CN115926139A - Block polyether sulfonate anionic surfactant and synthesis and application thereof - Google Patents
Block polyether sulfonate anionic surfactant and synthesis and application thereof Download PDFInfo
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Abstract
The invention discloses a block polyether sulfonate anionic surfactant, which has a structural general formula as follows: R-O-PO a ‑EO b ‑SO 3 M, wherein R is C1-C22 alkyl or alkenyl, PO is propoxy, EO is ethoxy, PO and EO are block copolymerization in any sequence, a and b are the average polymerization degree of PO or EO, a is 10-45, and b is 12-120. The block polyether sulfonate anionic surfactant has balanced and excellent performance and is not influenced by electrolyte, pH and temperature; the emulsifying capacity is strong, the interfacial activity is high, and under the condition that the dosage is 1% -10%, oil drops can be emulsified into nanometer-level smaller drops; applied to an aqueous suspension system, can solve the problems of aggregation, expansion and unstable storage of effective substance particles of the aqueous suspension system, and effectively reduce the aqueous propertyThe suspension system has high viscosity, high solid content, low foam and high oil-water compatibility.
Description
Technical Field
The invention relates to an alkoxy polyether surfactant, in particular to a block polyether sulfonate anionic surfactant, a synthesis method thereof and application thereof in an aqueous suspension system.
Background
The surfactant can cause obvious change of the interface state of a solution system, and is a substance with high performance. The surfactant molecules have two different groups of hydrophilicity and hydrophobicity, so that the surfactant substances have hydrophilicity and lipophilicity, and can generate directional arrangement on the interface of the solution. The effective application of the surfactant in the field of aqueous suspension systems in the preparation not only has a relatively large influence on the actual using effect of products, but also has a profound influence on the development of the suspension system surfactant, such as the development of industries of pesticides, printing ink, paint, dye and the like. Especially in recent years, the influence of these industries on safety and environmental protection is highly valued in the world, and the development of environment-friendly green products and corresponding medicaments is urgently needed. Therefore, the development of surfactants for suspension systems is also required to follow the development of the times, and the development is directed toward the development of aqueous and environmental protection.
Conventional anionic surfactants are sensitive to acid and base, have poor tolerance to electrolytes, but are not sensitive to temperature, whereas conventional nonionic surfactants, including block copolymers, are sensitive to temperature, but have strong tolerance to both acid and base and electrolytes, with the advantages and disadvantages of both types of surfactants being evident. In addition, most of the existing block polyether sulfonates are prepared by taking alkylphenol, triethylphenol and the like as initial segments, have large influence on the environment and are not easy to degrade.
In practical applications, development of a functional dispersant which is not easily desorbed from an interface of an original solution system and has relatively good adsorption capacity and stability has been gradually emphasized.
Disclosure of Invention
The invention aims to provide a block polyether sulfonate anionic surfactant, overcomes the defects of the conventional anionic surfactant, and provides a novel surfactant with balanced and excellent performance, acid and alkali resistance and electrolyte resistance; the surfactant can improve the solid content of the aqueous suspension system, reduce the viscosity and solve the problems of aggregation, expansion, unstable storage and the like of effective substance particles of the aqueous suspension system.
The invention also aims to provide a synthesis method of the block polyether sulfonate anionic surfactant.
The invention also aims to provide application of the block polyether sulfonate anionic surfactant.
In order to achieve the purpose, the invention adopts the following technical scheme: a block polyether sulfonate anionic surfactant has a structural general formula as follows: R-O-PO a -EO b -SO 3 M, wherein R is C1-C22 alkyl or alkenyl, PO is propoxy, EO is ethoxy, PO and EO are block copolymerization in any sequence, a and b are the average polymerization degree of PO or EO, a ranges from 10 to 45, and b ranges from 12 to 120.
The block polyether sulfonate anionic surfactant has a structural general formula, wherein R is preferably C1-C18 alkyl or alkenyl.
Preferably, the value range of a in the structural general formula of the block polyether sulfonate anionic surfactant is 20-40, and the value range of b in the structural general formula of the block polyether sulfonate anionic surfactant is 20-60.
The block polyether sulfonate anionic surfactant is preferably represented by the structural general formula, wherein M is Na, K or NH 4 And any one of Mg and Ca.
The synthesis method of the block polyether sulfonate anionic surfactant comprises the following steps:
1) Taking C1-C22 fatty alcohol as an initiator, and carrying out block alkoxylation reaction with propylene oxide and ethylene oxide under the action of a catalyst to obtain block polyether;
2) And (2) carrying out sulfonation reaction on the block polyether obtained in the step 1) by taking sulfamic acid as a sulfonating agent and urea as a catalyst, and neutralizing to obtain the block polyether sulfonate anionic surfactant.
More specifically, the steps of the method include:
A. adding an initiator C1-C22 fatty alcohol and an alkali metal catalyst into a reaction kettle, replacing with nitrogen, heating, and dehydrating under a vacuum condition;
B. introducing metered propylene oxide, carrying out etherification reaction at the temperature of 100-160 ℃ in the kettle, keeping the reaction pressure not more than 0.4Mpa, and carrying out heat preservation and aging after the material introduction is finished;
C. introducing metered ethylene oxide, carrying out etherification reaction at the temperature of 100-160 ℃ in the kettle under the reaction pressure of not more than 0.4Mpa, carrying out heat preservation and aging after the material introduction is finished, and cooling after vacuum degassing to obtain block polyether;
D. and adding a sulfonating agent sulfamic acid and a catalyst urea into the obtained block polyether, performing sulfonation reaction at 80-150 ℃, and neutralizing to obtain the block polyether sulfonate anionic surfactant.
Preferably, the alkali metal catalyst is selected from sodium hydroxide, potassium hydroxide, sodium methoxide or potassium methoxide, and the amount of the catalyst is 1-15% of the weight of the initiator.
In the step A, the dehydration temperature is 80-130 ℃, preferably 100-120 ℃, and the dehydration time is 0.5-6h, preferably 1-3h.
In the step B, the etherification reaction temperature is preferably 110-150 ℃ and the reaction time is preferably 2-20h.
In the step C, preferably, the etherification reaction is carried out at 120-150 ℃ for 2-20h.
In the method, the molar ratio of the initiator to the propylene oxide and the ethylene oxide is 1: (10-45): (12-120), preferably 1: (20-40): (20-60).
In the step D, the sulfonation reaction temperature is preferably 100-120 ℃, and the reaction time is preferably 1-9h, and preferably 2-6h.
In the step D, the mol ratio of the block polyether to the sulfamic acid is 1:1-2, preferably 1:1.05-1.2.
The invention also provides an application of the block polyether sulfonate anionic surfactant in an aqueous suspension system.
Further, the dosage of the block polyether sulfonate anionic surfactant in the aqueous suspension system is 1-10%.
The water-based suspension system is a uniform and stable dispersion system formed by dispersing water-insoluble or water-insoluble effective components (functional components or active components) into water by taking water as a continuous phase. In the above technical solution, the application is not particularly limited, and includes but is not limited to aqueous suspension systems such as pesticides, inks, coatings, electrolytes, detergents, fertilizers, electronics, and personal care products, for example, when the surfactant of the present invention is applied to a pesticide suspension, the solid content of the raw pesticide can be increased from 5% to 45% to 30% to 70%, and the surfactant has low viscosity, less foam, good self-dispersibility, reduced pesticide cost, and improved use effect.
Has the advantages that: the block polyether sulfonate anionic surfactant contains lipophilic groups initiated by fatty alcohol, contains functional groups such as block polyether EO and PO, which are typical of nonionic surfactants, can improve the affinity with effective substances in a suspension system, is not easy to fall off from the particle surface of the effective substances, and provides steric hindrance; meanwhile, the suspension system contains anionic sulfonic acid groups, provides electrostatic repulsion, and is more stable and not influenced by electrolyte, pH and temperature.
The block polyether sulfonate anionic surfactant has the following advantages in an aqueous suspending agent:
1) The emulsifying capacity is strong, the interfacial activity is high, and under the condition that the dosage is 1% -10%, oil drops can be emulsified into nanometer-level smaller drops; the problems of particle aggregation, expansion and unstable storage of effective substances of an aqueous suspension system, wherein the particle size of the effective substances is less than or equal to 5 micrometers and even less than 100 nanometers, are solved, the smaller the particles, the larger the specific surface area, and the larger the amount of the conventional surfactant is needed, and the small amount of the surfactant can well inhibit the particle aggregation expansion, so that the storage stability of the surfactant is greatly improved.
2) High resistance to high temp, acid, alkali and electrolyte, and balanced and excellent performance.
3) The aqueous suspension system has the advantages of effectively reducing the viscosity of the aqueous suspension system, improving the solid content, reducing bubbles, having good oil-water compatibility and inhibiting the aggregation and growth of particles when being applied to the aqueous suspension system. The block polyether sulfonate anionic surfactant can solve the problem of high solid content of an aqueous suspension system, improve the solid content of the aqueous suspension system to 20-70%, and reduce the proportion of water in the system so as to reduce the unit cost and the transportation cost of effective substances and carbon emission. Moreover, the viscosity of the system can be reduced, and the crushing efficiency of the aqueous suspension system can be improved, so that the unit energy consumption is reduced, and the productivity is improved. The special molecular structure of the block polyether sulfonate anionic surfactant can well solve the problems of defoaming under the condition of high solid content of an aqueous suspension system and incompatibility of oil phase and water phase mixing.
4) The raw materials have wide sources, the preparation process is simple, and the cost is low. The related synthesis method has the characteristics of simple synthesis process, mild reaction conditions, no reaction conditions such as ultrahigh temperature and high pressure, high yield and the like.
5) The obtained product is easy to biodegrade, environment-friendly and safe.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples are provided only for illustrating the present invention, and the scope of the present invention is not limited to the specific embodiments but is defined by the claims.
Example 1
A structural formula of C 10 H 21 -O-PO 10 -EO 12 -SO 3 The preparation method of the Na block polyether sulfonate anionic surfactant comprises the following steps:
when the temperature of a kettle is 25 ℃, 158g (1 mol) of decanol and 3.8g of KOH are added into the reaction kettle, air is replaced by nitrogen for 2 times, then the reaction kettle is vacuumized until the vacuum degree is-0.085 Mpa, the temperature is raised to 120 ℃, and the temperature is kept at 120 ℃ for dewatering for 2 hours; and (3) closing the vacuum pump, starting to introduce 580g (10 mol) of propylene oxide, ensuring that the temperature of the materials in the kettle is 125 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 2h after the materials are introduced, continuing to introduce 528g of ethylene oxide (12 mol), ensuring that the temperature of the materials in the kettle is 120 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 2h after the materials are introduced, starting vacuum after the reaction is finished, and cooling after degassing for 0.5h to obtain the intermediate product, namely the block polyether.
Adding the obtained block polyether into a 5000mL flask, adding 102 g of sulfamic acid and 30g of urea, starting stirring, heating to 110 ℃, reacting for 4 hours at 105-110 ℃, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 1.
Example 2
A structural formula of C 10 H 21 -O-PO 12 -EO 120 -SO 3 The block polyether sulfonate anionic surfactant of Na is prepared by the following steps:
when the temperature of a kettle is 25 ℃, 158g (1 mol) of decanol and 8.7g of sodium methoxide are added into the reaction kettle, air is replaced by nitrogen for 2 times, then the reaction kettle is vacuumized until the vacuum degree is-0.085 Mpa, the temperature is raised to 100 ℃, and the temperature is kept at 100 ℃ for dehydration for 3 hours; closing the vacuum pump, starting to introduce 696g (12 mol) of propylene oxide, ensuring the temperature of materials in the kettle to be 130 ℃ during the reaction, ensuring the reaction pressure not to exceed 0.4Mpa, preserving heat and aging for 2h after the materials are introduced, continuing to introduce 5280g (120 mol) of ethylene oxide, ensuring the temperature of materials in the kettle to be 120 ℃ during the reaction, ensuring the reaction pressure not to exceed 0.4Mpa, preserving heat and aging for 4h after the materials are introduced, starting vacuum after the reaction is finished, degassing for 1h, and cooling to obtain the intermediate product, namely the block polyether.
Adding the obtained block polyether into a 10L reactor, adding 102 g of sulfamic acid and 30g of urea, starting stirring, heating to 110 ℃, reacting for 4 hours at 105-110 ℃, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 2.
Example 3
A structural formula of C 10 H 21 -O-PO 40 -EO 12 -SO 3 The block polyether sulfonate anionic surfactant of Na is prepared by the following steps:
when the temperature of a kettle is 25 ℃, 158g (1 mol) of decanol and 9.7g of potassium methoxide are added into the reaction kettle, air is replaced by nitrogen for 2 times, then the reaction kettle is vacuumized until the vacuum degree is-0.085 Mpa, the temperature is raised to 100 ℃, and the temperature is kept at 100 ℃ for dehydration for 3 hours; and (3) closing the vacuum pump, starting to introduce 2320g (40 mol) of propylene oxide, ensuring that the temperature of the materials in the kettle is 130 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 5h after the materials are introduced, continuing to introduce 1320g (30 mol) of ethylene oxide, ensuring that the temperature of the materials in the kettle is 120 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 3h after the materials are introduced, starting vacuum after the reaction is finished, degassing for 1h, and cooling to obtain the intermediate product, namely the block polyether.
Adding the obtained block polyether into a 10L reactor, adding 128 g of sulfamic acid and 30g of urea, starting stirring, heating to 110 ℃, reacting for 4 hours at 105-110 ℃, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 3.
Example 4
A structural formula of C 10 H 21 -O-PO 45 -EO 120 -SO 3 The block polyether sulfonate anionic surfactant of Na is prepared by the following steps:
when the temperature of the kettle is 25 ℃, 158g (1 mol) of decanol and 9.0g of sodium hydroxide are added into the reaction kettle, air is replaced by nitrogen for 2 times, the reaction kettle is vacuumized until the vacuum degree is-0.085 Mpa, the temperature is raised to 100 ℃, and the heat preservation and dehydration are carried out for 3 hours at the temperature of 100 ℃; closing the vacuum pump, starting to introduce 2610g (45 mol) of propylene oxide, ensuring the temperature of the materials in the kettle to be 130 ℃ during the reaction, ensuring the reaction pressure not to exceed 0.4Mpa, preserving heat and aging for 5h after the material introduction is finished, continuing to introduce 5280g (120 mol) of ethylene oxide, ensuring the temperature of the materials in the kettle to be 120 ℃ during the reaction, ensuring the reaction pressure not to exceed 0.4Mpa, preserving heat and aging for 6h after the material introduction is finished, starting the vacuum after the reaction is finished, degassing for 1h, and cooling to obtain the intermediate product, namely the block polyether.
Adding the obtained block polyether into a 20L reactor, adding 158g of sulfamic acid and 50g of urea, starting stirring, heating to 110 ℃, reacting for 4 hours at 105-110 ℃, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 4.
Example 5
A structural formula of C 22 H 45 -O-PO 45 -EO 12 -SO 3 The block polyether sulfonate anionic surfactant of Ka is prepared through the following steps:
adding 326g (1 mol) of behenyl alcohol and 12.6g of KOH into a reaction kettle at the kettle temperature of 25 ℃, replacing air with nitrogen for 2 times, vacuumizing to the vacuum degree of-0.085 Mpa, heating to 100 ℃, and preserving heat at 100 ℃ for dewatering for 2 hours; closing the vacuum pump, starting to introduce 2610g (45 mol) of propylene oxide, ensuring the temperature of the materials in the kettle to be 130 ℃ during the reaction, ensuring the reaction pressure not to exceed 0.4Mpa, preserving heat and aging for 4h after the material introduction is finished, continuing to introduce 528g (12 mol) of ethylene oxide, ensuring the temperature of the materials in the kettle to be 120 ℃ during the reaction, ensuring the reaction pressure not to exceed 0.4Mpa, preserving heat and aging for 2h after the material introduction is finished, starting the vacuum after the reaction is finished, degassing for 0.5h, and cooling to obtain the intermediate product, namely the block polyether.
Adding the block polyether into a flask with the volume of 5000mL, adding 102 g of sulfamic acid and 30g of urea, starting stirring, heating to 110 ℃, reacting for 3 hours at the temperature of 105-110 ℃, and adding potassium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 5.
Example 6
A structural formula of C 2 H 5 -O-PO 12 -EO 25 -SO 3 The preparation method of the Na block polyether sulfonate anionic surfactant comprises the following steps:
adding 46g (1 mol) of ethanol and 3.8g of KOH into a reaction kettle at the kettle temperature of 25 ℃, replacing air with nitrogen for 2 times, vacuumizing to the vacuum degree of-0.085 Mpa, heating to 120 ℃, and preserving heat at 120 ℃ for dewatering for 2 hours; closing the vacuum pump, starting to introduce 696g (12 mol) of propylene oxide, ensuring that the temperature of materials in the kettle is 125 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 2h after the materials are introduced, continuing to introduce 1100g of ethylene oxide (25 mol), ensuring that the temperature of materials in the kettle is 120 ℃ and the reaction pressure is not more than 0.05Mpa during the reaction, preserving heat and aging for 2h after the materials are introduced, starting vacuum after the reaction is finished, and cooling after degassing for 0.5h to obtain the intermediate product, namely the block polyether.
And adding the obtained block polyether into a 5000mL flask, adding 102 g of sulfamic acid and 30g of urea, starting stirring, heating to 110 ℃, reacting at 105-110 ℃ for 3 hours, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 6.
Example 7
A structural formula of C 4 H 9 -O-PO 20 -EO 50 -SO 3 The preparation method of the Na block polyether sulfonate anionic surfactant comprises the following steps:
when the kettle temperature is 25 ℃, adding 74g (1 mol) of butanol and 9.0g of sodium hydroxide into a reaction kettle, replacing air with nitrogen for 2 times, vacuumizing to the vacuum degree of-0.085 Mpa, heating to 100 ℃, and preserving heat at 100 ℃ for dehydration for 3 hours; closing the vacuum pump, starting to introduce 1160g (20 mol) of propylene oxide, ensuring the temperature of the materials in the kettle to be 130 ℃ and the reaction pressure to be not more than 0.4Mpa during the reaction, preserving heat and aging for 3h after the material introduction is finished, continuously introducing 2200g (50 mol) of ethylene oxide, ensuring the temperature of the materials in the kettle to be 120 ℃ and the reaction pressure to be not more than 0.05Mpa during the reaction, preserving heat and aging for 4h after the material introduction is finished, starting vacuum after the reaction is finished, and cooling after the reaction is finished and degassing is carried out for 1h to obtain the intermediate product block polyether.
Adding the obtained block polyether into a 5000mL flask, adding 102 g of sulfamic acid and 30g of urea, starting stirring, heating to 110 ℃, reacting for 5 hours at 105-110 ℃, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 7.
Example 8
A structural formula of C 12 H 25 -O-PO 30 -EO 60 -SO 3 The block polyether sulfonate anionic surfactant of Na is prepared by the following steps:
when the temperature of the kettle is 25 ℃, adding 186.3g (1 mol) of dodecanol and 9.7g of potassium methoxide into the reaction kettle, replacing air with nitrogen for 2 times, vacuumizing to the vacuum degree of-0.085 Mpa, heating to 100 ℃, and preserving heat and dehydrating for 3 hours at the temperature of 100 ℃; closing the vacuum pump, starting to introduce 1740g (30 mol) of propylene oxide, ensuring the temperature of the materials in the kettle to be 130 ℃ and the reaction pressure not to exceed 0.4Mpa during the reaction, preserving heat and aging for 5h after the materials are introduced, continuing to introduce 2640g (60 mol) of ethylene oxide, ensuring the temperature of the materials in the kettle to be 120 ℃ and the reaction pressure not to exceed 0.05Mpa during the reaction, preserving heat and aging for 5h after the materials are introduced, starting the vacuum after the reaction is finished, degassing for 1h, and cooling to obtain the intermediate product, namely the block polyether.
Adding the obtained block polyether into a 10L reactor, adding 128 g of sulfamic acid and 30g of urea, starting stirring, heating to 110 ℃, reacting for 4 hours at 105-110 ℃, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 8.
Example 9
A compound of formulaC 8 H 17 -O-PO 25 -EO 40 -SO 3 The preparation method of the Na block polyether sulfonate anionic surfactant comprises the following steps:
adding 130g (1 mol) of octanol and 9.7g of potassium methoxide into a reaction kettle at the kettle temperature of 25 ℃, replacing air with nitrogen for 2 times, vacuumizing to the vacuum degree of-0.085 Mpa, heating to 100 ℃, and preserving heat at 100 ℃ for dehydration for 3 hours; and (3) closing the vacuum pump, starting to introduce 1450g (45 mol) of propylene oxide, ensuring that the temperature of the materials in the kettle is 130 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 5h after the materials are introduced, continuing to introduce 1760g (120 mol) of ethylene oxide, ensuring that the temperature of the materials in the kettle is 120 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 6h after the materials are introduced, starting vacuum after the reaction is finished, degassing for 1h, and cooling to obtain the intermediate product, namely the block polyether.
And adding the obtained block polyether into a 5000mL flask, adding 158g of sulfamic acid and 40g of urea, starting stirring, heating to 110 ℃, reacting for 4 hours at 105-110 ℃, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 9.
Example 10
A structural formula of C 18 H 37 -O-PO 40 -EO 20 -SO 3 The preparation method of the Na block polyether sulfonate anionic surfactant comprises the following steps:
when the temperature of the kettle is 25 ℃, adding 270.5g (1 mol) of octadecanol and 12.6g of KOH into the reaction kettle, replacing air with nitrogen for 2 times, vacuumizing to the vacuum degree of-0.085 Mpa, heating to 100 ℃, and preserving heat and dehydrating for 2 hours at 100 ℃; and (3) closing the vacuum pump, starting to introduce 2320g (40 mol) of propylene oxide, ensuring that the temperature of the materials in the kettle is 130 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 4 hours after the material introduction is finished, continuously introducing 880g (20 mol) of ethylene oxide, ensuring that the temperature of the materials in the kettle is 120 ℃ and the reaction pressure is not more than 0.4Mpa during the reaction, preserving heat and aging for 2 hours after the material introduction is finished, starting vacuum after the reaction is finished, degassing for 0.5 hour, and cooling to obtain the intermediate product block polyether.
Adding the obtained block polyether into a 5000mL flask, adding 102 g of sulfamic acid and 30g of urea, starting stirring, heating to 110 ℃, reacting for 4 hours at 105-110 ℃, and adding sodium hydroxide for ion exchange to obtain the block polyether sulfonate anionic surfactant 10.
Evaluation of emulsifying ability of surfactant
An appropriate amount of mineral spirit No. 150 was taken, 8% by weight of the block polyether sulfonate anionic surfactant prepared in examples 1 to 10 was added, stirring was carried out for 30 minutes, the obtained sample was added to 250ml of standard hard water with a measuring cylinder to dilute 200 times, and after emulsification was carried out uniformly, the particle size was measured, and the smaller the particle size, the stronger the emulsifying ability was indicated. The results are shown in Table 1.
Comparative example 1
The emulsifying ability was evaluated in the same manner by substituting commercially available conventional nonionic block polyether (designated structural formula shown below) surfactants for the block polyether sulfonate anions of the present invention, and the results are shown in Table 1.
Comparative example 2
With commercially available conventional anionic emulsifiers (C) 12 H 25 C 6 H 4 SO 3 ) 2 The Ca surfactant was used in place of the block polyether sulfonate anion of the present invention, and the emulsifying ability was evaluated in the same manner, and the results are shown in Table 1.
Comparative example 3
The conventional surfactants of comparative example 1 and comparative example 2 were mixed in a mass ratio of 1.
TABLE 1 examples 1-10 emulsification Properties
| Examples | Dilute 200 times droplet size (D90) |
| Example 1 | 98 nm |
| Example 2 | 82 nm |
| Example 3 | 38 nm |
| Example 4 | 91 nm |
| Example 5 | 76 nm |
| Example 6 | 92 nm |
| Example 7 | 40 nm |
| Example 8 | 55 nm |
| Example 9 | 64 nm |
| Example 10 | 42 nm |
| Comparative example 1 | Can not emulsify |
| Comparative example 2 | 2153 nm |
| Comparative example 3 | 1652 nm |
As can be seen from Table 1, under the same conditions, the surfactant prepared by the invention has excellent emulsifying performance, and the single emulsifier can emulsify the solvent oil No. 150 into a nanometer level, so that the emulsifying performance is excellent. The traditional emulsifier needs to be matched and used, and the emulsifying capacity can only meet the conventional requirement.
Example 11
The water-based disperse dye ink comprises the following specific formula (wt%):
dispersing red: 20 percent of
Thiodiglycol: 15 percent of
Diethylene glycol: 8 percent of
Propylene glycol: 3 percent of
Sodium benzoate: 0.3 percent of
Surfactant of example 3: 2 percent
Alkyl naphthalene sulfonate formaldehyde polycondensate sodium salt: 2 percent of
AEO3:5％
Deionized water: make up to 100%
The sanding efficiency of the disperse dye ink is high, the dye can be sanded to D90:72 nm within 5 hours, and after the aging storage test at 54 ℃ for 14 days, a suspension system has no layering, no bottom coagulation and good fluidity, the viscosity of the system is 1.8CPS, the particle size of suspended particles is about 80 nm, and the particle size is basically unchanged.
Example 12
The water-based color paste comprises the following specific formula (wt%):
permanent red: 30 percent of
2 percent of maleic acid acrylic acid copolymer sodium salt
Surfactant 3% of example 5
Xanthan gum 0.1%
0.5 percent of sodium benzoate
0.1 percent of defoaming agent
Deionized water to make up to 100%
The sanding efficiency of the water-based color paste of the embodiment is high, the permanent red particle size can be sanded to D90:80 nm within 40 minutes, which is far higher than the application requirement of the color paste, and the color paste can develop more bright color and has higher refractive index. After a 14-day 54 ℃ aging storage test, the suspension is slightly delaminated, no bottom is formed, the fluidity is good, the viscosity of the system is 100cps, the particle size is not changed, and the application performance of the color paste is greatly improved.
Example 13
The high-content pesticide water suspending agent has the following specific formula (wt%):
diuron: 64 percent
Maleic acid acrylic acid copolymer sodium salt: 4 percent
Surfactant of example 7: 2 percent of
Xanthan gum: 0.1 percent of
Sodium benzoate: 0.5 percent
Glycerol (b): 3 percent of
Defoaming agent: 0.2 percent
Deionized water: make up to 100%
The water suspending agent of the embodiment has high sanding efficiency, the particle size of diuron can be sanded to D90:70 nm within 60 minutes, which is far higher than the sanding efficiency of a conventional surfactant, so that the particle size of the original pesticide is smaller, and the original pesticide is easier to absorb by crops when being used in the field. After the aging storage test at 54 ℃ for 14 days, the suspension is slightly delaminated, no bottom is formed, the fluidity is good, the viscosity of the system is 400cps, the particle size is unchanged, and the application performance of the pesticide is greatly improved.
A large amount of foam is easily generated in the crushing process of the aqueous suspension system, particularly the high-solid-content aqueous suspension system, and the conventional defoaming agent is difficult to eliminate, so that the crushing efficiency is low, the viscosity of the system is increased, the temperature is increased, and even the system is directly solidified in crushing equipment, so that production accidents occur. In the preparation process of the pesticide, the block polyether sulfonate anionic surfactant is added and a small amount of conventional defoaming agent is matched, and even the defoaming agent is not added, the problem of defoaming can be well solved.
Example 14
A nano-pesticide in a nano-aqueous suspension system has the following specific formula:
methylamino abamectin benzoate: 28 percent
Maleic acid acrylic acid copolymer sodium salt: 6 percent
Surfactant of example 10: 3 percent
White oil: 3 percent
Glycerol (b): 3 percent of
Attapulgite clay: 1.5 percent
Sodium benzoate: 0.2 percent of
Defoaming agent: 0.1 percent
Deionized water: make up to 100%
The embodiment has high sanding efficiency, the grain diameter of the emamectin benzoate can be sanded to D90:92 nm within 6 hours, which is far higher than that of the conventional surfactant, so that the grain diameter of the original pesticide particles is smaller, and the original pesticide particles are easier to be absorbed by crops when being used in the field. After the aging storage test at 54 ℃ for 14 days, the suspension system has no layering, no bottom formation, good fluidity, 100cps system viscosity and no change of particle size, and greatly improves the application performance of the pesticide.
As can be seen from examples 11-14, the surfactant disclosed by the invention can be widely applied to an aqueous suspension system, has the advantages of high sanding efficiency, low viscosity of the suspension system and low foam, can effectively inhibit the problem of large particle size expansion in the suspension system, improves the storage stability, and improves the shelf life of goods and the end use performance.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A block polyether sulfonate anionic surfactant, characterized in that the structural general formula of the anionic surfactant is as follows: R-O-PO a -EO b -SO 3 M, wherein R is C1-C22 alkyl or alkenyl, PO is propoxy, EO is ethoxy, PO and EO are block copolymerization in any sequence, a and b are the average polymerization degree of PO or EO, a is 10-45, and b is 12-120.
2. The anionic block polyether sulfonate surfactant as claimed in claim 1, wherein R is C1-C18 alkyl or alkenyl.
3. The anionic block polyether sulfonate surfactant as claimed in claim 1, wherein a is 20-40 and b is 20-60.
4. The anionic block polyether sulfonate surfactant as claimed in claim 1, wherein M is Na, K, NH 4 Mg or Ca.
5. A method of synthesizing the block polyether sulfonate anionic surfactant of claim 1, comprising the steps of:
1) Taking C1-C22 fatty alcohol as an initiator, and carrying out block alkoxylation reaction with propylene oxide and ethylene oxide under the action of a catalyst to obtain block polyether;
2) And (2) carrying out sulfonation reaction on the block polyether obtained in the step 1) by taking sulfamic acid as a sulfonating agent and urea as a catalyst, and neutralizing to obtain the block polyether sulfonate anionic surfactant.
6. The method of synthesis according to claim 5, characterized in that it comprises the following steps:
A. adding an initiator C1-C22 fatty alcohol and an alkali metal catalyst into a reaction kettle, replacing with nitrogen, heating, and dehydrating under a vacuum condition;
B. introducing metered propylene oxide, carrying out etherification reaction at the temperature of 100-160 ℃ in the kettle, keeping the reaction pressure not more than 0.4Mpa, and carrying out heat preservation and aging after the material introduction is finished;
C. introducing metered ethylene oxide, carrying out etherification reaction at the temperature of 100-160 ℃ in the kettle under the reaction pressure of not more than 0.4Mpa, carrying out heat preservation and aging after the material introduction is finished, and cooling after vacuum degassing to obtain block polyether;
D. and adding a sulfonating agent sulfamic acid and a catalyst urea into the obtained block polyether, performing sulfonation reaction at 80-150 ℃, and neutralizing to obtain the block polyether sulfonate anionic surfactant.
7. The synthesis method according to claim 6, wherein the alkali metal catalyst is selected from sodium hydroxide, potassium hydroxide, sodium methoxide or potassium methoxide, and the amount of the catalyst is 1-15% of the weight of the initiator.
8. The synthesis method of claim 6, wherein in the step B, the etherification reaction temperature is 110-150 ℃, and the reaction time is 2-20h;
in the step C, the etherification reaction is carried out at 120-150 ℃ for 2-20h;
in the step D, the sulfonation reaction temperature is 100-120 ℃, and the reaction time is 1-9h;
the molar ratio of the initiator to the propylene oxide and the ethylene oxide is 1: (10-45): (12-120) the molar ratio of the block polyether to the sulfamic acid is 1:1-2.
9. Use of the block polyethersulfonate anionic surfactant of claim 1 in an aqueous suspension system.
10. The use according to claim 9, wherein the block polyethersulphonate anionic surfactant is present in the aqueous suspension in an amount of 1% to 10%.
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