CN112457224A - Acid-failure surfactant and preparation method thereof - Google Patents

Acid-failure surfactant and preparation method thereof Download PDF

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Publication number
CN112457224A
CN112457224A CN202011123934.6A CN202011123934A CN112457224A CN 112457224 A CN112457224 A CN 112457224A CN 202011123934 A CN202011123934 A CN 202011123934A CN 112457224 A CN112457224 A CN 112457224A
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surfactant
acid
sodium
deactivating
hydrazide
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卞雨琦
柳森
陈欣
李嘉洁
任毅恒
陈逸菲
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Huaiyin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/59—Nitrogen analogues of carboxyl groups
    • C—CHEMISTRY; METALLURGY
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    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

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Abstract

The invention discloses an acid-ineffective surfactant and a preparation method thereof, belonging to the technical field of surfactants and comprising the following two steps: (a) dissolving sodium carboxyl benzene sulfonate in an organic solvent, adding EDC and sulfo-NHS with the same molar weight, reacting for 2 hours at room temperature to activate carboxyl, adding excessive hydrazine hydrate for reacting overnight, and purifying to obtain a hydrazide-based product of the sodium carboxyl benzene sulfonate; (b) mixing the hydrazide product of sodium carboxybenzenesulfonate and alkyl aldehyde in the same molar amount, dissolving in ethanol, heating, refluxing, cooling and purifying to obtain the surfactant with acid response characteristic. The method has the characteristics of simple synthesis, high stability before use and in use, controllable degradation and the like, and has excellent application prospect, and the surface activity of the method can be comparable with that of the traditional surfactant; the surfactant has good practical effect and excellent controllable decomposition characteristic, can be quickly decomposed and removed under the weak acid regulation, and has strong practicability and innovation.

Description

Acid-failure surfactant and preparation method thereof
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to an acid-losing surfactant and a preparation method thereof.
Background
The surfactant is a new chemical material product which has certain activity and can obviously reduce the surface tension of a solution, is known as industrial monosodium glutamate, has the performances of solubilization, emulsification, wetting, sterilization, disinfection, decontamination and the like, and is widely applied to a plurality of industrial fields of pesticide and medicine processing, cosmetics preparation, textile printing and dyeing and finishing, fiber processing, food processing, oil exploitation, mineral flotation and the like. By 2005, the amount of surfactant used has exceeded 1520 million tons, and the usage rapidly increased at a rate of 3% per year, with a tremendous demand.
However, in most applications, the surfactant residue causes various disadvantages such as foaming, emulsification and the like, seriously affects the industrial production process, and also seriously harms the environment for human bodies and environmental ecosystems. The addition of certain amount of surfactant to detergent can raise the solubility and detergency of detergent, but owing to the toxicity of the surfactant, the surfactant has obvious irritation to skin. Surfactants can also be potentially harmful to ecosystem. In order to meet the increasing health care requirements of people and ensure the sustainable development of human living environment, the development of a surfactant which is as nontoxic and harmless as possible to human bodies and has no pollution to the ecological environment is imperative.
Degradable surfactants are surfactants that can be decomposed into non-surface active substances or converted into new surface active compounds under specific conditions. The weak bonds between the polar and hydrophobic groups of the molecule present in such surfactants break down and can break down into both water soluble and water insoluble products, which can generally be removed by subsequent standardized procedures. This makes them have good surfactant properties under normal conditions, but after use, they can be decomposed and transformed by giving specific conditions to avoid their influence on the subsequent industrial production, environment, etc. Typical decomposition factors include acids, bases, salts, heat, light, and biological factors.
Ideally, the degradable surfactant should degrade rapidly under the lysing conditions and should not require too much lysing agent to achieve sufficient degradation. Unfortunately, none of the existing chemically degradable surfactants possess all of these properties, and there is a need for improved chemically degradable surfactants to better meet commercial needs.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides an acid-ineffective surfactant and a preparation method thereof, which solve the problems that the residue of the surfactant causes troubles to certain industrial production and a series of environmental problems caused by the surfactant.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
an acid-deactivating surfactant, the surfactant being a compound of the structure:
Figure BDA0002732975920000021
wherein R is1、R2、R3、R4Are respectively one of H, OH and COOH, and n is more than or equal to 16.
Further, the preparation method of the acid-ineffective surfactant comprises the following steps:
(a) hydrazidation of sodium carboxybenzenesulfonate
Dissolving sodium carboxybenzenesulfonate in an organic solvent, adding 1-1.5 times molar weight of EDC and sulfo-NHS, reacting at room temperature for more than 2 hours to activate carboxyl, adding 2-10 times molar weight of hydrazine hydrate, reacting overnight, and purifying to obtain a hydrazide-based product of the sodium carboxybenzenesulfonate;
Figure BDA0002732975920000022
(b) preparation of acid-deactivating surfactants
And (3) carrying out hydrazide alkylation on the sodium carboxyl benzene sulfonate in the last step and alkyl aldehyde in a molar ratio of 1: (0.8-1.2), dissolving in ethanol, reacting at 50-70 ℃ for 48 hours, cooling, and purifying to obtain the product with acid response characteristic
Figure BDA0002732975920000023
The surfactant of (1);
in this compound, n.gtoreq.16.
Further, in the step (a), the organic solvent is any one of dichloromethane, chloroform and N, N-dimethylformamide.
Further, in the steps (a) - (b), the sodium carboxybenzene sulfonate is sodium 3-carboxybenzene sulfonate and derivatives thereof.
Further, the sodium carboxybenzene sulfonate, the hydrazide product of the sodium carboxybenzene sulfonate and the R on the benzene ring of the surfactant with acid response characteristics1、R2、R3、R4Respectively is any one of H, OH and COOH.
Further, in the step (b), the alkyl chain of the alkylaldehyde is a hydrocarbon group of 18 carbon atoms or more.
The introduction of a decomposable functional group between a hydrophilic head group and a hydrophobic tail group of the surfactant is an effective way for realizing the degradability of the surfactant, and the method has the characteristics of simple synthesis, comparable surface activity with the traditional surfactant, high stability before use and in use, controllable degradation and the like, and has excellent application prospect.
Has the advantages that: compared with the prior art, the acid-deactivated surfactant and the preparation method thereof have the advantages that the surfactant not only has the characteristics of common surfactants, but also has the acid response characteristic, can normally play a role under neutral and alkaline conditions, and can be rapidly removed due to the fact that hydrazone bonds between hydrophilic groups and hydrophobic groups are hydrolyzed under the acidic condition to be deactivated. Thereby solving the troubles caused by the residue of the surfactant to certain industrial production and a series of environmental problems caused by the complete surfactant entering a natural water system.
Drawings
Fig. 1 is a TEM image of a carbon nanotube.
Detailed Description
In order to further illustrate the present invention, the following detailed description is given with reference to examples.
Further, it is understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope defined in the present application.
An acid-deactivating surfactant, the surfactant being a compound of the structure:
Figure BDA0002732975920000041
in the compound, R1、R2、R3、R4Are respectively one of H, OH and COOH, and n is more than or equal to 16.
A method for preparing an acid-deactivating surfactant, comprising the steps of:
(a) hydrazidation of sodium carboxybenzenesulfonate
Dissolving sodium carboxybenzenesulfonate in an organic solvent, adding 1-1.5 times molar weight of EDC and sulfo-NHS, reacting at room temperature for more than 2 hours to activate carboxyl, adding 2-10 times molar weight of hydrazine hydrate, reacting overnight, and purifying to obtain a hydrazide-based product of the sodium carboxybenzenesulfonate;
Figure BDA0002732975920000042
in the compound, R1、R2、R3、R4Are respectively one of H, OH and COOHAnd (4) seed preparation.
(b) Preparation of acid-deactivating surfactants
And (3) carrying out hydrazide alkylation on the sodium carboxyl benzene sulfonate in the last step and alkyl aldehyde in a molar ratio of 1: (0.8-1.2), dissolving in ethanol, reacting at 50-70 ℃ for 48 hours, cooling, and purifying to obtain the product with acid response characteristic
Figure BDA0002732975920000043
The surfactant of (1).
In the compound, R1、R2、R3、R4Are respectively one of H, OH and COOH, and n is more than or equal to 16.
In the step (a), the organic solvent is any one of dichloromethane, chloroform and N, N-dimethylformamide.
In the steps (a) - (b), the sodium carboxybenzene sulfonate is 3-sodium carboxybenzene sulfonate and derivatives thereof, sodium carboxybenzene sulfonate, hydrazide products of sodium carboxybenzene sulfonate and R on benzene ring of surfactant with acid response characteristic1、R2、R3、R4Respectively is any one of H, OH and COOH.
In the step (b), the alkyl chain of the alkylaldehyde is a hydrocarbon group having 18 or more carbon atoms.
Example 1
A method for preparing an acid-deactivating surfactant, comprising the steps of:
(a) hydrazidation of sodium carboxybenzenesulfonate
Dissolving 3-sodium carboxybenzenesulfonate in N, N-dimethylformamide, adding 1.1 times molar amount of EDC and sulfo-NHS, reacting at room temperature for 3 hours to activate carboxyl, adding 5 times molar amount of hydrazine hydrate, reacting overnight, and purifying to obtain the product;
(b) preparation of acid-deactivating surfactants
And (3) carrying out hydrazide alkylation on the sodium carboxyl benzene sulfonate in the last step and alkyl aldehyde in a molar ratio of 1: 1, dissolving in ethanol, reacting at 65 ℃ for 48 hours, cooling and purifying to obtain the surfactant with acid response characteristic.
Example 2
A method for preparing an acid-deactivating surfactant, comprising the steps of:
(a) hydrazidation of sodium carboxybenzenesulfonate
Dissolving 3, 5-dicarboxybenzenesulfonic acid sodium salt in dimethyl sulfoxide, adding equal molar amount of EDC and sulfo-NHS, reacting for 2 hours at room temperature to activate carboxyl, adding hydrazine hydrate with 2 times molar amount to react overnight, and purifying to obtain a hydrazide-based product of the carboxybenzenesulfonate sodium salt;
(b) preparation of acid-deactivating surfactants
And (3) carrying out hydrazide alkylation on the sodium carboxyl benzene sulfonate in the last step and alkyl aldehyde in a molar ratio of 1: 1.2, dissolving in ethanol, reacting at 60 ℃ for 48 hours, cooling and purifying to obtain the surfactant with acid response characteristic.
Example 3
The surfactant prepared in example 1 was purified and characterized for its hydrogen nuclear magnetic resonance spectrum (1H-NMR) in deuterated chloroform (CDCl)3) From the position of each peak, it can be confirmed that the desired surfactant has been synthesized, as shown in FIG. 1.
Example 4
The surfactant obtained in example 1 was divided into three equal portions of 1g each, and added to phosphate buffers having pH values of 6, 7 and 8, respectively, and after stirring sufficiently for 10min, dialyzed using a dialysis bag having a molecular weight cut-off of 500Da, and after drying, the molecular weight of the powder was measured using Gel Permeation Chromatography (GPC), and as shown in table 1, the molecular weight was measured after the surfactant was left in an environment of different pH values for 10min and after the water-soluble components were removed. Theoretically, at pH 6 the surfactant is completely hydrolyzed, the hydrophilic part is removed by dialysis, the remaining hydrophobic part, molecular weight 237, the surfactant is not decomposed in both pH 7 and 8, and the molecular weight remains 488. The molecular weight was measured by GPC and found that the molecular weight of the pH 6 group was 241, most of which had decomposed, leaving a small amount of undecomposed residue. The 10min decomposition rate of the surfactant was calculated to be 98.4%.
TABLE 1 Gel Permeation Chromatography (GPC) measurement of the molecular weight of powders
pH value of PBS buffer solution Theoretical molecular weight GPC measured molecular weight
6 237 251
7 488 485
8 488 487

Claims (6)

1. An acid-deactivating surfactant characterized by: the surfactant is a compound with the following structure:
Figure FDA0002732975910000011
wherein R is1、R2、R3、R4Are respectively one of H, OH and COOH, and n is more than or equal to 16.
2. A method of making an acid-deactivating surfactant according to claim 1, wherein: the method comprises the following steps:
(a) hydrazidation of sodium carboxybenzenesulfonate
Dissolving sodium carboxybenzenesulfonate in an organic solvent, adding 1-1.5 times molar weight of EDC and sulfo-NHS, reacting at room temperature for more than 2 hours to activate carboxyl, adding 2-10 times molar weight of hydrazine hydrate, reacting overnight, and purifying to obtain a hydrazide-based product of the sodium carboxybenzenesulfonate;
Figure FDA0002732975910000012
(b) preparation of acid-deactivating surfactants
And (3) carrying out hydrazide alkylation on the sodium carboxyl benzene sulfonate in the last step and alkyl aldehyde in a molar ratio of 1: (0.8-1.2), mixing and dissolving in ethanol, reacting at 50-70 ℃, cooling, and purifying to obtain the surfactant with acid response characteristics;
Figure FDA0002732975910000013
in this compound, n.gtoreq.16.
3. The method of claim 2, wherein the acid-deactivating surfactant comprises: in the step (a), the organic solvent is any one of dichloromethane, chloroform and N, N-dimethylformamide.
4. The method of claim 2, wherein the acid-deactivating surfactant comprises: in the steps (a) - (b), the sodium carboxybenzene sulfonate is 3-sodium carboxybenzene sulfonate and derivatives thereof.
5. The method of claim 2, wherein the acid-deactivating surfactant comprises: the sodium carboxyl benzene sulfonate, the hydrazide product of the sodium carboxyl benzene sulfonate and the compound with acid response characteristicR on benzene ring of surfactant1、R2、R3、R4Respectively is any one of H, OH and COOH.
6. The method of claim 2, wherein the acid-deactivating surfactant comprises: in the step (b), the alkyl chain of the alkylaldehyde is a hydrocarbon group with 18 carbon atoms or more.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4491538A (en) * 1982-10-18 1985-01-01 Texaco Inc. Schiff base surfactants
US20190247294A1 (en) * 2017-01-23 2019-08-15 Firmenich Sa Cleavable surfactant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4491538A (en) * 1982-10-18 1985-01-01 Texaco Inc. Schiff base surfactants
US20190247294A1 (en) * 2017-01-23 2019-08-15 Firmenich Sa Cleavable surfactant

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ABD EL-SALAM, F. H.: "Novel fatty heterocyclic compounds: synthesis, surface, antimicrobial and toxic activities", 《OLAJ, SZAPPAN, KOZMETIKA》 *
EISSA, A. M.: "Anionic surface active agents from fatty acid hydrazides containing heterocyclic moiety", 《OLAJ, SZAPPAN, KOZMETIKA》 *
录华 主编: "《精细化工概论》", 30 November 1999 *
王宁 等: "《全国高职高专教育"十三五"规划教材 有机化学 第2版》", 31 January 2018 *
范红俊 主编: "《化学基础》", 31 July 2017 *

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Application publication date: 20210309