, 1.853 g (0.025 mol) of tert-butyl alcohol and 0.158 g (25 wt.% C10 dimer olefin compound) of dodecylbenzenesulfonic acid.

[0168] After sealing the reaction tube with a rubber stopper, the reaction was stirred at 30°C for 48 hours. After the reaction was completed, a mixture containing C9 branched fatty tertiary alcohol and C9 olefin dimer isomerization product was obtained through extraction, water washing, drying and vacuum concentration. After the obtained mixture was separated by vacuum distillation, C9 branched fatty tertiary alcohol product and C9 olefin dimer isomerization product were obtained respectively.

[0169] (3) Sulfation reaction

[0170] A capillary microchannel reactor is used, and a mixture of sulfur trioxide and dry air is used as the sulfonating agent. The SO3 volume fraction is 4.9%, and is measured by a gas flowmeter to enter the capillary microchannel reactor. The C9 branched fatty tertiary alcohol product is measured by a constant flow pump to enter the capillary microchannel reactor and mix with sulfur trioxide to ensure that the molar ratio of the C9 branched fatty tertiary alcohol product to sulfur trioxide is 1:1.4.

[0171] The reaction temperature was controlled at 65°C by a constant temperature water bath and the reaction was carried out for 3.0 h. After the reaction was completed, impurities were removed by neutralization extraction, desalination, filtration, vacuum distillation, drying and dehydration, and the product C9 branched-chain fatty tertiary alcohol sulfate was obtained by ethanol recrystallization.

[0172] (4) Sulfonation reaction

[0173] A capillary microchannel reactor is used, and a mixed gas of sulfur trioxide and dry air is used as a sulfonating agent, with a SO3 volume fraction of 5.0%. The SO3 is metered into the capillary microchannel reactor by a gas flow meter, and the C9 olefin dimer isomerization product is metered into the capillary microchannel reactor by a constant flow pump to mix with sulfur trioxide, ensuring that the molar ratio of the C9 olefin dimer isomerization product to sulfur trioxide is 1:1.3.

[0174] The reaction temperature was controlled at 80°C by a constant temperature water bath and the reaction was carried out for 2.0 h. After the reaction was completed, impurities were removed by neutralization, extraction, desalination, vacuum distillation, drying and dehydration, and the product C9 branched alkyl sulfonate was obtained by recrystallization with ethanol.

[0175] Effect example 1:

[0176] The C6 branched fatty tertiary alcohol product and the C6 olefin dimer isomerization product obtained by the hydration reaction in Example 1 were analyzed by infrared spectroscopy to obtain Figure 2 and Figure 3 .

[0177] See also Figure 2 , Figure 2 This is the infrared spectrum of the C6 branched fatty tertiary alcohol product prepared in Example 1 of the present application. As shown in the figure, the wave numbers 2934 and 2863 cm -1 The stretching vibration peaks of -CH3 and -CH2- are at 1462cm -1 It is the stretching vibration peak of -CH, with a wave number of 3075cm -1 (CH stretching vibration peak of olefin) and 886cm -1 The characteristic peak corresponding to (=CH out-of-plane bending vibration peak) is Figure 1 It does not appear in the wave number 3369cm -1 The characteristic stretching vibration peak of -OH appeared at . It can be seen that the vinylidene olefin compound undergoes hydration reaction to synthesize the target product C6 branched fatty tertiary alcohol.

[0178] See also Figure 3 , Figure 3 This is the infrared spectrum of the C6 olefin dimer isomerization product prepared in Example 1 of the present application. As shown in the figure, the wave numbers 2920 and 2856 cm -1 The stretching vibration peaks of -CH3 and -CH2- are at 1456cm -1 It is the stretching vibration peak of -CH, with a wave number of 3073cm -1 The characteristic peak corresponding to (CH stretching vibration peak of olefin) is Figure 2 It does not appear in the wave number 1667cm -1 (-C=C- of olefin) and 886 cm -1 A stretching vibration peak appeared at (=CH out-of-plane bending vibration peak). It can be seen that the vinylidene olefin compound underwent a hydration reaction to synthesize the target product C6 olefin dimer isomerization product.

[0179] The C6 branched fatty tertiary alcohol sulfate and C6 branched alkyl sulfonate surfactants prepared in Example 1 were analyzed by infrared spectroscopy to obtain Figure 4 and Figure 5 .

[0180] See also Figure 4 , Figure 4 This is the infrared spectrum of the C6 branched fatty tertiary alcohol sulfate prepared in Example 1 of the present application. As shown in the figure, the wave numbers 2925 and 2856 cm -1 The stretching vibration peaks of -CH3 and -CH2- are at 1462cm -1 It is the stretching vibration peak of -CH, with a wave number of 3075cm -1 (CH stretching vibration peak of olefin) and 886cm-1 The characteristic peak corresponding to (=CH out-of-plane bending vibration peak) is Figure 3 It does not appear in the wave number 1172 and 1045 cm -1 The characteristic stretching vibration peak of sulfate appears at . It can be seen that the product synthesized in Example 1 is the target product C6 branched chain fatty tertiary alcohol sulfate.

[0181] See also Figure 5 , Figure 5 This is the infrared spectrum of the C6 branched alkyl sulfonate prepared in Example 1 of the present application. As shown in the figure, the wave numbers 2935 and 2866 cm -1 The stretching vibration peaks of -CH3 and -CH2- are at 1457cm -1 It is the stretching vibration peak of -CH, with a wave number of 3075cm -1 (CH stretching vibration peak of olefin) and 886cm -1 The characteristic peak corresponding to (=CH out-of-plane bending vibration peak) is Figure 4 It does not appear in the wavenumbers 642, 1175 and 1045 cm -1 The characteristic stretching vibration peak of sulfonate appears at 40°C. Therefore, it can be known that the product synthesized in Example 1 is the target product C6 branched alkyl sulfonate.

[0182] Effect Example 2:

[0183] The surface tension of the surfactants C6 branched fatty tertiary alcohol sulfate and C6 branched alkyl sulfonate prepared in Example 1 was tested respectively.

[0184] The specific test method of the surface tension test is: take 1.0g of surfactant sample to prepare a surfactant aqueous solution with a concentration of 1g / L, use the German KRUSS K100C surface tension tester, based on the Wilhelmy Plate method, by using a platinum plate to contact the surface of the surfactant aqueous solution to test the surface tension, and use the circulating water bath of Ulabo Technology Co., Ltd. to control the test temperature to 25℃±0.5℃.

[0185] When the instrument starts testing, it first measures the surface tension of pure water, and then continuously injects an equal volume of surfactant solution into the test container while keeping the volume of the measured solution constant, and accurately extracts the corresponding volume of solution. In this way, the concentration of the surfactant 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 surface tension and concentration can be obtained.

[0186] See also Figure 6 , Figure 6 This is a surface tension diagram of the C6 branched fatty tertiary alcohol sulfate prepared in Example 1 of the present application at different concentrations.

[0187] like Figure 6 As shown, the critical micelle concentration (CMC) of the C6 branched fatty tertiary alcohol sulfate prepared in Example 1 is 3.02 mmol / L, and the corresponding surface tension (γCMC) at this concentration is 27.4 mN / m.

[0188] See also Figure 7 , Figure 7 This is a surface tension diagram of the C6 branched alkyl sulfonate prepared in Example 1 of the present application at different concentrations.

[0189] like Figure 7 As shown, the critical micelle concentration (CMC) of the C6 branched alkyl sulfonate prepared in Example 1 is 3.71 mmol / L, and the corresponding surface tension (γCMC) at this concentration is 27.61 mN / m.

[0190] It can be seen from the above experiments that the two branched surfactants prepared in Example 1 have typical surfactant properties and can effectively reduce the surface tension of water.

[0191] Effect example 3:

[0192] The foaming performance of the surfactants C6 branched fatty tertiary alcohol sulfate and C6 branched alkyl sulfonate prepared in Example 1 was tested respectively.

[0193] The specific test method for the foaming performance test is as follows: 1.0 g of surfactant sample is taken to prepare a surfactant aqueous solution with a concentration of 1 g / L, and the foaming performance of the surfactant aqueous solution at 25±0.1°C is measured using a DFA100 fully automatic foam analyzer; 50 mL of the surfactant aqueous solution is placed in a cylindrical glass column with a length of 250 mm and an inner diameter of 40 mm, and foaming is performed by mechanical stirring. The rotor speed is 6000 r / min, the foaming time is 30 s, and the total operating time is 1200 s. The surfactant foam is dynamically analyzed, and the foam stability is calculated according to foam stability = (foam volume measured after 5 min / foam volume measured after 30 s) × 100%, and the data in the following table are obtained.

[0194]

[0195] As can be seen from the data in the above table, the C6 branched fatty tertiary alcohol sulfate and C6 branched alkyl sulfonate synthesized in Example 1 both have excellent foaming properties, produce more foam, and have good foam stability, reaching more than 72%.

[0196] The above description of the present disclosure is provided to enable any person of ordinary skill in the art to implement or use the present disclosure. Various modifications to the present disclosure will be apparent to those of ordinary skill in the art, and the general principles corresponding to the present disclosure may be applied to other variations without departing from the scope of protection of the present disclosure. Therefore, the present disclosure is not limited to the examples and designs described herein, but is consistent with the widest range of principles and novel features disclosed herein.

Claims

1. A method for co-producing branched-chain fatty tertiary alcohol sulfate and branched-chain alkyl sulfonate, characterized in that: include: A mixture of α-olefins and alkanes with the same carbon chain length is used as a raw material, and a dimerization reaction is carried out under the action of a catalyst. After the reaction is completed, water is added to quench the reaction, and the alkanes are separated by washing, extraction, drying and distillation in sequence to obtain vinylidene olefin compounds, wherein the α-olefin is C4 ~ C 16 Any of the alkenes; In the presence of an acidic catalyst, the vinylidene olefin compound and deionized water are used as reactants, and a low-carbon alcohol is used as a solvent to carry out a hydration reaction. After the reaction is completed, extraction, water washing, drying, and concentration are performed in sequence to obtain a mixture, and the mixture is distilled and separated to obtain a branched fatty tertiary alcohol product and an α-olefin dimer isomerization product, wherein the low-carbon alcohol is selected from one or a combination of ethylene glycol and tert-butyl alcohol, the molar ratio of the vinylidene olefin compound to the deionized water is 1: (1-20), the acidic catalyst is one or more combinations of a cation exchange resin catalyst, a zeolite catalyst, and an organic acid catalyst, and the cation exchange resin catalyst is Amberlyst 36, Amberlyst 35, Amberlyst15, Aquivion PW98, Aquivion PW87S, NKC-9, the zeolite catalyst is one or more combinations of H-ZSM-5, H-β, mordenite, the organic acid catalyst is one or more combinations of trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, the mass ratio of the acid catalyst to the vinylidene olefin compound is (5-50):100, the reaction temperature of the hydration reaction is 30-120°C, and the reaction time is 6-48h; The branched fatty tertiary alcohol product is used as a raw material, mixed with a mixture of sulfur trioxide and dry air, and subjected to a sulfation reaction. After the reaction is completed, impurities are removed and recrystallization is performed to obtain a branched fatty tertiary alcohol sulfate; The α-olefin dimer isomerization product is used as a raw material, mixed with a mixed gas of sulfur trioxide and dry air, and subjected to a sulfonation reaction. After the reaction is completed, impurities are removed and recrystallization is performed to obtain a branched alkyl sulfonate; Wherein, the branched fatty tertiary alcohol sulfate has the following chemical formula: Wherein, R is a saturated hydrocarbon group of C1 to C13; The branched alkyl sulfonate has the general chemical formula shown below: Wherein, R is a saturated hydrocarbon group of C1 to C13.

2. The co-production method according to claim 1, characterized in that: In the step of using a mixture of α-olefins and alkanes with the same carbon chain length as raw materials and carrying out a dimerization reaction under the action of a catalyst, the catalyst comprises zirconocene dichloride and methylaluminoxane, the molar ratio of the zirconocene dichloride to methylaluminoxane is 1:(1-20), the molar ratio of the α-olefin to the catalyst is 1:(0.020-0.080), the reaction temperature of the dimerization reaction is 30-80°C, and the reaction time is 5-20h.

3. The co-production method according to claim 1, characterized in that: In the step of using the branched fatty tertiary alcohol product as a raw material and mixing it with a mixed gas of sulfur trioxide and dry air to carry out a sulfation reaction, the volume fraction of sulfur trioxide in the mixed gas is 3.0-5.0%, the molar ratio of the branched fatty tertiary alcohol product to the sulfur trioxide is 1:(1.0-1.6), the reaction temperature of the sulfation reaction is 20-80°C, and the reaction time is 0.5-3.0h.

4. The co-production method according to claim 1, characterized in that: The α-olefin dimer isomerization product is used as a raw material and mixed with a mixed gas of sulfur trioxide and dry air to carry out a sulfonation reaction. The molar ratio of the α-olefin dimer isomerization product to the sulfur trioxide is 1:(1.0-1.6), the volume fraction of sulfur trioxide in the mixed gas is 3.0-5.0%, the reaction temperature of the sulfonation reaction is 20-80°C, and the reaction time is 0.5-3.0h.

5. The co-production method according to claim 1, characterized in that: The step of removing impurities after the reaction is completed specifically comprises extracting, desalting, filtering, distilling and drying the product after the reaction is completed.

6. The co-production method according to any one of claims 1 to 5, characterized in that: The mixture of alpha-olefins and alkanes with the same carbon chain length is separated from coal-based synthetic oil.

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