CN111068578B

CN111068578B - Surfactant, preparation method and application thereof

Info

Publication number: CN111068578B
Application number: CN201911333636.7A
Authority: CN
Inventors: 殷玲; 秦承群; 鞠昌迅; 石正阳; 刘洋; 吕树卫; 房士强; 黎源
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2019-12-23
Filing date: 2019-12-23
Publication date: 2021-07-23
Anticipated expiration: 2039-12-23
Also published as: CN111068578A

Abstract

The invention discloses a surfactant, a preparation method and application thereof. The surfactant comprises a compound with the following structural general formula:

Description

Surfactant, preparation method and application thereof

Technical Field

The invention relates to the field of surfactants, in particular to a novel surfactant and a preparation method thereof.

Background

Surfactants belong to an amphiphilic structure and simultaneously have a hydrophilic group and a hydrophobic group, and due to the special structure and action of the surfactants, the surfactants play a very important role in the fields of daily life and industrial production of modern society. The functional requirements of people on surfactants are more and more complicated, most of China is hard water and contains polyvalent metal cations, and most of the surfactants are sensitive to the polyvalent metal cations, so that the use of the surfactants in a high-hardness water environment is limited. Manufacturers usually meet the requirements by compounding, however, integrating two or more functional groups into the same surfactant molecular structure is a better choice to reduce the complexity and cost of the formulation and improve the performance.

The Chinese invention patent CN107236593A discloses an environment-friendly vegetable oil-based emulsified cutting fluid for machine tool processing, wherein a hard water resisting agent and an auxiliary surfactant, namely a nonylphenol ethylene oxide condensate NP-4, are added in a formula to improve the hard water resisting performance and the emulsifying performance of the cutting fluid, but the hard water resisting agent is easy to generate an unstable condition in the formula, and the NP-4 belongs to a national prohibited chemical and can cause environmental pollution.

Chinese invention patent CN101514314 discloses a transparent neutral laundry detergent containing high-concentration chelating agent and a preparation method thereof, wherein high-concentration chelating agent polyacrylate and sodium citrate are added into a formula to complex calcium ions and magnesium ions in hard water. Whether the complex is cleaned up or not in the washing process of the detergent is not easy to judge, and if the complex is not cleaned up, white crystals appear on the surface of the clothes after the clothes are dried, so that the attractiveness is influenced, and the service life of the clothes is influenced.

The structure-activity relationship research of aromatic linking group and gemini surfactant discloses a gemini surfactant with semi-rigid linking group

The foaming ability and hard water resistance are not high due to intramolecular hydrogen bonding between hydroxyl groups and adjacent sulfonic acid groups in the molecular structure. Simultaneously discloses a stretching polyoxyethylene ether surfactant-dinonyl benzene polyoxypropylene ether methane

The polyoxypropylene is introduced to enhance hydrophobicity and maintain good hydrophilicity, but the structure lacks a sulfonate structure, so that the oil displacement effect of the surfactant is general.

Disclosure of Invention

The invention provides a surfactant and a preparation method thereof, the surfactant has the structure and the advantages of a gemini surfactant and a nonionic surfactant, and simultaneously, because oxygen atoms with lone pair electrons are introduced into a linking group, the hard water resistance of the surfactant is more excellent.

In order to achieve the purpose, the invention adopts the technical scheme that:

a surfactant comprising a compound of the general structural formula:

wherein n is an integer of 1-15, x and p are independent integers of 0-100, y and q are independent integers of 0-100, x and y are not 0 at the same time, p and q are not 0 at the same time, and R is C1-C6 alkylene;

preferably, n is an integer of 3-10, x and p are independent integers of 30-90, y and q are independent integers of 0-30, and R is methylene, ethylene or propylene; or n is an integer of 3 to 10, x + p is 30 to 180, preferably 70 to 120, y + q is 0 to 60, preferably 0 to 30, and R is methylene, ethylene, or propylene.

The novel surfactants of the invention have a weight average molecular weight in the range from 780g/mol to 12000g/mol, preferably from 3000g/mol to 8000 g/mol.

A method of making the surfactant comprising the steps of:

1) adding alkyl diacyl dichloride into a mixture of aluminum trichloride, dichloromethane and p-alkyl anisole under ice bath, reacting for 5-7 h, and separating by a chromatographic column to obtain a product;

2) dropwise adding iodotrimethylsilane into the product obtained in the step 1) under the condition of stirring at room temperature, and reacting for 5-7 h; after the reaction is finished, quenching excessive iodotrimethylsilane by methanol, distilling under reduced pressure to remove volatile components, washing residues by sodium bisulfite water solution and sodium bicarbonate water solution respectively for three times, and then drying;

3) taking the product obtained in the step 2) as an initiator, controlling the reaction temperature to be 100-180 ℃, preferably 120-140 ℃ and the pressure to be 0.1-0.6 MPa (by gauge pressure), preferably 0.1-0.3MPa, in the presence of a catalyst, adding an epoxide into a reaction container, and reacting until the pressure is not reduced any more, wherein the obtained product has the following structural formula:

4) slowly dripping halosulfonic acid into the product obtained in the step 3) under the condition of ice-water bath, violently stirring, heating to 30-60 ℃ for 3 hours, neutralizing to obtain a product, and purifying to obtain the surfactant.

In step 1) of the present invention, the ratio of p-alkyl anisole: aluminum trichloride: the molar ratio of alkyl diacyl dichlorides is 2 (2.0-3.0): 1.3-2.0), preferably 2 (2.0-2.2): 1.3-1.8, wherein the aluminum trichloride preferably uses dichloromethane as solvent, and the concentration is generally 15-35 wt%.

Preferably, the eluent used for the chromatographic column separation in the step 1) is dichloromethane: the volume ratio of petroleum ether is 3: 1.

In the step 2), the molar ratio of the product obtained in the step 1) to the iodotrimethylsilane is 1: 1.0-2.0, preferably 1: 1.1-1.4.

In the step 2), the molar ratio of the methanol to the product obtained in the step 1) is 4-5: 1, the concentration of the sodium bisulfite aqueous solution is 10-15 wt%, and the concentration of the sodium bicarbonate aqueous solution is 5-10 wt%.

In the step 3), the mass ratio of the initiator to the epoxide is 1: 2-30, preferably 1: 5-20, and more preferably 1: 7-15.

In step 3), the catalyst is one or more of NaOH, KOH, sodium methoxide, potassium methoxide, phosphazene, lewis acid, magnesium hydroxide, barium hydroxide, and calcium hydroxide, preferably potassium hydroxide and/or sodium hydroxide.

In step 3) of the present invention, the amount of the catalyst is 0.01 to 0.5%, preferably 0.05 to 0.2% of the total mass of the initiator and the epoxide.

The epoxide of the present invention is ethylene oxide and/or propylene oxide.

The reaction vessel of step 3) according to the present invention is preferably any one of a jet reactor, a tubular reactor, a stirred tank, and a loop reactor.

In the step 4), the molar ratio of the product obtained in the step 3) to the halosulfonic acid is 1: 4.0-6.0, and preferably 1: 4.2-4.7.

The halosulfonic acid can be one or more of fluorosulfonic acid, chlorosulfonic acid and bromosulfonic acid.

As a preferable scheme, the neutralization in the step 4) of the invention is preferably performed by using sodium hydroxide; the purification comprises the following steps: the non-sulfonated substance is removed by extraction with a low polarity solvent such as petroleum ether, and the organic phase is dried by a rotary evaporator and then recrystallized for a plurality of times (the solvent is ethyl acetate) to obtain a purified product.

The novel surfactant provided by the invention can be applied to the fields of spinning, washing, medicine and petroleum.

The invention also provides a laundry detergent, which is prepared from the following raw materials in parts by weight:

in the laundry detergent, the alkali of the alkali liquor is selected from sodium bicarbonate, sodium carbonate or sodium hydroxide, and sodium bicarbonate is preferred.

Further preferably, the concentration of the alkali liquor is 20-40 wt%, preferably 30 wt%.

In the laundry detergent, the thickening agent is sodium chloride.

The essence provided by the invention is lemon essence.

The pigment is indigo pigment.

Compared with the prior art, the novel surfactant and the preparation method thereof have the outstanding characteristics and excellent effects that: (1) the production or domestic water often containsThere are polyvalent metal cations to which most surfactants are sensitive, which limits their use in high hard water environments. The linking group of the surfactant contains lone pair electrons which are easy to react with Mg²⁺、Ca²⁺And the two oxygen atoms and the two benzene rings form a conjugated system, so that the hard water resistance of the surfactant is very excellent.

(2) The surfactant disclosed by the invention has a polyoxyethylene chain segment nonionic structural unit and a sulfonate anion structural unit on a molecular skeleton, and a conjugated system is formed by introducing a linking group with two oxygen atoms and two benzene rings, so that the surfactant has the advantages of excellent foaming capacity and oil displacement and detergency, and has a remarkable effect in the field of household and personal washing.

(3) The reaction condition is mild; the reaction raw materials are easy to obtain; the product is easy to separate and purify; the reaction process is easy to operate.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of the product of step 1) of example 1;

FIG. 2 is a nuclear magnetic hydrogen spectrum of the product of step 2) of example 1;

FIG. 3 is nuclear magnetic hydrogen spectrum of the product of step 4) of example 1;

FIG. 4 is nuclear magnetic hydrogen spectrum of the product of step 1) of example 2;

FIG. 5 is nuclear magnetic hydrogen spectrum of the product of step 2) of example 2;

FIG. 6 is nuclear magnetic hydrogen spectrum of the product of step 4) of example 2;

FIG. 7 is a nuclear magnetic hydrogen spectrum of the product of step 1) of example 3;

FIG. 8 is a nuclear magnetic hydrogen spectrum of the product of step 2) of example 3;

FIG. 9 is nuclear magnetic hydrogen spectrum of the product of step 4) of example 3;

FIG. 10 is a nuclear magnetic hydrogen spectrum of the product of step 1) of comparative example 1;

FIG. 11 is a nuclear magnetic hydrogen spectrum of the product of step 2) of comparative example 1;

FIG. 12 is a nuclear magnetic hydrogen spectrum of the product of step 3) of comparative example 1;

FIG. 13 is a nuclear magnetic hydrogen spectrum of the product of step 1) of comparative example 2;

FIG. 14 is a nuclear magnetic hydrogen spectrum of the product of step 3) of comparative example 2.

Detailed Description

The chemical structure of the prepared product was tested by NMR (Varian INOVA 500 MHz). The sample preparation method comprises the following steps: and adding a small amount of dried test sample powder into a nuclear magnetic tube, adding deuterated dimethyl sulfoxide (DMSO-d6) for dissolving, and performing test characterization after uniform ultrasonic dispersion. Test range: 0 to 16 ppm.

The molecular weight of the prepared product was tested using high resolution mass spectrometry (Waters Xevo G2 QTof). A small amount of dried sample powder was taken and dissolved in methanol or acetonitrile for testing.

Example 1

1) Stirring 0.2mol of aluminum trichloride (30ml of dichloromethane is used as a solvent) and 0.2mol of p-butyl anisole for 45min under ice bath, adding 0.15mol of malonyl dichloride into the mixed solution under ice bath condition, reacting for 6h, performing rotary evaporation at 50 ℃ to obtain a solid, and separating by using a chromatographic column to obtain 0.19mol of a product in the step 1), wherein the eluent is dichloromethane and petroleum ether with a volume ratio of 3: 1.¹H NMR(500MHz,Chloroform)δ7.74(s,1H),7.35(s,1H),7.02(s,1H),4.89(s,1H),3.90(s,3H),2.63(s,2H),1.56(s,2H),1.33(s,2H),0.89(s,3H).

2) Under the condition of stirring at room temperature, 0.13mol of iodotrimethylsilane is added dropwise to 0.1mol of the product obtained in the step 1) and reacted for 6 hours. After the reaction is finished, 0.4mol of methanol is used for quenching excessive iodotrimethylsilane, volatile components are removed by reduced pressure distillation at 100 ℃, and the residues are washed for three times by 100ml of 10 percent sodium bisulfite aqueous solution and 100ml of 5 percent sodium bicarbonate aqueous solution respectively, and are dried to obtain 0.09mol of the product in the step 2).¹H NMR(500MHz,Chloroform)δ7.59(s,2H),7.20(s,2H),6.89(s,2H),4.38(s,2H),2.64(s,2H),1.56(s,3H),1.33(s,2H),0.89(s,3H).

3) Adding 0.0814mol of the product of the step 2) and a KOH catalyst (0.1 w.t percent of the total amount of the product of the step 2) and the ethylene oxide of the reaction raw materials) into a reaction vessel containing 100ml of DMF solution, heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature to be 120 ℃, keeping the pressure between 0.1MPa and 0.3MPa, continuously adding 6.818mol of ethylene oxide into the reaction vessel, reacting until the pressure is not reduced any more, and obtaining 0.079mol of the product obtained in the step 3), wherein the molecular weight is 4048 g/mol.

4) Slowly dropwise adding 0.045mol of fluorosulfonic acid into 0.01mol of the product obtained in the step 3) under the condition of an ice-water bath, violently stirring, and heating to 50 ℃ for reacting for 3 hours. And adding 0.045mol of sodium hydroxide into the reaction solution, neutralizing, extracting with petroleum ether for three times to remove non-sulfonated substances, drying an organic phase by using a rotary evaporator, and recrystallizing for multiple times (the solvent is ethyl acetate) to obtain 0.008mol of the surfactant containing the compound with the following structural formula. Mw: 4456g/mol, nuclear magnetism:¹H NMR(500MHz,Chloroform)δ8.15(s,1H),7.69(s,1H),4.73(s,1H),4.31(s,2H),3.78(d,J＝9.2Hz,4H),3.53(d,J＝10.0Hz,162H),2.64(s,2H),1.56(s,2H),1.33(s,2H),0.89(s,3H).

example 2

1) Stirring 0.2mol of aluminum trichloride (30ml of dichloromethane is used as a solvent) and 0.2mol of p-amyl anisole for 45min under ice bath, adding 0.15mol of succinyl dichloride into the mixed solution under ice bath condition, reacting for 6h, carrying out rotary evaporation at 50 ℃ to obtain a solid product, and separating by using a chromatographic column to obtain 0.18mol of the product obtained in the step 1), wherein the eluent is dichloromethane and petroleum ether with the volume ratio of 3: 1.¹H NMR(500MHz,Chloroform)δ7.79(s,1H),7.36(s,1H),7.01(s,1H),3.91(s,3H),3.25(s,2H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

2) Under the condition of stirring at room temperature, 0.13mol of iodotrimethylsilane is added dropwise into 0.1mol of the product obtained in the step 1) to react for 6 hours. After the reaction is finished, 0.4mol of methanol is used for quenching excessive iodotrimethylsilane, volatile components are removed by reduced pressure distillation at 100 ℃, and the residues are washed for three times by 100ml of 10 percent sodium bisulfite aqueous solution and 100ml of 5 percent sodium bicarbonate aqueous solution respectively, and are dried to obtain 0.09mol of the product in the step 2).¹H NMR(500MHz,Chloroform)δ7.62(s,1H),7.19(s,1H),6.86(s,1H),3.25(s,2H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

3) Adding 0.073mol of the product obtained in the step 2) and a KOH catalyst (0.1 w.t percent of the total amount of the product obtained in the step 2) and ethylene oxide in a reaction vessel containing 100ml of DMF solution, heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature to be 120 ℃, keeping the pressure to be between 0.1MPa and 0.3MPa, continuously adding 6.818mol of ethylene oxide into the reaction vessel, reacting until the pressure is not reduced any more, and obtaining 0.071mol of the product in the step 3) and the molecular weight of 4521 g/mol.

4) Slowly dropwise adding 0.045mol of fluorosulfonic acid into 0.01mol of the product obtained in the step 3) under the condition of an ice-water bath, violently stirring, and heating to 50 ℃ for reacting for 3 hours. Neutralizing the reaction liquid with 0.045mol of sodium hydroxide, extracting with petroleum ether for three times to remove non-sulfonated substances, drying the organic phase by using a rotary evaporator, and recrystallizing for multiple times (the solvent is ethyl acetate) to obtain 0.008mol of the surfactant containing the compound with the following structural general formula. Mw: 4929g/mol, nuclear magnetism:¹H NMR(500MHz,Chloroform)δ8.18(s,1H),7.68(s,1H),4.31(s,2H),3.82(s,2H),3.77(s,2H),3.53(d,J＝10.0Hz,182H),3.25(s,2H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H)。

example 3

1) Stirring 0.2mol of aluminum trichloride (30ml of dichloromethane is used as a solvent) and 0.2mol of p-propyl anisole for 45min under ice bath, adding 0.15mol of glutaryl dichloride into the mixed solution under ice bath condition, reacting for 6h, performing rotary evaporation at 50 ℃ to obtain a solid product, and separating by using a chromatographic column to obtain 0.2mol of the product obtained in the step 1), wherein the eluent is dichloromethane and petroleum ether with the volume ratio of 3: 1.¹H NMR(500MHz,Chloroform)δ7.76(s,1H),7.37(s,1H),7.04(s,1H),4.24(s,1H),3.91(s,3H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

2) Under the condition of stirring at room temperature, 0.13mol of iodotrimethylsilane is added dropwise into 0.1mol of the product obtained in the step 1) to react for 6 hours. After the reaction, the excess iodotrimethylsilane was quenched with 0.4mol of methanol, the volatile components were distilled off at 100 ℃ under reduced pressure, and the residue was treated with 100ml of 10% strength sodium bisulfite solutionThe solution is washed three times with 100ml of 5% aqueous sodium bicarbonate solution and dried to obtain 0.1mol of the product of step 2).¹H NMR(500MHz,Chloroform)δ7.58(s,1H),7.19(s,1H),6.88(s,1H),4.70(s,1H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

3) Adding 0.0815mol of the product obtained in the step 2) and a KOH catalyst (based on 0.1 w.t.% of the total amount of the product obtained in the step 2) and ethylene oxide in a reaction vessel containing 100ml of DMF solution, heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature to be 120 ℃, keeping the pressure lower than 0.1 MPa-0.3 MPa, continuously adding 300g of ethylene oxide into the reaction vessel, reacting until the pressure is not reduced any more, and obtaining 0.079mol of the product obtained in the step 3), wherein the molecular weight is 4048 g/mol.

4) Slowly dropwise adding 0.045mol of fluorosulfonic acid into 0.01mol of the product obtained in the step 3) under the condition of an ice-water bath, violently stirring, and heating to 50 ℃ for reacting for 3 hours. Neutralizing the reaction liquid with 0.045mol of sodium hydroxide, extracting with petroleum ether for three times to remove non-sulfonated substances, drying the organic phase by using a rotary evaporator, and recrystallizing for multiple times (the solvent is ethyl acetate) to obtain 0.009mol of the surfactant containing the compound with the following structural general formula. Mw: 4456 g/mol.¹H NMR(500MHz,Chloroform)δ8.15(s,1H),7.69(s,1H),4.31(s,2H),4.27(s,1H),3.88(s,2H),3.77(s,2H),3.53(d,J＝10.0Hz,158H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

Comparative example 1

Adopting a conventional process, synthesizing the surfactant without methoxy protection:

1) stirring 0.2mol of aluminum trichloride (30ml of dichloromethane is used as a solvent) and 0.2mol of 4-pentylphenol for 45min under ice bath, adding 0.15mol of succinyl dichloride into the mixed solution under ice bath condition, reacting for 6h, performing rotary evaporation at 50 ℃ to obtain a solid product, and separating by using a chromatographic column to obtain 0.19mol of the product obtained in the step 1), wherein the eluent is dichloromethane and petroleum ether with the volume ratio of 4: 1.¹H NMR(500MHz,Chloroform)δ7.17(s,2H),3.05(s,1H),2.64(s,1H),1.63(s,1H),1.34(s,2H),0.91(s,2H).

2) Adding 0.073mol of the product obtained in the step 1) and a KOH catalyst (0.1 w.t.% of the total amount of the product obtained in the step 1) and ethylene oxide in a reaction vessel containing 100ml of DMF solution, heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature to be 120 ℃, keeping the pressure to be between 0.1MPa and 0.3MPa, when 1.364mol of ethylene oxide is continuously added into a reaction container, because the last step of reaction is not protected by methoxyl group, the phenolic hydroxyl group is replaced by succinyl dichloride, so that active hydrogen is lost to react with the ethylene oxide, the reaction pressure exceeds 0.3MPa, and the reaction is stopped to obtain 0.06mol of the product obtained in the step 2) and the molecular weight is 411 g/mol.¹H NMR(500MHz,Chloroform)δ7.17(s,2H),3.05(s,1H),2.64(s,1H),1.63(s,1H),1.34(s,2H),0.91(s,2H).

3) Slowly dropwise adding 0.045mol of fluorosulfonic acid into 0.01mol of the product obtained in the step 2) under the condition of an ice-water bath, violently stirring, and heating to 50 ℃ for reaction for 3 hours. The reaction solution is neutralized by 0.045mol of sodium hydroxide, petroleum ether is used for three times to extract and remove non-sulfonated substances, and the organic phase is dried by a rotary evaporator and then is recrystallized for multiple times (the solvent is ethyl acetate) to obtain a final product of 0.009 mol. Mw: 615 g/mol.¹H NMR(500MHz,Chloroform)δ7.57(s,1H),7.50(s,1H),7.47(s,1H),3.05(s,2H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

Comparative example 2

Synthesis of surfactants using oxygen atom-free methylene as linker:

1) adding 1.2mol of 4-pentylphenol, 0.3mol of paraformaldehyde, 0.1mol of oxalic acid (35% oxalic acid aqueous solution) and 30ml of n-octane into a reaction kettle, replacing nitrogen for three times, heating to 130 ℃, and vigorously stirring for 5 hours. The crude product is washed five times with 200ml of water, freed from solvent and dried in vacuo to give 0.6mol of a colorless, transparent viscous liquid.¹H NMR(500MHz,Chloroform)δ6.91(s,1H),6.77(s,1H),6.71(s,1H),6.17(s,1H),3.96(s,1H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

2) Adding 0.147mol of the product obtained in the step 1) and a KOH catalyst (based on 0.1 w.t.% of the total amount of the product obtained in the step 1) and ethylene oxide in a reaction vessel containing 100ml of DMF solution, heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature to be 120 ℃, keeping the pressure to be between 0.1MPa and 0.3MPa, continuously adding 11.36mol of ethylene oxide into the reaction container, and reacting until the pressure is not reduced any more, thereby obtaining 0.144mol of the product in the step 2) and the molecular weight of the product is 3740 g/mol.

3) Slowly dropwise adding 0.045mol of chlorosulfonic acid into 0.01mol of the product obtained in the step 2) under the condition of ice-water bath, violently stirring, and heating to 50 ℃ for reaction for 3 h. Neutralizing the reaction liquid with 0.045mol of sodium hydroxide, then using petroleum ether for three times to extract and remove non-sulfonated substances, drying the residual solvent, using absolute ethyl alcohol to remove salt, and then using ethyl acetate for recrystallization for multiple times to obtain 0.008mol of surfactant containing the compound with the following structural general formula. Mw: 4148g/mol, 1H NMR (500MHz, Chloroform) δ 7.40(s,1H),7.27(s,1H),4.31(s,2H),3.96(s,1H),3.81(d, J ═ 36.6Hz,4H),3.53(d, J ═ 10.0Hz,150H),2.64(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

Test example 1

The formula of the laundry detergent comprises: 12 wt% of example or comparative example product, 1.3 wt% of 6501 alkanolamide, 2 wt% of sodium fatty alcohol-polyoxyethylene ether sulfate, 2.5 wt% of sodium bicarbonate with the concentration of 30%, 0.4 wt% of NaCl, 1 wt% of lemon essence and 0.01 wt% of indigo pigment, adding water to 100%, and uniformly mixing.

The determination method comprises the following steps:

detergency: the determination is carried out according to GB/T13174-2008 'determination of detergency and circulating washing performance of detergents for clothing'.

Foaming power: 2.5g of the laundry detergent was weighed out and made up with 150mg/kg of hard water at 40 ℃ and the foaming power was measured in accordance with GB/T13173.6-91 "measurement of foaming power of detergents (Ross-Miles method)".

Hard water resistance: 50ml of 0.5% distilled water surfactant solution was transferred into a 500ml ground conical flask with a pipette, and after shaking, 96% calcium chloride solution was added dropwise, the flask was vigorously shaken after each addition, and left to stand for 30s until the foam duration was shorter than 10s, indicating that titration was complete, at which time the amount of calcium chloride consumed represented hard water resistance.

The laundry detergent test results are shown in table 1.

Table 1 laundry detergent test results

Claims

1. A surfactant comprising a compound of the general structural formula:

wherein n is an integer of 1 to 15, x and p are independent integers of 0 to 100, y and q are independent integers of 0 to 100, x and y are not 0 at the same time, p and q are not 0 at the same time, and R is a C1 to C6 alkylene group.

2. The surfactant according to claim 1, wherein n is an integer of 3 to 10, x and p are each independently an integer of 30 to 90, y and q are each independently an integer of 0 to 30, and R is a methylene group, an ethylene group or a propylene group.

3. The surfactant according to claim 1, wherein n is an integer of 3 to 10, x + p =30 to 180, y + q =0 to 60, and R is a methylene group, an ethylene group, or a propylene group.

4. The surfactant according to claim 3, wherein x + p = 70-120 and y + q = 0-30.

5. The surfactant according to claim 1, wherein the weight average molecular weight of the surfactant is in the range of 780g/mol to 12000 g/mol.

6. The surfactant according to claim 1, wherein the weight average molecular weight of the surfactant is in the range of 3000g/mol to 8000 g/mol.

7. A process for preparing the surfactant of claim 1 comprising the steps of:

1) adding alkyl diacyl dichloride into a mixture of aluminum trichloride and p-alkyl anisole under ice bath, and purifying after reaction to obtain a product in the step 1);

2) dropwise adding iodotrimethylsilane into the product obtained in the step 1) for reaction, and after the reaction is finished, purifying to obtain a product obtained in the step 2);

3) taking the product obtained in the step 2) as an initiator, controlling the reaction temperature to be 100-180 ℃ and the pressure to be 0.1-0.6 MPa in the presence of a catalyst, adding an epoxide into a reaction container, and reacting until the pressure is not reduced any more;

4) reacting the halosulfonic acid with the product obtained in the step 3) under the ice-water bath condition, and purifying to obtain the surfactant.

8. The method as claimed in claim 7, wherein the reaction temperature in step 3) is controlled to 120 to 140 ℃ and the pressure is controlled to 0.1 to 0.3 MPa.

9. The method according to claim 7, wherein in the step 1), the ratio of p-alkyl anisole: aluminum trichloride: the molar ratio of the alkyl diacyl dichloride is 2 (2.0-3.0) to 1.3-2.0.

10. The method according to claim 9, wherein in the step 1), the ratio of p-alkyl anisole: aluminum trichloride: the molar ratio of the alkyl diacyl dichlorides is 2 (2.0-2.2) to 1.3-1.8.

11. The method as claimed in claim 7, wherein in the step 2), the molar ratio of the product of the step 1) to the iodotrimethylsilane is 1: 1.0-2.0.

12. The method as claimed in claim 7, wherein in the step 2), the molar ratio of the product of the step 1) to the iodotrimethylsilane is 1: 1.1-1.4.

13. The method according to claim 7, wherein in the step 3), the mass ratio of the initiator to the epoxide is 1: 2-30.

14. The method according to claim 7, wherein in the step 3), the mass ratio of the initiator to the epoxide is 1: 5-20.

15. The method according to claim 7, wherein in the step 3), the mass ratio of the initiator to the epoxide is 1: 7-15.

16. The method according to claim 7, wherein in the step 4), the molar ratio of the product obtained in the step 3) to the halosulfonic acid is 1: 4.0-6.0.

17. The method according to claim 7, wherein in the step 4), the molar ratio of the product obtained in the step 3) to the halosulfonic acid is 1: 4.2-4.7.

18. The method according to claim 7, wherein in the step 2), after the reaction is finished, the excess iodotrimethylsilane is quenched with methanol, the volatile components are removed by distillation under reduced pressure, and the residue is washed with an aqueous sodium bisulfite solution and an aqueous sodium bicarbonate solution, respectively, and then dried.

19. Use of the surfactant according to any one of claims 1 to 6 or the surfactant prepared by the process according to any one of claims 7 to 18 for textile, detergent, pharmaceutical, petroleum applications.