CN111117787B

CN111117787B - Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent

Info

Publication number: CN111117787B
Application number: CN201911333450.1A
Authority: CN
Inventors: 殷玲; 秦承群; 鞠昌迅; 刘斌; 李付国; 刘洋; 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: 2021-05-14
Anticipated expiration: 2039-12-23
Also published as: CN111117787A

Abstract

The invention discloses a bactericidal acarus killing surfactant, a preparation method thereof and a laundry detergent. The surfactant comprises a compound of the following structural formula:

Description

Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent

Technical Field

The invention relates to the field of surfactants, and particularly relates to a bactericidal acarus killing surfactant and a laundry detergent.

Background

The laundry detergent is a detergent variety which is developed rapidly in recent years in fabric care markets at home and abroad. In China, the laundry detergent has already entered families. With the continuous improvement of living standard, the requirements of people on the laundry detergent are only satisfied with the basic decontamination effect, and people hope that the laundry detergent has other effects while washing off dirt.

The mites are miniature pests which are not easy to see by naked eyes, the dead bodies, secretions and excretions of the mites are all allergen sources, the mites can directly bite the skin to cause insect-bite dermatitis, and can also cause skin inflammation through the generated secretions such as excrement, saliva and the like, if the live mites directly invade the human body, the people can suffer from asthma, bronchitis, nephritis, allergic rhinitis and the like, and the health of the human body is seriously harmed. Therefore, the development of the bacteriostatic acarid-removing laundry detergent just meets the diversified demands of the market.

The Chinese invention patent CN107619724A discloses a mite-removing laundry detergent with plants as main components, wherein, the costustoot extract solution is used for removing mites and the Chinese herbal medicine liquid is used for sterilization, the two components account for 60-80 wt% of the total laundry detergent, while the component with the real detergency only accounts for about 1% (by weight) of the total laundry detergent, thus the laundry detergent achieves good mite-removing and sterilization effects, but cannot meet the decontamination effect of the conventional laundry detergent.

In view of the above situation, it is necessary to develop a surfactant with both strong detergency and bactericidal and acaricidal effects, so as to ensure that the surfactant has high bactericidal and acaricidal effects on the basis of not losing the original effect of the laundry detergent.

Disclosure of Invention

The invention provides a sterilization and mite removal surfactant, which takes ester group as a linking group to form ester group quaternary ammonium salt with quaternary ammonium salt, so that the softness of fabrics is increased, and the addition of a softening agent can be reduced or even not added in the cleaning process; fluorine elements are introduced into two ends of the surfactant to enhance the sterilization and mite removal effects of the quaternary ammonium salt, and the polysiloxane vinyl ether with good hydrophilicity is introduced to have the combined action with the alkane which is hydrophobic and has a certain chain length, so that the surfactant has an excellent decontamination effect. The preparation method of the surfactant is simple and efficient, mild in condition and easy to industrialize.

The invention also provides a laundry detergent which contains the bactericidal acarus-killing surfactant.

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

a bactericidal acarus killing surfactant comprises a compound with the following structural general formula:

wherein n is an integer of 2-8, m is an integer of 2-20, x and p are mutually independent integers of 0-100, y and q are mutually independent integers of 0-100, x and y are not 0 at the same time, and p and q are not 0 at the same time;

preferably, n is an integer of 5-8, m is an integer of 5-15, x and p are independent integers of 10-70, and y and q are independent integers of 0-70; or n is an integer of 5 to 8, m is an integer of 5 to 15, x + p is 20 to 140, preferably 20 to 110, and y + q is 0 to 140, preferably 0 to 80.

The weight average molecular weight of the surfactant of the invention is 1000g/mol to 12000g/mol, preferably 2000g/mol to 6000 g/mol.

A method of making the surfactant of the present invention, comprising the steps of:

1) using isopropanol as a solvent, reacting 1H, 1H-perfluoroalkyl amine and 1-bromoalkane for 20-24H under a reflux state, carrying out reduced pressure distillation to remove volatile components, and recrystallizing with ethyl acetate and acetone to obtain a compound shown in the formula I;

2) using isopropanol as a solvent, reacting the compound of the formula I with 1-chloroethyl chloroformate for 30-40 h under a reflux state, carrying out reduced pressure distillation to remove volatile components, and recrystallizing with ethyl acetate and acetone to obtain a compound of the formula II;

3) in the presence of sodium hydroxide, acetonitrile is used as a solvent, the compound of the formula II and 2-chloroethanol react for 50-60 hours at the temperature of 80-90 ℃, after the reaction is finished, volatile components are removed through reduced pressure distillation, the mixed solution of ethanol and acetone is used for recrystallization, and the compound of the formula III is obtained after drying;

4) taking a compound shown in a formula III as an initiator, in the presence of a catalyst, adding an epoxide into the mixture at the reaction temperature of 100-180 ℃, preferably 120-140 ℃ and the pressure of 0.1-0.6 MPa (by gauge pressure), preferably 0.1-0.3 MPa, and reacting until the pressure is not reduced, thus obtaining the surfactant.

In the step 1), the molar ratio of the 1H, 1H-perfluoroalkyl amine to the 1-bromoalkane is 1: 0.8-1.5, preferably 1: 0.9-1.2.

The volume ratio of the recrystallization solvent ethyl acetate and acetone in the step 1) is 1: 8 to 12.

The 1H, 1H-perfluorinated alkylamine comprises one or more of 1H, 1H-perfluorinated ethylamine, 1H-perfluorinated propylamine, 1H-perfluorinated butylamine, 1H-perfluorinated pentylamine, 1H-perfluorinated hexylamine, 1H-perfluorinated heptylamine and 1H, 1H-perfluorinated octylamine, and preferably one or more of 1H, 1H-perfluorinated pentylamine, 1H-perfluorinated hexylamine, 1H-perfluorinated heptylamine and 1H, 1H-perfluorinated octylamine.

The 1-bromoalkane comprises one or more of 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane, 1-bromotetradecane, 1-bromopentadecane, 1-bromohexadecane, 1-bromoheptadecane, 1-bromooctadecane, 1-bromononadecane and 1-bromoeicosane, preferably 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane, One or more of 1-bromotetradecane and 1-bromopentadecane.

In the step 2) of the invention, the molar ratio of the compound of formula I to 1-chloroethyl chloroformate is 2.0-3.0: 1, preferably 2.2-2.5: 1.

The volume ratio of the recrystallization solvent ethyl acetate and acetone in the step 2) is 1:5 to 10.

In the step 3), the molar ratio of the compound of the formula II to 2-chloroethanol is 1: 2.0-3.0, preferably 1: 2.1-2.4.

Preferably, the volume ratio of ethanol to acetone used as the recrystallization solvent in the step 3) is 1:5 to 10.

In the step 4), the molar ratio of the initiator to the epoxide is 1: 10-150, preferably 1: 30-130.

In the step 4), 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 the step 4), the amount of the catalyst is 0.01-0.5%, preferably 0.05-0.2% of the total mass of the compound of the formula III and the epoxide.

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

Step 4) according to the invention is preferably carried out in a jet reactor, a tubular reactor, a stirred tank or a loop reactor.

The surfactant disclosed by the invention has excellent dirt-removing power and sterilization and mite-killing effects.

The invention also provides the application of the surfactant in laundry detergent in the field of washing and chemical industry.

The laundry detergent comprises the following components in parts by weight:

in the laundry detergent, the alkali in the alkali liquor is selected from one or more of 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 25-35 wt%.

In the laundry detergent, the viscosity modifier is sodium chloride.

In the laundry detergent, the pigment is indigo pigment.

In the laundry detergent, the essence is lavender essence.

The laundry detergent disclosed by the invention uses the surfactant with the sterilization and mite removal effects, so that the laundry detergent has excellent detergency and sterilization performance.

As a preferred scheme, the invention also provides a preparation method of the laundry detergent, which comprises the following steps: according to the proportion:

(1) heating the surfactant, the sodium fatty acid methyl ester sulfonate, 6501 alkanolamide and water to 50-60 ℃ under stirring until the surfactant, the sodium fatty acid methyl ester sulfonate, the 6501 alkanolamide and the water are dissolved;

(2) cooling to 40 deg.C, adding viscosity regulator, alkali solution, essence and pigment under stirring, and stirring for 15 min;

(3) and cooling to room temperature to obtain the laundry detergent.

The invention has the following beneficial effects:

1. the invention synthesizes the surfactant containing the fluorine element and the quaternary ammonium salt, and the laundry detergent prepared by using the surfactant increases the antibacterial property of the laundry detergent.

2. The synthesized surfactant is an esterquat cationic surfactant in the transverse direction, so that the flexibility of the fabric is enhanced; the non-ionic surface active agent is arranged in the longitudinal direction, so that the dirt-removing capability of the laundry detergent is improved.

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; meanwhile, the reaction does not need a catalyst, so that the cost is saved and the price is low.

Drawings

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

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

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

FIG. 4 is a nuclear magnetic hydrogen spectrum of the product of step 4) of comparative example 1.

Detailed Description

NMR (Varian INOVA 500 MHz): adding a small amount of dried azobenzene 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.

And (3) testing detergency: the determination is carried out according to GB/T13174-2008 'determination of detergency and circulating washing performance of detergents for clothing'.

Mite killing test: according to the pesticide test (bioassay) letter [2003]No. 45, test method and evaluation standard for killing and expelling mite, comprises placing the powder mites cultured by Shanghai light industry research institute Co., Ltd on filter paper, placing the filter paper in the center of a culture dish, diluting the laundry liquid with water at a ratio of 1:50, and adding 20mg/cm²The dose of (A) was evenly spread on filter paper for mite killing rate test.

Example 1

1) Using 30ml of isopropanol as a solvent, reacting 0.3mol of 1H, 1H-perfluorohexylamine and 0.33mol of 1-bromopentane under reflux for 24H at 85 ℃, removing volatile components by reduced pressure distillation after the reaction is finished, and recrystallizing for 1 time by using 400ml of mixed solution of ethyl acetate and acetone (volume ratio of 1:10) to obtain 0.23mol of a product I-1.

2) Mixing 0.22mol of the product obtained in the step 1) with 0.1mol of 1-chloroethyl chloroformate, carrying out reflux reaction for 40h at 85 ℃ by taking 30ml of isopropanol as a solvent, carrying out reduced pressure distillation after the reaction is finished to remove volatile components, washing the mixture for 1 time by using 100ml of petroleum ether and 50ml of diethyl ether respectively, and recrystallizing the mixture for 1 time by using 400ml of mixed solution (volume ratio is 1:6) of ethyl acetate and acetone to obtain 0.08mol of the product II-1.

3) 0.07mol of the above product II-1 was mixed with 0.154mol of 2-chloroethanol in the presence of 0.154mol of sodium hydroxide, and reacted at 85 ℃ for 60 hours with 30ml of acetonitrile as a solvent, after the reaction was completed, volatile components were distilled off under reduced pressure, and the mixture was dissolved in 400ml of a mixed solution of ethanol and acetone (volume ratio: ethanol: acetone 1:6) and dried in vacuo to give 0.056mol of product III-1.

4) Taking 0.05mol of the product obtained in the step 3) as an initiator, adding a KOH catalyst (based on 0.1 wt% of the total amount of the product III-1 and the ethylene oxide), heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature at 120 ℃, keeping the pressure between 0.1MPa and 0.3MPa, adding 1.53mol of ethylene oxide into the reaction vessel, and reacting until the pressure is not reduced any more, thereby obtaining 0.039mol of a product IV-1. Mw: 2042.6 g/mol.

Example 2

1) Using 30ml of isopropanol as a solvent, reacting 0.3mol of 1H, 1H-perfluorooctylamine and 0.33mol of 1-bromodecane for 24 hours under a reflux state at 85 ℃, removing volatile components by reduced pressure distillation after the reaction is finished, and recrystallizing for 1 time by using 400ml of mixed solution of ethyl acetate and acetone (volume ratio of 1:10) to obtain 0.24mol of a product I-2.

2) Mixing 0.22mol of the product obtained in the step 1) with 0.1mol of 1-chloroethyl chloroformate, carrying out reflux reaction for 40h at 85 ℃ by taking 30ml of isopropanol as a solvent, removing volatile components by reduced pressure distillation after the reaction is finished, washing 3 times by using 100ml of petroleum ether and 50ml of diethyl ether respectively, and recrystallizing 1 time by using 400ml of mixed solution (volume ratio is 1:6) of ethyl acetate and acetone to obtain 0.09mol of a product II-2.

3) 0.07mol of the above product II-2 was mixed with 0.154mol of 2-chloroethanol in the presence of 0.154mol of sodium hydroxide, and reacted at 85 ℃ for 60 hours with 30ml of acetonitrile as a solvent, after the reaction was completed, volatile components were distilled off under reduced pressure, and the mixture was dissolved in 400ml of a mixed solution of ethanol and acetone (volume ratio: ethanol: acetone 1:6) three times, and vacuum drying gives 0.063mol of product III-2.

4) Taking 0.05mol of the product obtained in the step 3) as an initiator, adding a KOH catalyst (based on 0.1 wt% of the total amount of the product III-2 and the ethylene oxide), heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature at 120 ℃, keeping the pressure between 0.1MPa and 0.3MPa, adding 3.37mol of ethylene oxide into the reaction vessel, and reacting until the pressure is not reduced any more, thereby obtaining 0.041mol of product IV-2. Mw: 3879 g/mol.

Example 3

1) Using 30ml of isopropanol as a solvent, reacting 0.3mol of 1H, 1H-heptadecafluorononanamine and 0.33mol of 1-bromopentadecane for 24 hours under a reflux state at 85 ℃, removing volatile components by reduced pressure distillation after the reaction is finished, and recrystallizing for 1 time by using 400ml of mixed solution of ethyl acetate and acetone (volume ratio is 1:10) to obtain 0.23mol of a product I-3.

2) Mixing 0.22mol of the product obtained in the step 1) with 0.1mol of 1-chloroethyl chloroformate, carrying out reflux reaction for 40h at 85 ℃ by taking 30ml of isopropanol as a solvent, removing volatile components by reduced pressure distillation after the reaction is finished, washing for 1 time by using 100ml of petroleum ether and 50ml of diethyl ether respectively, and recrystallizing for 1 time by using 400ml of mixed solution (volume ratio is 1:6) of ethyl acetate and acetone to obtain 0.07mol of a product II-3.

3) 0.07mol of the above product II-3 was mixed with 0.154mol of 2-chloroethanol in the presence of 0.154mol of sodium hydroxide, and reacted at 85 ℃ for 60 hours with 30ml of acetonitrile as a solvent, after the reaction was completed, volatile components were distilled off under reduced pressure, and the mixture was dissolved in 400ml of a mixed solution of ethanol and acetone (ethanol: acetone 1:6) and dried in vacuo to yield 0.0595mol of product III-3.

4) Taking 0.05mol of the product obtained in the step 3) as an initiator, adding a KOH catalyst (based on 0.1 wt% of the total amount of the product III-3 and the ethylene oxide), heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature at 120 ℃, keeping the pressure between 0.1MPa and 0.3MPa, adding 6.098mol of ethylene oxide into the reaction vessel, and reacting until the pressure is not reduced any more, thereby obtaining 0.032mol of product IV-3. Mw: 5879 g/mol.

Comparative example 1

The comparative example differs from the present invention in that the intermediate linker group employs an alkyl chain, and the substance providing the linker structure is

1) Using 30ml of isopropanol as a solvent, reacting 0.3mol of 1H, 1H-perfluorooctylamine and 0.33mol of 1-bromodecane for 24 hours under a reflux state at 85 ℃, removing volatile components by reduced pressure distillation after the reaction is finished, and recrystallizing for 1 time by using 400ml of mixed solution of ethyl acetate and acetone (volume ratio of 1:10) to obtain 0.22mol of a product D-1.

2) Mixing 0.22mol of the product obtained in the step 1) with 0.1mol of 1, 3-dichloropropane, carrying out reflux reaction for 40h at 85 ℃ by taking 30ml of isopropanol as a solvent, carrying out reduced pressure distillation after the reaction is finished to remove volatile components, washing the mixture for 1 time by using 100ml of petroleum ether and 50ml of diethyl ether respectively, and recrystallizing the mixture for 1 time by using 400ml of mixed solution (volume ratio is 1:6) of ethyl acetate and acetone to obtain 0.07mol of product D-2.

3) 0.07mol of the product D-2 was mixed with 0.154mol of 2-chloroethanol in the presence of 0.154mol of sodium hydroxide, and the mixture was reacted at 85 ℃ for 60 hours in 30ml of acetonitrile as a solvent, after the reaction was completed, volatile components were distilled off under reduced pressure, and the mixture was dissolved in 400ml of a mixed solution of ethanol and acetone (volume ratio: ethanol: acetone 1:6) and dried in vacuo to give 0.056mol of product D-3.

4) Taking 0.05mol of the product obtained in the step 3) as an initiator, adding a KOH catalyst (based on 0.1 wt% of the total amount of the product D-3 and the ethylene oxide), heating to 100 ℃, and vacuumizing for dehydration; controlling the reaction temperature at 120 ℃, keeping the pressure between 0.1MPa and 0.3MPa, adding 3.449mol of ethylene oxide into the reaction vessel, and reacting until the pressure is not reduced any more, thereby obtaining 0.04mol of product D-4. Mw: 3849 g/mol.

Preparation of laundry detergent

Example 4

1) Heating 12 parts by weight of product IV-1, 2 parts by weight of 6501 alkanolamide, 2 parts by weight of sodium fatty acid methyl ester sulfonate and 80.09 parts by weight of water to 60 ℃ under stirring until the product IV-1, the 6501 alkanolamide, the sodium fatty acid methyl ester sulfonate and the water are dissolved;

2) cooling to 40 deg.C, adding 0.4 weight parts of sodium chloride, 2.5 weight parts of 30 wt% sodium bicarbonate water solution, 1 weight part of lavender essence and 0.01 weight part of indigo pigment under stirring, and stirring for 15 min;

3) and cooling to room temperature to obtain the laundry detergent.

Examples 5 and 6

The products IV-2 and IV-3 were used in place of the product IV-1 in example 4, respectively, and the rest was the same as in example 4.

Comparative example 2

The product D-4 was used instead of the product IV-1 from example 4, the remainder being identical to example 4.

Comparative example 3

The procedure of example 4 was repeated except that sodium alcohol ether sulfate AES (Zhejiang Jiehang) was used instead of the product IV-1 in example 4.

And (4) carrying out detergency test and mite killing test on the prepared laundry detergent. Table 1 shows the results of the detergency test of the laundry detergent, and table 2 shows the mite-killing effect of the laundry detergent.

TABLE 1 detergency test results for laundry detergents

TABLE 2 mite-killing effect of laundry detergent

By comparing tables 1 and 2, the laundry detergent of example 5 is the most excellent in both detergency and acarid-repelling effect. It was found by comparing comparative example 2 and example 5 that the detergency and the mite-killing effect are deteriorated after the linker is replaced with the rigid chain, i.e., the flexible chain in the present invention is more advantageous. The comparison between comparative example 3 and examples 4-6 shows that the detergency and the sterilizing and mite-killing effects of the laundry detergent of the invention are better than those of the common laundry detergent of comparative example 3.

And (3) softness testing: the flexibility performance is tested by referring to the hand feeling evaluation method which is commonly used at home and abroad at present. The towel using pure cotton was divided into five groups of 5 towels. And (3) fully rinsing the towel with tap water for 5min for desizing, and naturally drying the towel after dehydration for later use. Respectively adding IV-1, IV-2 and IV-3 obtained in examples 1-3, D-4 of comparative example 1 and 3g of AES into 2kg of water, uniformly stirring, then putting the cotton towel into the water, soaking for 20min, taking out the cotton towel, dehydrating and naturally drying. 5 testers with certain experience and sensitive hand feeling respectively evaluate the towel, the evaluation is divided into 1-5 grades according to the softness, the smaller the numerical value is, the softer the towel is, the softness of the towel is compared according to the total number, and the evaluation result is shown in the following table 3:

TABLE 3 evaluation results of flexibility

It is apparent from table 3 that the surfactant of example 2 gave the highest softness after washing the towels, followed by example 3, example 1, comparative example 1 and AES, respectively, more closely.

Claims

1. A bactericidal acarus killing surfactant comprises a compound with the following structural general formula:

wherein n is an integer of 2-8, m is an integer of 2-20, x and p are mutually independent integers of 0-100, y and q are mutually 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 x and p are not 0 at the same time.

2. The surfactant according to claim 1, wherein n is an integer of 5 to 8, m is an integer of 5 to 15, x and p are each independently an integer of 10 to 70, and y and q are each independently an integer of 0 to 70.

3. The surfactant according to claim 2, wherein n is an integer of 5 to 8, m is an integer of 5 to 15, x + p is 20 to 140, and y + q is 0 to 140.

4. The surfactant according to claim 3, wherein x + p is 20 to 110 and y + q is 0 to 80.

5. The surfactant according to claim 1, wherein the weight average molecular weight of the surfactant is 1000g/mol to 12000 g/mol.

6. The surfactant according to claim 1, wherein the weight average molecular weight of the surfactant is 2000g/mol to 6000 g/mol.

7. A process for preparing the surfactant of any one of claims 1-6, comprising the steps of:

1) reaction of 1H, 1H-perfluoroalkylamine and 1-bromoalkane to give the compound of formula I

2) Reacting the compound of formula I with 1-chloroethyl chloroformate to obtain a compound of formula II

3) Reacting the compound of formula II with 2-chloroethanol to obtain a compound of formula III

4) And (3) taking the compound in the formula III as an initiator, and adding epoxide to carry out ring-opening polymerization reaction to obtain the surfactant.

8. The method of claim 7, wherein in the step 1), the molar ratio of the 1H, 1H-perfluoroalkyl amine to the 1-bromoalkane is 1: 0.8-1.5.

9. The method of claim 7, wherein in the step 1), the molar ratio of the 1H, 1H-perfluoroalkyl amine to the 1-bromoalkane is 1: 0.9-1.2.

10. The method of claim 7, wherein the 1H, 1H-perfluoroalkylamine comprises one or more of 1H, 1H-perfluoroethylamine, 1H-perfluoropropylamine, 1H-perfluorobutylamine, 1H-perfluoropentylamine, 1H-perfluorohexylamine, 1H-perfluoroheptylamine, and 1H, 1H-perfluorooctylamine.

11. The method of claim 7, wherein the 1-bromoalkane comprises one or more of 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane, 1-bromotetradecane, 1-bromopentadecane, 1-bromohexadecane, 1-bromoheptadecane, 1-bromooctadecane, 1-bromononadecane, and 1-bromoeicosane.

12. The method according to claim 7, wherein in the step 2), the molar ratio of the compound of formula I to 1-chloroethyl chloroformate is 2.0-3.0: 1.

13. The method according to claim 7, wherein in the step 2), the molar ratio of the compound of formula I to 1-chloroethyl chloroformate is 2.2-2.5: 1.

14. The method according to claim 7, wherein in the step 3), the molar ratio of the compound of formula II to 2-chloroethanol is 1: 2.0-3.0.

15. The method according to claim 7, wherein in the step 3), the molar ratio of the compound of formula II to 2-chloroethanol is 1: 2.1-2.4.

16. The method of claim 7, wherein in step 4), the molar ratio of the starter to the epoxide is 1:10 to 150, and the epoxide comprises ethylene oxide and optionally propylene oxide.

17. The method of claim 7, wherein in step 4), the molar ratio of the initiator to the epoxide is 1:30 to 130.

18. The laundry detergent comprises the following components in parts by weight: