Alkylbenzene sulfonic acid and its preparation method and application

Abstract

The present invention provides an alkylbenzene sulfonic acid and a preparation method and application thereof, and relates to the technical field of surfactants. The alkylbenzene sulfonic acid of the present invention has a structure as shown in Formula I, and has the advantages of being biodegradable, having strong resistance to hard water, and having low irritation. The alkylbenzene sulfonic acid of the present invention is prepared by the following method: using fatty alcohol polyoxyethylene ether and phenol as reactants, adding a catalyst, and reacting to obtain phenyl alkyl ether polyoxyethylene ether; using phenyl alkyl ether polyoxyethylene ether and sulfur trioxide as reactants, and reacting to obtain the alkylbenzene sulfonic acid shown in Formula I. The alkylbenzene sulfonic acid of the present invention has the advantages of strong resistance to hard water, strong emulsification ability, and easy biodegradation, and can be used to prepare pesticide emulsifiers.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, in particular to an alkylbenzene sulfonic acid and a preparation method and application thereof, in particular to the application in preparing a pesticide emulsifier. Background Art

[0002] Alkylbenzenesulfonic acid ( Where R = C 11 ~C 13 ), commonly used as a raw material for detergents, to produce sodium and ammonium salts of alkylbenzene sulfonic acid. Alkylbenzene sulfonate is the neutralization product of alkylbenzene sulfonic acid and is an important anionic surfactant. Alkylbenzene sulfonate mainly includes linear alkylbenzene sulfonate (LAS) and branched alkylbenzene sulfonate (ABS).

[0003] Due to poor biodegradability, branched alkylbenzene sulfonates have been gradually replaced by linear alkylbenzene sulfonates. Linear alkylbenzene sulfonates have strong detergency, good foaming ability and foam stability, and have good stability in acidic, alkaline and even oxidant solutions. In addition, they are abundant in source, mature in manufacturing process and low in cost. They are excellent detergents and foaming agents. As active substances in detergents, linear alkylbenzene sulfonates are easy to spray dry and form, and are very suitable for making washing powders. They can also be added to shampoo, foam bath and other bath liquids in appropriate amounts. They can also be used as cleaning agents, dyeing aids, and raw materials for metal cleaning and deinking agents in the papermaking industry.

[0004] However, linear alkylbenzene sulfonates also have some defects, such as being sensitive to water hardness, rapidly reducing washing ability in hard water, and easily reacting with calcium and magnesium ions in water to form organic deposits that remain on clothing. Organic deposits can reduce the performance of fabrics, such as increasing the hydrophobicity of fabrics, reducing capillary effects, reducing the climate regulation of clothing, and aggravating the retention of stains on fabrics. In addition, linear alkylbenzene sulfonates, as personal care raw materials, are more irritating than fatty alcohol sulfates and fatty alcohol polyoxyethylene ether sulfates, resulting in limited usage and scope of application.

[0005] Alkylphenol polyoxyethylene ether It is often used to replace linear alkylbenzene sulfonate. Alkylphenol polyoxyethylene ethers undergo initial biodegradation to obtain alkylphenols, which are also difficult to biodegrade. Although it has good emulsification, leveling, penetration and wetting effects, it also has the problem of being difficult to biodegrade. Summary of the invention

[0006] Based on this, it is necessary to provide an alkylbenzene sulfonic acid with the advantages of strong hard water resistance, strong emulsification ability and easy biodegradation to address the above problems.

[0007] An alkylbenzene sulfonic acid having a structure as shown in Formula I:

[0008]

[0009]

[0010] Wherein, R is a C8-C16 straight chain alkyl or branched chain alkyl, and n is selected from 7 to 9.

[0011] The above-mentioned alkylbenzene sulfonic acid has the advantages of being biodegradable, having strong resistance to hard water and having strong emulsifying ability.

[0012] The present invention also provides a method for preparing the above alkylbenzene sulfonic acid, which is synthesized via the route shown in Formula II:

[0013]

[0014] S1, using fatty alcohol polyoxyethylene ether and phenol as reactants, adding a catalyst, and reacting to obtain phenyl alkyl ether polyoxyethylene ether;

[0015] S2. Using phenyl alkyl ether polyoxyethylene ether and sulfur trioxide as reactants, a reaction is performed to obtain an alkylbenzene sulfonic acid as shown in formula I.

[0016] In one embodiment, the catalyst in S1 is a MgO-supported metal-based catalyst, the supported metal is selected from: one or more of zinc, nickel, and titanium, and the supported amount of the metal is 5-10% of the weight of MgO.

[0017] In one embodiment, the loaded metals are two of zinc, nickel and titanium, and the mass ratio of the two metals is 1:(0.25-4).

[0018] In one embodiment, the reaction temperature in S1 is 120-200°C, and the pressure is 2.5-4.5Mpa. Preferably, the reaction temperature in S1 is 150-180°C, and the pressure is 2-4Mpa.

[0019] In one embodiment, the molar ratio of fatty alcohol polyoxyethylene ether to phenol is 1:(0.5-2). Preferably, the molar ratio of fatty alcohol polyoxyethylene ether to phenol is 1:(0.6-1.5).

[0020] In one embodiment, S2 is specifically as follows: reacting in a sulfonation reactor, mixing phenyl alkyl ether polyoxyethylene ether and sulfur trioxide-air mixed gas, the concentration of sulfur trioxide in the sulfur trioxide-air mixed gas is 4-6vt%, the amount of substance ratio of phenyl alkyl ether polyoxyethylene ether to sulfur trioxide is (1.02-1.04):1, the inlet temperature of the sulfur trioxide-air mixed gas is 48-58°C, and the sulfonation reactor is cooled by circulating cooling water so that the gas temperature at the outlet of the sulfonation reactor is 43-48°C.

[0021] The present invention also provides an alkylbenzene sulfonate having a structure as shown in Formula III:

[0022]

[0023] Wherein, R is a C8-C16 straight chain alkyl or branched chain alkyl, n is selected from 7 to 9, and M is selected from: Na + , K + NH4 + 、C2H7NOH + 、C4H 11 NO2H + 、C6H 15 NO3H + 、C3H9ONH + .

[0024] The above-mentioned alkylbenzene sulfonate has good hard water resistance, emulsification power and biodegradability.

[0025] The present invention also provides a method for preparing the alkylbenzene sulfonate. The alkaline solution and the alkylbenzene sulfonic acid are used as raw materials, and the alkylbenzene sulfonate is obtained through a neutralization reaction.

[0026] In one embodiment, the alkaline solution is selected from: sodium hydroxide solution, potassium hydroxide solution, ammonia water, and alcohol amine.

[0027] The present invention also provides a use of the above alkylbenzene sulfonic acid or alkylbenzene sulfonate in preparing pesticide emulsifiers. The pesticide emulsifiers prepared by using the alkylbenzene sulfonic acid or alkylbenzene sulfonate of the present invention have the advantages of strong emulsification ability and easy biodegradation.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The alkylbenzene sulfonic acid of the present invention has the advantages of being biodegradable, having strong hard water resistance and strong emulsification ability. The alkylbenzene sulfonate of the present invention not only has a good emulsification effect, but also does not produce alkylphenol after degradation, and its biodegradability is comparable to that of conventional linear sodium alkylbenzene sulfonate. The alkylbenzene sulfonic acid and alkylbenzene sulfonate of the present invention are added as surfactants to pesticide emulsifiers to improve the hard water resistance and biodegradability of detergents. DETAILED DESCRIPTION

[0030] For ease of understanding of the present invention, the present invention will be described more fully below in conjunction with preferred embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0032] Example 1

[0033] An alkylbenzene sulfonic acid, the structural formula of which is shown in Formula I, wherein R is C 16 H 33 Straight chain alkyl, n is 7. Its preparation method is as follows:

[0034] (1) Phenol and fatty alcohol polyoxyethylene ether are mixed in a molar ratio of 2:1, and a MgO-loaded metal-based catalyst (the loading amount is 10% of the weight of MgO, and the loaded metals are Zn and Ti, and the mass ratio of the two is 1:4) is added. After mixing evenly, the temperature is controlled to be 195-200°C, the pressure is 2.5-2.8 MPa, and the reaction is carried out for 50-70 minutes to obtain phenyl alkyl ether polyoxyethylene ether. The conversion rate of fatty alcohol polyoxyethylene ether is 70% after testing.

[0035] (2) placing phenyl alkyl ether polyoxyethylene ether in a membrane sulfonation reactor, introducing a sulfur trioxide-air mixed gas, wherein the concentration of sulfur trioxide in the sulfur trioxide-air mixed gas is 5vt%, the molar ratio of phenyl alkyl ether polyoxyethylene ether to sulfur trioxide in the sulfonation reactor is 1:1, and the temperature of the sulfur trioxide-air mixed gas is 50° C. During the reaction, the sulfonation reactor is cooled by circulating cooling water so that the gas temperature at the outlet of the sulfonation reactor is 45° C. After the reaction is completed, alkylbenzene sulfonic acid is obtained after aging.

[0036] An ammonium alkylbenzene sulfonate is prepared by using the alkylbenzene sulfonic acid of Example 1, specifically comprising the following steps: taking concentrated ammonia water and alkylbenzene sulfonic acid, wherein the molar ratio of NH3·H2O to alkylbenzene sulfonic acid is 1:1, adding alkylbenzene sulfonic acid to the concentrated ammonia water while stirring, and after the neutralization reaction is completed, obtaining ammonium alkylbenzene sulfonate. The reaction formula is as follows.

[0037]

[0038] Example 2

[0039] An alkylbenzene sulfonic acid, the structural formula of which is shown in Formula I, wherein R is C 10 H 21 (isodecyl), n is 9. The preparation method is basically the same as that of Example 1, except that step (1): phenol and fatty alcohol polyoxyethylene ether are mixed in a molar ratio of 1:2, MgO-loaded metal-based catalyst (loaded amount is 5% of the weight of MgO, and the loaded metals are Zn and Ni, and the mass ratio of the two is 4:1) with a molar ratio of 8% of the mass of phenol is added, and after mixing evenly, the temperature is controlled to be 120-125°C, the pressure is 4.3-4.5Mpa, and the reaction is carried out for 45-65min to obtain phenyl alkyl ether polyoxyethylene ether, and the conversion rate of fatty alcohol polyoxyethylene ether is 70% after detection.

[0040] A potassium alkylbenzene sulfonate is prepared by using the alkylbenzene sulfonic acid of Example 2, and specifically comprises the following steps: taking a potassium hydroxide solution and an alkylbenzene sulfonic acid, wherein the concentration of the potassium hydroxide solution is 15wt%, and the molar ratio of potassium hydroxide to the alkylbenzene sulfonic acid is 1:1, adding the alkylbenzene sulfonic acid to the potassium hydroxide solution while stirring, and after the neutralization reaction is completed, obtaining the potassium alkylbenzene sulfonate.

[0041] The reaction formula is as follows.

[0042]

[0043] Example 3

[0044] An alkylbenzene sulfonic acid, the structural formula of which is shown in Formula I, wherein R is C8H 17 (4-methylheptyl), n is 7. The preparation method is basically the same as that of Example 1, except that step (1): phenol and fatty alcohol polyoxyethylene ether are mixed at a molar ratio of 1.5:1, MgO-loaded metal-based catalyst (loaded amount is 5% of the weight of MgO, loaded metal is Ni and Ti, and the mass ratio of the two is 1:2) with a molar ratio of 6% of the mass of phenol is added, after mixing evenly, the temperature is controlled to be 150-155°C, the pressure is 3.0-3.2Mpa, the reaction is carried out for 40-60min, and phenyl alkyl ether polyoxyethylene ether is obtained. The conversion rate of fatty alcohol polyoxyethylene ether is 83% after detection.

[0045] An alkylbenzenesulfonic acid diethanolamine is prepared by using the alkylbenzenesulfonic acid of Example 3, and specifically comprises the following steps: taking diethanolamine and alkylbenzenesulfonic acid, wherein the molar ratio of diethanolamine to alkylbenzenesulfonic acid is 1:1, slowly adding alkylbenzenesulfonic acid into the diethanolamine while stirring to avoid violent heat release of the system, and obtaining the alkylbenzenesulfonic acid diethanolamine after the neutralization reaction is completed.

[0046] The reaction formula is as follows.

[0047]

[0048] Example 4

[0049] An alkylbenzene sulfonic acid, the structural formula of which is shown in Formula I, wherein R is C 12 H 25 Straight-chain alkyl, n is 9. The preparation method is basically the same as that of Example 1, except that step (1): phenol and fatty alcohol polyoxyethylene ether are mixed at a molar ratio of 1:1.5, MgO-loaded metal-based catalyst (loaded amount is 5% of the weight of MgO, loaded metal is Ni and Zn, and the mass ratio of the two is 2:1) with a molar ratio of 7% of the mass of phenol is added, after mixing evenly, the temperature is controlled to be 175-180°C, the pressure is 3.8-4.0Mpa, the reaction is carried out for 45-65min, and phenyl alkyl ether polyoxyethylene ether is obtained. The conversion rate of fatty alcohol polyoxyethylene ether is 85% after detection.

[0050] An alkylbenzenesulfonic acid triethanolamine is prepared by using the alkylbenzenesulfonic acid of Example 4, and specifically comprises the following steps: taking triethanolamine and alkylbenzenesulfonic acid, wherein the molar ratio of triethanolamine to alkylbenzenesulfonic acid is 1:1, slowly adding alkylbenzenesulfonic acid into the triethanolamine while stirring to avoid violent heat release of the system, and obtaining the alkylbenzenesulfonic acid triethanolamine after the neutralization reaction is completed.

[0051] The reaction formula is as follows.

[0052]

[0053] Example 5

[0054] An alkylbenzene sulfonic acid, whose structural formula is the same as that of Example 1. The preparation method thereof is substantially the same as that of Example 1, except that step (1) is as follows: phenol and fatty alcohol polyoxyethylene ether are mixed at a molar ratio of 1:1, MgO-loaded metal-based catalyst (loaded amount is 7.2% of the weight of MgO, and the loaded metals are Ti and Ni, and the mass ratio of the two is 1:1) with a molar ratio of 6.5% of the mass of phenol is added, after uniform mixing, the temperature is controlled to be 160-168°C, the pressure is 3.4-3.6Mpa, and the reaction is performed for 50-70min to obtain phenyl alkyl ether polyoxyethylene ether, and the conversion rate of fatty alcohol polyoxyethylene ether is 87% after detection.

[0055] Example 6

[0056] An alkylbenzene sulfonic acid, the structural formula of which is different from that of Example 1 in that n is 9. The preparation method thereof is substantially the same as that of Example 1, except that step (1) comprises mixing phenol and fatty alcohol polyoxyethylene ether at a molar ratio of 1.2:1, adding MgO-supported metal-based catalyst (the supported amount is 8.4% of the weight of MgO, and the supported metals are Zn and Ti, and the mass ratio of the supported metals is 3:4) with a phenol mass ratio of 6.3% by mass, mixing evenly, controlling the temperature to 170-175°C, the pressure to 3.2-3.4 MPa, reacting for 50-70 minutes, and obtaining phenyl alkyl ether polyoxyethylene ether, wherein the conversion rate of the fatty alcohol polyoxyethylene ether is 80% by detection.

[0057] Example 7

[0058] An alkylbenzene sulfonic acid, whose structural formula is the same as that of Example 1. The preparation method thereof is substantially the same as that of Example 1, except that step (1) is as follows: phenol and fatty alcohol polyoxyethylene ether are mixed in a molar ratio of 4:5, MgO-loaded metal-based catalyst (loaded amount is 6.8% of the weight of MgO, and the loaded metals are Zn and Ni, and the mass ratio of the two is 3:2) is added, and after uniform mixing, the temperature is controlled to be 155-165°C, the pressure is 4.4-4.6Mpa, and the reaction is carried out for 45-65min to obtain phenyl alkyl ether polyoxyethylene ether, and the conversion rate of fatty alcohol polyoxyethylene ether is 84% ​​after detection.

[0059] Example 8

[0060] An alkylbenzene sulfonic acid, the difference between its structural formula and that of Example 1 is that n is 9. The preparation method thereof is substantially the same as that of Example 1, except that step (1) comprises mixing phenol and fatty alcohol polyoxyethylene ether at a molar ratio of 1.8:1, adding MgO-supported metal-based catalyst (the loading amount is 9.5% of the weight of MgO, and the supported metals are Ti and Zn, and the mass ratio of the two is 1:3) with a phenol mass ratio of 5.5% by mass, mixing evenly, controlling the temperature to 140-145°C, the pressure to 4.2-4.4 MPa, reacting for 40-60 minutes, and obtaining phenyl alkyl ether polyoxyethylene ether, wherein the conversion rate of the fatty alcohol polyoxyethylene ether is 75% by detection.

[0061] Example 9

[0062] An alkylbenzene sulfonic acid, the structural formula of which is shown in Formula I, wherein R is C 14 H 29Straight-chain alkyl, n is 8. The preparation method is basically the same as that of Example 1, except that step (1): phenol and fatty alcohol polyoxyethylene ether are mixed in a molar ratio of 3:5, MgO-loaded metal-based catalyst (loaded amount is 5.5% of the weight of MgO, and the loaded metals are Ni and Zn, and the mass ratio of the two is 3:1) with a molar ratio of 7.5% of the mass of phenol is added, and after mixing evenly, the temperature is controlled to be 185-190°C, the pressure is 2.7-2.9Mpa, and the reaction is carried out for 50-70min to obtain phenyl alkyl ether polyoxyethylene ether, and the conversion rate of fatty alcohol polyoxyethylene ether is 72% after detection.

[0063] An alkylbenzenesulfonate isopropanolamine is prepared by using the alkylbenzenesulfonic acid of Example 9, and specifically comprises the following steps: taking isopropanolamine and alkylbenzenesulfonic acid, wherein the molar ratio of isopropanolamine to alkylbenzenesulfonic acid is 1:1, slowly adding alkylbenzenesulfonic acid to the isopropanolamine while stirring to avoid violent heat release of the system, and obtaining the alkylbenzenesulfonate isopropanolamine after the neutralization reaction is completed.

[0064] The reaction formula is as follows.

[0065]

[0066] Embodiments 10 to 17

[0067] Examples 10 to 17 are all pesticide microemulsions, and the raw material composition of each example and the mass fraction of each component are shown in Table 1.

[0068] The preparation method of the pesticide microemulsion comprises the following steps:

[0069] (1) Preparation of oil phase: Mix the active ingredient of the pesticide and the esterified vegetable oil, and stir until the active ingredient of the pesticide is completely dissolved in the esterified vegetable oil to obtain the oil phase;

[0070] (2) Preparation of microemulsion: Add emulsifier, hydrotrope, water and oil phase into a container and stir until the mixture is homogeneous and transparent to obtain pesticide microemulsion.

[0071] Table 1 Raw materials and proportions of pesticide microemulsions (wt%)

[0072]

[0073]

[0074] Experimental Example 1

[0075] The ammonium alkylbenzene sulfonate of Example 1 and the diethanolamine alkylbenzene sulfonate of Example 3 were tested for their anti-hard water emulsification and biodegradability. The test results are shown in Table 2.

[0076] Emulsifying power test: In a 100mL stoppered measuring cylinder, add 40mL of surfactant solution containing 0.1% active matter by mass, then add 40mL of 26# white mineral oil, shake 5 times, let stand for 1min, shake 5 times again, repeat 5 times, and observe the time (in seconds (s)) required for the water layer to separate 10mL. The water hardness for preparing the surfactant solution is soft water and 400ppm hard water respectively.

[0077] Biodegradability is characterized by the total BOD value elimination rate (%). When the BOD value is above 50%, it can be considered that the tested substance has basically achieved complete biodegradation.

[0078] Table 2 Performance test results

[0079]

[0080] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0081] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. An alkylbenzene sulfonic acid, characterized in that Having the structure shown in Formula I: Wherein, R is a C8-C16 straight chain alkyl or branched chain alkyl, and n is selected from 7 to 9; The alkylbenzene sulfonic acid is synthesized via the route shown in Formula II: S1, using fatty alcohol polyoxyethylene ether and phenol as reactants, adding a catalyst, and reacting to obtain phenyl alkyl ether polyoxyethylene ether; S2, using phenyl alkyl ether polyoxyethylene ether and sulfur trioxide as reactants to obtain an alkylbenzene sulfonic acid as shown in formula I; The catalyst in S1 is a MgO-supported metal-based catalyst, the supported metals are two of zinc, nickel and titanium, the mass ratio of the two metals is 1:(0.25-4), and the supported amount of the metal is 5-10% of the weight of MgO; In S1, the reaction temperature is 120-200° C., the pressure is 2.5-4.5 MPa, and the molar ratio of fatty alcohol polyoxyethylene ether to phenol is 1:(0.5-2).

2. Alkylbenzene sulfonic acid according to claim 1, characterized in that In S1, the reaction temperature is 150-180° C., the pressure is 2-4 MPa, and the molar ratio of fatty alcohol polyoxyethylene ether to phenol is 1:(0.6-1.5).

3. The alkylbenzene sulfonic acid according to claim 1, characterized in that The S2 is specifically as follows: reacting in a sulfonation reactor, mixing phenyl alkyl ether polyoxyethylene ether and sulfur trioxide-air mixed gas, wherein the concentration of sulfur trioxide in the sulfur trioxide-air mixed gas is 4-6vt%, the amount of substance ratio of phenyl alkyl ether polyoxyethylene ether to sulfur trioxide is (1.02-1.04):1, the inlet temperature of the sulfur trioxide-air mixed gas is 48-58°C, and the sulfonation reactor is cooled by circulating cooling water so that the gas temperature at the outlet of the sulfonation reactor is 43-48°C.

4. An alkylbenzene sulfonate, characterized in that Having the structure shown in Formula III: Wherein, R is a C8-C16 straight chain alkyl or branched chain alkyl, n is selected from 7 to 9, and M is selected from: Na + , K + NH4 + , The preparation method of the alkylbenzene sulfonate uses an alkaline solution and the alkylbenzene sulfonic acid according to claim 1 as raw materials, and obtains the alkylbenzene sulfonate through a neutralization reaction.

5. The alkylbenzene sulfonate according to claim 4, characterized in that The alkaline solution is selected from: sodium hydroxide solution, potassium hydroxide solution, ammonia water, and alcohol amine.

6. Use of the alkylbenzene sulfonic acid according to claim 1 or the alkylbenzene sulfonate according to claim 4 in the preparation of a pesticide emulsifier.

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