CN110694546A - Tall oil fatty acid imidazoline sulfonate surfactant and preparation method thereof - Google Patents
Tall oil fatty acid imidazoline sulfonate surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a tall oil fatty acid imidazoline sulfonate surfactant, which has the following main component structural formula:
wherein R is tall oil fatty acid alkyl. The tall oil fatty acid imidazoline sulfonate surfactant intermediate prepared by the invention has low content of diamide, the conversion rate of tall oil fatty acid is more than or equal to 98.5%, and the product isThe product has low irritation, the biodegradability of 7 days is 100%, the atom utilization rate is high, the alkali resistance and the acid resistance are high, the appearance and the stability are good, the excellent paraffin removal and corrosion inhibition effects are realized, the excellent emulsifying and oil stain stripping capabilities are realized on mineral oil such as buffer oil, antirust oil, cutting oil and the like, a new route is provided for the deep processing of tall oil products in China, the utilization rate of the tall oil products can be greatly improved, the added value of the products is improved, and the obvious economic benefit and social benefit are realized.
Description
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a tall oil fatty acid imidazoline sulfonate surfactant and a preparation method thereof.
Background
Tall oil fatty acid is composed of C16、C18The straight chain fatty acid with chain length comprises unsaturated fatty acid such as oleic acid and linoleic acid, and small amount of saturated palmitic acid, stearic acid and abietic acid, and tall oil fatty acid is rich in source, and is obtained by distilling crude tall oilTall oil (also known as tall oil, tall oil) is a by-product of pine alkaline pulping. At present, the direct use of tall oil as a raw material is relatively small, the amount of tall oil used is about 10% of the total amount of crude tall oil, and most of the crude tall oil is separated in multiple stages and then the raw materials are made into other products. Worldwide, the annual production of tall oil is enormous. However, in China, the development of deep processing of tall oil products and the application of the tall oil products to the production of surfactants and detergents with high added values is almost blank. The fatty acid component, which accounts for a large proportion of tall oil, is one of the important raw materials for the surfactant industry.
The imidazoline surfactant is a surfactant with excellent application performance, can generate good synergistic effect when being matched with all other types of surfactants, and has very wide application prospect in the fields of daily chemical industry, metal corrosion inhibition, oil exploitation, textile, printing and dyeing and the like. Nowadays, most commercially available imidazoline surfactant products are lauric acid imidazoline, the content of which is about 35%, and the imidazoline surfactant products are sold in basf, guangzhou Tiancio, guangzhou star industry, Shanghai Kai and the like, mainly because the used quaternizing agent is easy to hydrolyze, the product viscosity is too high, the mass transfer efficiency is influenced, and the conversion rate of an imidazoline intermediate, the product stability, the appearance and the like are further influenced. Tall oil fatty acids are composed primarily of long carbon chain straight chain fatty acids, and imidazoline products synthesized with them tend to be more viscous, while the complexity of the tall oil fatty acid composition also places high demands on the product technology.
The development and updating speed of the surfactant is high in China, the production of a large amount of surfactants completely meets the domestic requirements, but most of green high-efficiency high-value surfactants with high technical level requirements and unique performance still need to be imported in large quantities. Aiming at the market demand for the green renewable biomass raw material surfactant, the tall oil fatty acid derived from the byproduct of the pine papermaking industry is used as the raw material to prepare the tall oil fatty acid imidazoline sulfonate surfactant, so that a new route is provided for deep processing of tall oil products in China, the utilization rate of the tall oil products can be greatly improved, the added value of the products is improved, and the economic benefit and the social benefit are remarkable.
The applications of tall oil fatty acids are nowadays generally synthetic tall oil esters and are used in cutting fluids, which products are oil-soluble and have a very limited range of applications. Patent CN104193774A synthesizes tall oil acid diacetyl amide boric acid ester by using tall oil fatty acid, diethanol amine and boric acid as raw materials, can directly dilute cutting fluid used in metal processing, and has a very narrow application range. S. -F.Wang and the like use tall oil fatty acid and hydroxyethyl ethylenediamine as raw materials, xylene as a water carrying agent to synthesize a tall oil acid imidazoline intermediate, and then the tall oil acid imidazoline intermediate and 3-chlorine-2-hydroxy sodium propane sulfonate are synthesized into tall oil acid sulfonate. The content of diamide by-products in the tall oil acid imidazoline intermediate is too high, the obtained product has deep color and poor stability, and xylene is used as a solvent, the xylene is a 3-class carcinogenic solvent and is not beneficial to industrial popularization (S. -F. Wang, T. Furuno, Z. Cheng. Synthesis of 1-hydroxyhexyl-2-alkyl-2-imidozoline and its derivatives sulfonic acidic surfactant from gum oil fatty acid acid.J. Wood Sci.49(2003) 371-).
Disclosure of Invention
Aiming at the technical problems of component complexity, higher control requirement of a preparation process, too large viscosity of prepared imidazoline, influence on mass transfer efficiency and conversion rate of intermediates and the like of tall oil fatty acid, the invention aims to provide a tall oil fatty acid imidazoline sulfonate surfactant and a preparation method thereof. Aiming at the market demand for the green renewable biomass raw material surfactant, the tall oil fatty acid resource which is a byproduct in the pulping and papermaking industry is deeply processed and recycled, so that the tall oil fatty acid imidazoline sulfonate surfactant is prepared, the viscosity of the product is improved, the surfactant is low in stimulation, the 7-day biodegradability is 100%, the atom utilization rate is high, the alkali resistance is high, and the appearance and the stability are good.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a tall oil fatty acid imidazoline sulfonate surfactant, which has the following main component structural formula:
wherein R is tall oil fatty acid alkyl.
The tall oil fatty acid imidazoline sulfonate surfactant is prepared from commercially available tall oil fatty acid serving as a raw material, wherein the commercially available tall oil fatty acid mainly comprises oleic acid, linoleic acid, abietic acid and a small amount of saturated fatty acid, and R mainly comprises corresponding oleic acid, linoleic acid alkyl groups, abietic acid alkyl groups and saturated fatty acid groups;
oleic acid alkyl group: CH (CH)3(CH2)7CH＝CH(CH2)7 -
Linoleate alkyl group: CH (CH)3(CH2)4CH＝CHCH2CH＝CH(CH2)7 -
Abietic acid alkyl group:
trace saturated fatty acid groups: such as C16 acid alkyl moiety, C18 acid alkyl moiety, CH3(CH2)14-CH3(CH2)16-。
The tall oil fatty acid imidazoline sulfonate surfactant of the present invention contains the main component, water and by-products inevitable during the preparation process, and has a solid content of 30-40%, preferably 35%.
The second aspect of the invention provides a preparation method of the tall oil fatty acid imidazoline sulfonate surfactant, which comprises the following steps:
first step, synthesis of tall oil acid imidazoline intermediate:
under the protection of nitrogen, mixing tall oil fatty acid and organic polyamine, adding phosphoric acid as a catalyst, wherein the molar ratio of the tall oil fatty acid to the organic polyamine to the phosphoric acid is 1 (0.5-2) to (0.005-0.05), adjusting the vacuum residual pressure of a reaction system to 20-300 mmhg, then performing gradient heating reaction until no water is evaporated out, measuring the acid value, adjusting the vacuum, distilling out excessive raw materials, and cooling to obtain a tall oil acid imidazoline intermediate;
step two, quaternization reaction: mixing the tall oil acid imidazoline intermediate obtained in the first step, a low carbon alcohol, an alkali and deionized water, wherein the mass ratio of the tall oil acid imidazoline intermediate to the low carbon alcohol to the alkali to the deionized water is 1 (0.01-1): (0.1-0.4): 2-10), the mixture reacts with alkyl sodium sulfonate at the temperature of 40-100 ℃ (preferably 60-90 ℃), the molar ratio of the tall oil acid imidazoline intermediate to the alkyl sodium sulfonate is 1 (1-3), and the tall oil fatty acid imidazoline sulfonate surfactant is obtained after the reaction is carried out until the content of chloride ions is not changed.
The organic polyamine is at least one of hydroxyethyl ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine, preferably hydroxyethyl ethylenediamine and diethylenetriamine.
The mol ratio of the tall oil fatty acid to the organic polyamine to the phosphoric acid is 1 (1.1-1.5) to 0.005-0.01.
The gradient heating reaction is to heat the mixture from room temperature to 90-110 ℃, perform a reaction for 1-48 h by heating the mixture to 160-180 ℃ in a gradient manner at a heating rate of 5-25 ℃/h, and perform a cyclization reaction for 1-48 h by heating the mixture to 210-250 ℃.
The acid value is that the acid value of the intermediate is less than 3 mgKOH/g.
And adjusting the vacuum to be 2-3 mmhg.
The temperature reduction means that the temperature is 80-100 ℃, and preferably 90 ℃.
The lower alcohol is methanol, ethanol, isopropanol or ethylene glycol, preferably ethanol and isopropanol.
The alkali is NaOH, KOH or Na2CO3。
The mass ratio of the tall oil acid imidazoline intermediate to the low carbon alcohol to the alkali to the deionized water is 1 (0.4-0.6) to (0.1-0.4) to (2.5-4).
The sodium alkyl sulfonate is 3-chloro-2-hydroxy sodium propane sulfonate, 2-bromoethyl sodium sulfonate, 2-chloroethyl sodium sulfonate and sodium allyl sulfonate, and is preferably 3-chloro-2-hydroxy sodium propane sulfonate.
The molar ratio of the tall oil acid imidazoline intermediate to the alkyl sodium sulfonate is 1 (1.1-2).
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the tall oil fatty acid imidazoline sulfonate surfactant intermediate prepared by the invention has low content of diamide, the conversion rate of tall oil fatty acid (kraton FA2) is more than or equal to 98.5%, the product has low irritation, the 7-day biodegradability is 100%, the atom utilization rate is high, the high alkali resistance and acid resistance are realized, the appearance and the stability are good, the excellent wax removal and corrosion inhibition effects are realized, the excellent emulsifying and oil stain stripping capabilities are realized on mineral oil such as buffer oil, rust preventive oil and cutting oil, a new route is provided for deep processing of tall oil products in China, the utilization rate of the tall oil products can be greatly improved, the added value of the products is improved, and the obvious economic benefit and social benefit are realized.
In the preparation method of the tall oil fatty acid imidazoline sulfonate surfactant, the gradient temperature rise is used for better saving energy consumption and avoiding overhigh temperature, too fast reaction and more by-products.
The method takes tall oil fatty acid as a raw material, realizes the intermediate selective regulation and control of complex raw materials through an intermediate measurement and control technology, and performs quaternization reaction by taking a small amount of low-carbon alcohol and water as solvents to obtain the tall oil fatty acid imidazoline sulfonate surfactant.
Drawings
Figure 1 is an infrared spectrum of tall oil fatty acid imidazoline sulfonate surfactant prepared according to example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Tall oil fatty acid (kraton FA2), a reagent used in the present invention, is technical grade, purity is not standard, COA acid number: 196, abietic acid content: 0.8%, unsaponifiable matter: 1.3, iodine value: 125, color, Gardner: 3, the purchasing manufacturer: wuxi Heng diligent Komao Co., Ltd.
The tall oil fatty acid imidazoline sulfonate surfactant prepared in the embodiment 1-10 of the invention has the following main component structural formula:
wherein R is tall oil fatty acid alkyl.
R is mainly corresponding oleic acid, linoleic acid alkyl group, abietic acid alkyl group and saturated fatty acid group;
oleic acid alkyl group: CH (CH)3(CH2)7CH＝CH(CH2)7 -
Linoleate alkyl group: CH (CH)3(CH2)4CH＝CHCH2CH＝CH(CH2)7 -
Abietic acid alkyl group:
trace saturated fatty acid groups: such as C16 acid alkyl moiety, C18 acid alkyl moiety, CH3(CH2)14-CH3(CH2)16-。
Example 1
Taking hydroxyethyl ethylenediamine as an example, the synthetic route of the invention is as follows:
wherein R is specifically:
oleic acid alkyl group: CH (CH)3(CH2)7CH＝CH(CH2)7 -
Linoleate alkyl group: CH (CH)3(CH2)4CH＝CHCH2CH＝CH(CH2)7 -
Abietic acid alkyl group:
trace saturated fatty acid groups: such as C16 acid alkyl moiety, C18 acid alkyl moiety, CH3(CH2)14-CH3(CH2)16-。
Adding (1.5 mol, 156.3 g) hydroxyethyl ethylenediamine into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding (1 mol, 286.2 g) tall oil fatty acid (kraton FA2) and 0.9 g of phosphoric acid under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum residual pressure of a reaction system to 150mmhg, starting timing when the temperature is increased to 100 ℃, increasing the temperature to 170 ℃ in a gradient manner at a temperature increasing rate of 20 ℃/h to react for 2h, increasing the temperature to 220 ℃ to carry out cyclization reaction for 2h, measuring the acid value to be 2.4mgKOH/g after anhydrous evaporation, increasing the conversion rate of the tall oil fatty acid (kraton FA2) to 98.5%, increasing the vacuum to 2mmhg, distilling excessive hydroxyethyl ethylenediamine, reducing the temperature to 90 ℃, obtaining 355.3 g of a tall oil acid imidazoline intermediate, and having a diamide content of 2.5%.
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser tube, the tall oil acid imidazoline intermediate (0.1 mol and 35.4 g), deionized water (132.4 g), ethylene glycol (21.2 g) and sodium hydroxide (0.2mol and 8 g) were added, the temperature was raised to 90 ℃, sodium 3-chloro-2-hydroxypropanesulfonate (0.2mol and 39.3 g) was added, and the reaction was carried out for 5 hours, whereby the chloride ion conversion rate was 99.9%, the conversion rate of the tall oil acid imidazoline intermediate was 92.6%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
The infrared spectra of tall oil fatty acid and tall oil fatty acid imidazoline sulfonate surfactant are shown in fig. 1, and fig. 1 is an infrared spectrum of the tall oil fatty acid imidazoline sulfonate surfactant prepared in example 1 of the present invention. Wherein 2922cm-1The vibration absorption peak of C-H is nearby; 2852cm-1The vibration absorption peak of C-N is nearby; 2852cm-1Is nearby CH2In which C-H bondThe symmetric stretching vibration of the vibrating plate; 1708cm-1The absorption peak is the carbonyl vibration peak on COOH; 1626cm-1The nearby absorption peak is a C ═ O characteristic absorption peak; the tall oil acid imidazoline ring hydrolysis during the quaternization reaction is illustrated; 1190cm-1The characteristic absorption peak of the sulfonic group, the characteristic of the functional group is consistent with the product structure, which indicates that the tall oil fatty acid imidazoline sulfonate surfactant is successfully synthesized.
Example 2
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, a tall oil acid imidazoline intermediate (0.1 mol, 35.4 g) prepared in example 1, 114 g of deionized water, 17.7 g of ethanol and (0.15 mol, 6 g) of sodium hydroxide were added, the temperature was raised to 80 ℃, then (0.15 mol, 29.5 g) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt was added, and reaction was carried out for 6 hours, whereby the conversion rate of chloride ions was 99.7%, the conversion rate of the tall oil acid imidazoline intermediate was 93.5%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Example 3
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, 99.9 g of deionized water, 14.2 g of methanol and 0.15 g of sodium hydroxide (0.4 g) were added to the tall oil acid imidazoline intermediate prepared in example 1, 99.9 g of deionized water, 14.2 g of methanol and 6 g of sodium hydroxide, the temperature was raised to 70 ℃, and then 3-chloro-2-hydroxypropanesulfonic acid sodium salt (0.11 g and 21.6 g) was added to the flask to carry out a reaction for 7 hours, whereby the conversion rate of chloride ions was 99.5%, the conversion rate of the tall oil acid imidazoline intermediate was 92.1%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Example 4
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, a tall oil acid imidazoline intermediate (0.1 mol, 35.4 g) prepared in example 1, 115 g of deionized water, 21.2 g of ethylene glycol and (0.15 mol, 8.4 g) of potassium hydroxide were added, the temperature was raised to 80 ℃, and then (0.15 mol, 29.5 g) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt was added to react for 6 hours, whereby the conversion rate of chloride ions was 99.3%, the conversion rate of the tall oil acid imidazoline intermediate was 93.4%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Example 5
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, a tall oil acid imidazoline intermediate (0.1 mol, 35.4 g) prepared in example 1, 142 g of deionized water, 17.7 g of isopropyl alcohol and (0.2mol, 11.2 g) of potassium hydroxide were added, the temperature was raised to 70 ℃, and then (0.2mol, 39.3 g) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt was added to react for 7 hours, whereby the conversion rate of chloride ions was 99.4%, the conversion rate of the tall oil acid imidazoline intermediate was 94.7%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Example 6
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, a tall oil acid imidazoline intermediate (0.1 mol, 35.4 g) prepared in example 1, 103.3 g of deionized water, 14.2 g of methanol and (0.11 mol, 6.2 g) of potassium hydroxide were added, the temperature was raised to 60 ℃, and then (0.11 mol, 21.6 g) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt was added, and reaction was carried out for 8 hours, whereby the conversion rate of chloride ions was 99.2%, the conversion rate of the tall oil acid imidazoline intermediate was 90.3%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Example 7
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser tube, 137 g of deionized water, 21.2 g of ethanol and 10.6 g of sodium carbonate (0.1 mol) were added to the tall oil acid imidazoline intermediate prepared in example 1, heated to 90 ℃, and then added with 39.3 g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt (0.2mol) to react for 6 hours, whereby the conversion rate of chloride ions was 98.9%, the conversion rate of the tall oil acid imidazoline intermediate was 92.2%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Example 8
Adding (1.2 mol, 123.8 g) diethylenetriamine into a 1L four-neck flask provided with an electric stirrer, a thermometer, a nitrogen inlet pipe and a reduced pressure distillation device, adding (1 mol, 286.2 g) tall oil fatty acid (kraton FA2) and 0.8 g phosphoric acid under the conditions of stirring and nitrogen protection, starting a vacuum pump to adjust the vacuum residual pressure of a reaction system to 180mmhg, starting timing when the temperature is increased to 100 ℃, increasing the temperature to 170 ℃ in a gradient manner at the temperature increasing rate of 20 ℃/h to react for 2h, increasing the temperature to 220 ℃ to carry out cyclization reaction for 3h, measuring the acid value to be 1.8mgKOH/g after anhydrous steaming out, increasing the conversion rate of the tall oil fatty acid (kraton FA2) to 98.9%, increasing the vacuum to 3mmhg, distilling excess diethylenetriamine out, and reducing the temperature to 90 ℃ to obtain 356.3 g of a tall oil acid imidazoline intermediate.
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser tube, the tall oil acid imidazoline intermediate (0.1 mol and 35.3 g), 132.1 g of deionized water, 21.2 g of ethylene glycol and (0.2mol and 8 g) of sodium hydroxide were added, the temperature was raised to 80 ℃, then (0.2mol and 39.3 g) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt was added, and the reaction was carried out for 6 hours, whereby the chloride ion conversion rate was 99.7%, the conversion rate of the tall oil acid imidazoline intermediate was 92.8%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Example 9
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, a tall oil acid imidazoline intermediate (0.1 mol, 35.3 g) prepared in example 8, 114.7 g of deionized water and 21.2 g of ethanol were added, the temperature was raised to 70 ℃, then sodium 3-chloro-2-hydroxypropanesulfonate and potassium hydroxide (0.15 mol, 8.4 g) were added, and the reaction was carried out for 7 hours, whereby the conversion rate of chloride ions was 99.5%, the conversion rate of the tall oil acid imidazoline intermediate was 92.5%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Example 10
In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, a tall oil acid imidazoline intermediate (0.1 mol, 35.3 g) prepared in example 8, 140.5 g of deionized water, 17.7 g of isopropyl alcohol and (0.1 mol, 10.6 g) of sodium carbonate were added, the temperature was raised to 90 ℃, and then (0.2mol, 39.3 g) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt was added, and after 6 hours of reaction, the conversion rate of chloride ions was 99.0%, the conversion rate of the tall oil acid imidazoline intermediate was 91.2%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
Comparative example 1
S. -F.Wang and the like use tall oil fatty acid and hydroxyethyl ethylenediamine as raw materials, xylene as a water carrying agent to synthesize a tall oil acid imidazoline intermediate, and then the tall oil acid imidazoline intermediate and 3-chlorine-2-hydroxy sodium propane sulfonate are synthesized into tall oil acid sulfonate. The content of diamide by-products in the tall oil acid imidazoline intermediate is too high, the obtained product has deep color and poor stability, and the xylene is used as a solvent, is a 3-class carcinogenic solvent and is not beneficial to industrial popularization.
The preparation method comprises the following steps: synthesizing an intermediate HEAI: a four-necked flask equipped with a stirrer, reflux condenser, water separator and thermometer was charged with 56.4g (0.2mol) of tall oil fatty acid, 0.2mol of hydroxyethylethylenediamine and 100 ml of xylene. The reaction was refluxed at 140 ℃ and 150 ℃ until no more water flowed from the trap. And (3) dismantling the water separator, adjusting the pressure of a reaction system to 14.66kPa, increasing the reaction temperature to 250 ℃, and reacting for 30min to obtain a semi-solid tall oil imidazoline intermediate HEAI, wherein the content of diamide is as follows: 4.1 percent.
Quaternization: a three-necked flask was charged with 20ml of deionized water, 10.5g (0.03mol) of HEAI and 5.9g (0.03mol) of 3-chloro-2-hydroxypropanesulfonate and heated to 80-90 ℃. Sodium hydroxide (about 12ml) was added slowly as a 10% aqueous solution with stirring. Until the pH of the reaction mixture drops to 7-8. The resultant mixture was then dried and the water was removed under vacuum. The dried product was dissolved in 50ml of absolute ethanol and the undissolved NaCl was removed by filtration. Distilling the filtrate to recover alcohol to obtain light yellow transparent semisolid.
The performance test of the tall oil fatty acid imidazoline sulfonate surfactants prepared in examples 1-10 and comparative examples is shown in table 1, and the biodegradation degree is tested according to the test method of the biodegradation degree of the GB/T15818-2006 surfactant (foam method determination, degradation degree on the seventh day).
The alkali resistance test is carried out according to the enterprise standard: the surfactant was prepared as a 10.0 wt% aqueous solution, to which a 40.0 wt% aqueous NaOH solution was slowly added with constant stirring, and the addition was immediately stopped when the solution became cloudy as observed.
The alkali resistance was calculated as follows: (1000 Xm)2)/m3
In the formula, m2Represents the mass of NaOH added when becoming turbid, g; m is3Represents the mass of water when becoming cloudy, g.
And (3) viscosity testing: conditions are as follows: temperature 25 ℃, rotation speed: 20PRM, 64 rotors, standard: FORD FLTM BJ 003-02-2001, measurement of Low temperature viscosity, Brookfield viscometer.
The conversion of the intermediate was determined by calculation according to QB/T2118-2012, the free amide content of the test product.
TABLE 1 shows the performance of tall oil fatty acid imidazoline sulfonate surfactants of the present invention
As shown in Table 1, the tall oil fatty acid imidazoline sulfonate surfactant has alkali resistance of more than 300g NaOH/L (lauric acid imidazoline has alkali resistance of about 200g NaOH/L), good alkali resistance, and good fluidity at a solid content of 35%.
The tall oil fatty acid imidazoline sulfonate surfactant is a novel amphoteric surfactant, has good decontamination, solubilization and emulsification, is resistant to strong acid and strong base, has excellent wax removal and corrosion inhibition effects, has excellent emulsification and oil stain stripping capabilities on mineral oil such as buffer oil, antirust oil and cutting oil, and is suitable for systems requiring strong acid (60% sulfuric acid) and strong base (20% NaOH) resistance and temperature resistance.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A tall oil fatty acid imidazoline sulfonate surfactant is characterized in that the structural formula of the main components is as follows:
wherein R is oleic acid alkyl group, linoleic acid alkyl group, abietic acid alkyl group, saturated fatty acid group.
2. The tall oil fatty acid imidazoline sulfonate surfactant of claim 1, wherein in the structural formula:
oleic acid alkyl group: CH (CH)3(CH2)7CH＝CH(CH2)7 -
Linoleate alkyl group: CH (CH)3(CH2)4CH＝CHCH2CH＝CH(CH2)7 -
Abietic acid alkyl group:
saturated fatty acid group: CH (CH)3(CH2)14-CH3(CH2)16-。
3. The tall oil fatty acid imidazoline sulfonate surfactant of claim 1, wherein the solids content is 30-40%.
4. A method of producing the tall oil fatty acid imidazoline sulfonate surfactant of any of claims 1 to 3, comprising the steps of:
first step, synthesis of tall oil acid imidazoline intermediate:
under the protection of nitrogen, mixing tall oil fatty acid and organic polyamine, adding phosphoric acid as a catalyst, wherein the molar ratio of the tall oil fatty acid to the organic polyamine to the phosphoric acid is 1 (0.5-2) to (0.005-0.05), adjusting the vacuum residual pressure of a reaction system to 20-300 mmhg, then performing gradient heating reaction until no water is evaporated out, measuring the acid value, adjusting the vacuum, distilling out excessive raw materials, and cooling to obtain a tall oil acid imidazoline intermediate;
step two, quaternization reaction: mixing the tall oil acid imidazoline intermediate obtained in the first step, a low carbon alcohol, an alkali and deionized water, wherein the mass ratio of the tall oil acid imidazoline intermediate to the low carbon alcohol to the alkali to the deionized water is 1 (0.01-1) to (0.1-0.4) to (2-10), the mixture reacts with alkyl sodium sulfonate at the temperature of 40-100 ℃, the molar ratio of the tall oil acid imidazoline intermediate to the alkyl sodium sulfonate is 1 (1-3), and the tall oil fatty acid imidazoline sulfonate surfactant is obtained after the reaction is carried out until the content of chloride ions is not changed.
5. The method of claim 4, wherein the organic polyamine is at least one of hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine;
the mol ratio of the tall oil fatty acid to the organic polyamine to the phosphoric acid is 1 (1.1-1.5) to 0.005-0.01.
6. The method for preparing the tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the gradient temperature rise reaction is a reaction of raising the temperature from room temperature to 90-110 ℃, raising the temperature to 160-180 ℃ at a rate of 5-25 ℃/h in a gradient manner for 1-48 h, raising the temperature to 210-250 ℃ for 1-48 h, and carrying out cyclization reaction;
the acid value is that the acid value of the intermediate is less than 3 mgKOH/g;
and adjusting the vacuum to be 2-3 mmhg.
7. The method for preparing tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the temperature reduction is 80-100 ℃;
the lower alcohol is methanol, ethanol, isopropanol or ethylene glycol;
the alkali is NaOH, KOH or Na2CO3。
8. The method for preparing tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the mass ratio of the tall oil acid imidazoline intermediate, the low carbon alcohol, the alkali and the deionized water is 1 (0.4-0.6) to (0.1-0.4) to (2.5-4).
9. The method of claim 4, wherein the sodium alkyl sulfonate is selected from the group consisting of sodium 3-chloro-2-hydroxypropanesulfonate, sodium 2-bromoethylsulfonate, sodium 2-chloroethanesulfonate, and sodium allylsulfonate.
10. The method for preparing tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the molar ratio of the tall oil acid imidazoline intermediate to the sodium alkyl sulfonate is 1 (1.1-2).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721634A (en) * | 2019-09-11 | 2020-01-24 | 中国日用化学研究院有限公司 | Tall oil fatty acid imidazoline sulfonate surfactant and preparation method thereof |
| WO2021047588A1 (en) * | 2019-09-11 | 2021-03-18 | 中国日用化学研究院有限公司 | Tall oil fatty acid imidazoline sulfonate surfactant and preparation method therefor |
| CN114605980A (en) * | 2022-04-07 | 2022-06-10 | 上海玖宜聚合物技术有限公司 | Environment-friendly oilfield corrosion inhibitor and preparation method and application thereof |
| CN116178268A (en) * | 2022-12-15 | 2023-05-30 | 上海发凯化工有限公司 | Preparation method of tall oil-based imidazoline succinate sulfonate surfactant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2543852A (en) * | 1946-10-29 | 1951-03-06 | Sandoz Ltd | Surface active derivatives of nitrogen-containing sulfonic acids |
| US4414127A (en) * | 1981-07-06 | 1983-11-08 | Syntex (U.S.A.) Inc. | Contact lens cleaning solutions |
| CN1911938A (en) * | 2006-08-24 | 2007-02-14 | 中国日用化学工业研究院 | Imidazoline amophoteric surface active agent and its synthesis technology |
| CN109797047A (en) * | 2018-12-27 | 2019-05-24 | 上海发凯化工有限公司 | A kind of less salt type ready denier oil acid imidazoline surfactant and preparation method thereof |
-
2019
- 2019-09-11 CN CN201910857434.6A patent/CN110694546A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2543852A (en) * | 1946-10-29 | 1951-03-06 | Sandoz Ltd | Surface active derivatives of nitrogen-containing sulfonic acids |
| US4414127A (en) * | 1981-07-06 | 1983-11-08 | Syntex (U.S.A.) Inc. | Contact lens cleaning solutions |
| CN1911938A (en) * | 2006-08-24 | 2007-02-14 | 中国日用化学工业研究院 | Imidazoline amophoteric surface active agent and its synthesis technology |
| CN109797047A (en) * | 2018-12-27 | 2019-05-24 | 上海发凯化工有限公司 | A kind of less salt type ready denier oil acid imidazoline surfactant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHI-FA WANG ETAL.: "Synthesis of 1-hydroxyethyl-2-alkyl-2-imidazoline and its derivative sulfonate amphoteric surfactant from tall oil fatty acid", 《JOURNAL OF WOOD SCIENCE》 * |
| 王兴国: "《油料科学原理》", 31 August 2017, 中国轻工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721634A (en) * | 2019-09-11 | 2020-01-24 | 中国日用化学研究院有限公司 | Tall oil fatty acid imidazoline sulfonate surfactant and preparation method thereof |
| WO2021047588A1 (en) * | 2019-09-11 | 2021-03-18 | 中国日用化学研究院有限公司 | Tall oil fatty acid imidazoline sulfonate surfactant and preparation method therefor |
| CN114605980A (en) * | 2022-04-07 | 2022-06-10 | 上海玖宜聚合物技术有限公司 | Environment-friendly oilfield corrosion inhibitor and preparation method and application thereof |
| CN114605980B (en) * | 2022-04-07 | 2023-04-11 | 上海玖宜聚合物技术有限公司 | Environment-friendly oilfield corrosion inhibitor and preparation method and application thereof |
| CN116178268A (en) * | 2022-12-15 | 2023-05-30 | 上海发凯化工有限公司 | Preparation method of tall oil-based imidazoline succinate sulfonate surfactant |
| CN116178268B (en) * | 2022-12-15 | 2024-05-14 | 上海发凯化工有限公司 | Preparation method of tall oil-based imidazoline succinate sulfonate surfactant |
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