CN111013484B - Alkyl glycoside carboxyl betaine type zwitterionic surfactant and preparation method thereof - Google Patents
Alkyl glycoside carboxyl betaine type zwitterionic surfactant and preparation method thereof Download PDFInfo
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- CN111013484B CN111013484B CN201911162876.5A CN201911162876A CN111013484B CN 111013484 B CN111013484 B CN 111013484B CN 201911162876 A CN201911162876 A CN 201911162876A CN 111013484 B CN111013484 B CN 111013484B
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
Abstract
The invention provides an alkyl glycoside carboxyl betaine type zwitterionic surfactant which has a general formula as follows:
wherein n is the average polymerization degree of 1.1-3.0, and R is the alkyl chain with the carbon number of 8-18. The invention provides a preparation method of alkyl glycoside carboxyl betaine zwitterionic surfactant, which comprises the steps of taking long-chain alkyl polyglycoside, diethylamine, sodium chloroacetate and the like as raw materials, firstly carrying out substitution on the long-chain alkyl polyglycoside, sulfonyl chloride, diethylamine and the like to obtain a long-chain alkyl polyglycoside tertiary amine intermediate, and then carrying out quaternization reaction on the tertiary amine intermediate and sodium chloroacetate to obtain the alkyl glycoside carboxyl betaine zwitterionic surfactant. The alkyl glycoside carboxyl betaine surfactant prepared by the invention not only has the advantages of green, natural, low-toxicity and low-irritation of the original alkyl glycoside, but also has the advantages of good solubility, hard water resistance, temperature resistance, good foam stability and the like of a zwitterionic surfactant.
Description
Technical Field
The invention relates to a zwitterionic surfactant, in particular to a preparation method of an alkyl glycoside carboxyl betaine zwitterionic surfactant.
Background
The Alkyl glycoside (APG) is a mixture obtained by catalytic condensation dehydration of glucose and natural fatty alcohol acid under the condition of having both the characteristics of nonionic and anionic surfactants, has high surfactant content, excellent foaming performance, decontamination performance and compatibility, has small irritation to human skin, and is a nontoxic surfactant which is easy to biodegrade and is environment-friendly. The raw material glucoside is mainly from natural renewable resources such as corn, potato starch and the like, is not restricted by petroleum resources, and is widely applied to the fields of daily chemicals, textiles, food processing, pesticide pharmacy, petroleum exploitation and the like. Some properties are not ideal in practical application, such as the water solubility of alkyl glycoside is poor along with the increase of the length of the alkyl chain, the foam property is obviously reduced along with the increase of the hardness of water, and the like.
Disclosure of Invention
1. The technical problem to be solved is as follows:
the water solubility of the conventional alkyl glycoside surfactant is deteriorated along with the increase of the length of an alkyl chain, and the foam performance is obviously reduced along with the increase of the hardness of water.
2. The technical scheme is as follows:
in order to solve the problems, the invention provides an alkyl glycoside carboxyl betaine type zwitterionic surfactant which has the general formula:
wherein n is the average polymerization degree of 1.1-3.0, and R is the alkyl chain with the carbon number of 8-18.
N is the average polymerization degree of 1.1-2.0, and R is the carbon number of the alkyl chain of 8-14.
The invention also provides a preparation method of the alkyl glycoside carboxyl betaine type zwitterionic surfactant, which comprises the following steps: the first step is as follows: preparing raw materials, long-chain alkyl polyglycoside, diethylamine, sodium chloroacetate, sulfonyl chloride, long-chain alkyl polyglycoside: sulfonyl chloride: diethyl amine: the molar ratio of sodium chloroacetate is 1: 1.0-1.2: 1.1-1.5: 1.1-1.5, second step: carrying out substitution reaction on long-chain alkyl glycoside, sulfonyl chloride and diethylamine to obtain a long-chain alkyl polyglycoside tertiary amine intermediate; the third step: carrying out quaternization reaction on the long-chain alkyl polyglycoside tertiary amine intermediate and sodium chloroacetate to prepare the alkyl polyglycoside carboxyl betaine zwitterionic surfactant.
In the second step, the sulfonyl chloride is added into the long-chain alkyl polyglycoside in a slow dropwise adding mode, and the dropwise adding time is 0.5h-2.0 h.
In the second step, the reaction temperature of the sulfonyl chloride and the long-chain alkyl polyglycoside is 40.0-80.0 ℃.
In the second step, the reaction time of the sulfonyl chloride and the long-chain alkyl polyglycoside is 0.5h-2.0 h.
In the second step, the diethylamine is added dropwise after the reaction of the long-chain alkyl glycoside and the sulfonyl chloride is finished, the dropwise adding time is 0.5h-1.0h, the reaction temperature is 50.0-100.0 ℃, and the reaction time is 3.0h-8.0 h.
In the third step, quaternization of the long-chain alkyl polyglycoside tertiary amine intermediate with the sodium chloroacetate is carried out.
In the third step, the sodium chloroacetate is added in a one-time manner as solid particles.
The quaternization reaction temperature is 50.0-100.0 ℃, and the reaction time is 6.0-12.0 h.
3. Has the advantages that:
the alkyl glycoside carboxyl betaine surfactant prepared by the invention introduces zwitterionic groups of a betaine structure on the basis of the original molecular structure of alkyl glycoside so as to obtain the alkyl glycoside betaine surfactant directly, and the product not only has the advantages of green, natural, low toxicity, low irritation and the like of the original alkyl glycoside, but also has the advantages of good solubility, hard water resistance, temperature resistance, good foam stability and the like of the zwitterionic surfactant.
The invention optimizes the proportion of the raw materials, the reaction temperature, the reaction time, the raw material adding mode and the like in each step, so that the reaction condition is milder and the product yield is higher; by means of process condition optimization measures, the process is more reasonable, the utilization rate of equipment is improved, the production cost is effectively reduced, and industrial production is easier to implement. By optimizing the reaction conditions, the product performance is more stable, and the product quality is easy to control.
Drawings
FIG. 1 shows the surface tension of aqueous solutions of alkylglycoside carboxybetaine surfactants as a function of concentration.
FIG. 2 is a graph showing the change in foaming properties of aqueous solutions of alkylglycoside carboxybetaine surfactants with concentration.
FIG. 3 shows the foam stabilizing performance of aqueous solutions of alkylglycoside carboxybetaine surfactants as a function of concentration.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
The invention provides an alkyl glycoside carboxyl betaine type zwitterionic surfactant which has a general formula as follows:
n is an average polymerization degree of 1.1-3.0, preferably 1.1-2.0, and R is an alkyl chain with a carbon number of 8-18, preferably 8-14.
The invention also provides a preparation method of the alkyl glycoside carboxyl betaine type zwitterionic surfactant, which comprises the following steps: the first step is as follows: preparing raw materials, long-chain alkyl polyglycoside, diethylamine, sodium chloroacetate, sulfonyl chloride, long-chain alkyl polyglycoside: sulfonyl chloride: diethyl amine: the molar ratio of sodium chloroacetate is 1: 1.0-1.2: 1.1-1.5: 1.1-1.5, second step: carrying out substitution reaction on long-chain alkyl glycoside, sulfonyl chloride and diethylamine to obtain a long-chain alkyl polyglycoside tertiary amine intermediate; the third step: carrying out quaternization reaction on the long-chain alkyl polyglycoside tertiary amine intermediate and sodium chloroacetate to prepare the alkyl polyglycoside carboxyl betaine zwitterionic surfactant.
Example 1: adding long-chain alkyl polyglycoside APG0810 with solid content of APG0810 being 32.0g (0.05mol) into a 250ml four-neck flask with a thermometer, a stirrer and a condenser, placing 6.75g (0.05mol) of sulfonyl chloride into a constant-pressure dropping funnel, heating to 50.0 ℃, slowly dropping a sulfonyl chloride solution while stirring, continuing to react for 1.0h after 30min of dropping, and cooling to room temperature; weighing 4.38g (0.06mol) of diethylamine, placing in a constant pressure dropping funnel, heating to 50 ℃ again, slowly dropping diethylamine solution while stirring, continuing to react for 4.0h after dropping for 30min, and cooling to room temperature to obtain APG0810 tertiary amine intermediate; directly adding 7.0g (0.06mol) of sodium chloroacetate solid particles into APG0810 tertiary amine intermediate solution, heating to 80.0 ℃, reacting for 6.0h, distilling the obtained aqueous solution under reduced pressure to remove water, and desalting with a certain amount of ethanol to obtain the target product APG0810 carboxyl betaine surfactant with the product yield of 91.5%.
Example 2: adding long-chain alkyl polyglycoside APG0814 and 32.0g (0.05mol) of APG0814 (with the solid content of 50%) into a 250ml four-neck flask with a thermometer, a stirrer and a condenser, placing 6.75g (0.05mol) of sulfonyl chloride into a constant-pressure dropping funnel, heating to 60.0 ℃, slowly dropping a sulfonyl chloride solution while stirring, continuing to react for 2.0h after 30min of dropping, and cooling to room temperature; weighing 4.38g (0.06mol) of diethylamine, placing in a constant pressure dropping funnel, heating to 60.0 ℃ again, slowly dropping diethylamine solution while stirring, reacting for 4.0h after dropping for 30min, and cooling to room temperature to obtain APG0814 tertiary amine intermediate; directly adding 7.0g (0.06mol) of sodium chloroacetate solid particles into APG0814 tertiary amine intermediate solution, heating to 80.0 ℃, reacting for 6.0h, distilling the obtained aqueous solution under reduced pressure to remove water, and desalting with a certain amount of ethanol to obtain the target product APG0814 carboxyl betaine surfactant with the product yield of 92.4%.
Example 3: adding long-chain alkyl polyglycoside APG1214 and 32.0g (0.05mol) of APG1214 (with solid content of 50%) into a 250ml four-neck flask with a thermometer, a stirrer and a condenser, placing 6.75g (0.05mol) of sulfonyl chloride into a constant-pressure dropping funnel, heating to 60.0 ℃, slowly dropping a sulfonyl chloride solution while stirring, continuing to react for 2.0h after 30min of dropping is finished, and cooling to room temperature; weighing 4.38g (0.06mol) of diethylamine, placing in a constant pressure dropping funnel, heating to 60.0 ℃ again, slowly dropping diethylamine solution while stirring, reacting for 4.0h after dropping for 30min, and cooling to room temperature to obtain APG1214 tertiary amine intermediate; and (3) directly adding 7.0g (0.06mol) of sodium chloroacetate solid particles into APG1214 tertiary amine intermediate solution, heating to 80.0 ℃, reacting for 8.0h, distilling the obtained aqueous solution under reduced pressure to remove water, and desalting with a certain amount of ethanol to obtain the target product APG1214 carboxyl betaine surfactant with the product yield of 91.5%.
Example 4: distilled water was used as a solvent to prepare aqueous solutions of APG0810 carboxybetaine surfactant, APG0814 carboxybetaine surfactant, and APG1214 carboxybetaine surfactant at different concentrations, and the surface tensions thereof were measured at 25 ℃ by the loop method, and the measurement results are shown in FIG. 1. The curve in the figure shows that the surface tension of the solution starts to slightly decrease along with the increase of the concentration, then rapidly decreases and finally tends to be constant, the change rule of the surface tension of the common surfactant along with the concentration is met, and the curve can obtain that the lowest surface tension values of APG0810 carboxyl betaine surfactant, APG0814 carboxyl betaine surfactant and APG1214 carboxyl betaine surfactant respectively reach 30.8mN.m-1、29.5mN.m-1And 28.8mN.m-1The result shows that the synthesized alkyl glycoside carboxyl betaine surfactant has better surface activity.
Example 5: with reference to the modified Ross-Miles method specified in GB/T7462-94, aqueous solutions of APG0810 carboxybetaine surfactant, APG0814 carboxybetaine surfactant and APG1214 carboxybetaine surfactant at different concentrations were prepared, and foaming properties and foam stabilizing properties were measured at 25 ℃. The measurement results are shown in FIG. 2. As can be seen from the curve of FIG. 2, as the concentration of the aqueous solution of the alkyl glycoside carboxybetaine surfactant is increased, the foaming height (H) is increased, when the concentration reaches 0.8g/L, the foaming height tends to be stable, and the foaming height of the APG1214 carboxylic betaine surfactant can reach more than 120mm at most, which indicates that the synthesized alkyl glycoside carboxybetaine surfactant has better foaming property.
As shown in FIG. 3, FIG. 3 shows the foam stability of the alkylglycoside carboxybetaine surfactant, which is represented by the half-life (t1/2) of the time spent when the foam height decays to half of the maximum foam height, and the longer half-life of the alkylglycoside carboxybetaine surfactant indicates better foam stability.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (2)
1. A preparation method of alkyl glycoside carboxyl betaine type zwitterionic surfactant is disclosed, and the surfactant is represented by the general formula:
n is the average polymerization degree and is 1.1-3.0, R is the carbon number of an alkyl chain and is 8-18; the method comprises the following steps: preparing raw materials, long-chain alkyl polyglycoside, diethylamine, sodium chloroacetate, sulfonyl chloride, long-chain alkyl polyglycoside: sulfonyl chloride: diethyl amine: the molar ratio of sodium chloroacetate is 1: 1.0-1.2: 1.1-1.5: 1.1-1.5, second step: carrying out substitution reaction on long-chain alkyl polyglycoside, sulfonyl chloride and diethylamine to obtain a long-chain alkyl polyglycoside tertiary amine intermediate; the third step: carrying out quaternization reaction on the long-chain alkyl polyglycoside tertiary amine intermediate and sodium chloroacetate to prepare alkyl polyglycoside carboxyl betaine zwitterionic surfactant; in the second step, the sulfonyl chloride is added into the long-chain alkyl polyglycoside in a slow dropwise adding modeThe adding time is 0.5h-2.0 h; in the second step, the reaction temperature of the sulfonyl chloride and the long-chain alkyl polyglycoside is 40.0-80.0 ℃; in the second step, the reaction time of the sulfonyl chloride and the long-chain alkyl polyglycoside is 0.5h-2.0 h; in the second step, the diethylamine is added dropwise after the reaction of the long-chain alkyl polyglycoside and the sulfonyl chloride is finished, the dropwise adding time is 0.5h-1.0h, the reaction temperature is 50.0-100.0 ℃, and the reaction time is 3.0h-8.0 h; in the third step, the sodium chloroacetate is added in a one-time mode by solid particles; the quaternization reaction temperature is 50.0-100.0 ℃, and the reaction time is 6.0-12.0 h.
2. The method for producing an alkylglycoside carboxybetaine-type zwitterionic surfactant according to claim 1, wherein: n is the average polymerization degree and is between 1.1 and 2.0, and R is the carbon number of an alkyl chain and is between 8 and 14.
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Effective date of registration: 20221216 Address after: 066400 Xiazhai Xiang Xiang Zhai Cun, Lulong County, Qinhuangdao City, Hebei Province Patentee after: Qinhuangdao normanke Chemical Technology Co.,Ltd. Address before: No.188, Xinle Road, Jiangbei new district, Liuhe District, Nanjing City, Jiangsu Province, 210000 Patentee before: NANJING POLYTECHNIC INSTITUTE |