Cationic surfactant and non-yellowing fabric softener composition and method of making same

Abstract

The present application relates to a kind of cationic surfactants and its preparation method and purposes, softener composition and its preparation method and purposes.First, design, synthesize the cationic surfactant of new structure, using beta-(3,4-epoxycyclohexyl) ethyl trialkoxysilane introduces cycloalkyl and silicon oxygen group, the reason of epoxide group on cycloalkane for ring tension increases the internal stress of molecule, it is easy to carry out nucleophilic substitution reaction at lower temperature and occur ring-opening reaction, thus increase the steric hindrance around N atom, improve the anti-yellowing performance and the stability of surfactant at high temperature by steric hindrance effect.In addition, introduce Si-OR group that can hydrolyze, condense in cationic surfactant, can condense with the hydroxyl group of cellulose molecule, more firmly adsorbed on cellulose surface and play its effect by chemical bond effect, after treating fabric, make it have better softening performance.

Description

Technical Field

[0001] This invention belongs to the technical field of functional finishing agents for textiles, and specifically relates to a cationic surfactant and its preparation method and uses, and a softener composition and its preparation method and uses. Background Technology

[0002] Surfactants in fabric softeners play a significant role in improving the hand feel and softness of fabrics. Researching and developing new softeners is an effective way to increase the added value of textiles. Softeners are generally classified into silicone-based and non-silicone-based products, the latter mainly consisting of cationic products.

[0003] Cationic softeners are inherently positively charged, making them ideal for use as softeners in fabric finishing. Dimethyl quaternary ammonium salts, developed in the early 1950s, were once the most produced class of cationic surfactants. However, they suffered from poor biodegradability, environmental pollution, poor moisture absorption, and an oily feel in treated fabrics. Since the ban on dimethyl quaternary ammonium salts in Europe, the United States, and other countries and regions in the 1990s, ester-based quaternary ammonium salts, especially dimethyl ester-based quaternary ammonium salts, have made significant progress as alternatives to dimethyl quaternary ammonium salts.

[0004] Currently, ester-based quaternary ammonium salts have largely replaced di-long-chain alkyl di-quaternary ammonium salts as the most important fabric softeners on the market. Ester-based quaternary ammonium salts have better biodegradability and hydrolytic stability. However, some ester-based quaternary ammonium salts have poor water resistance after finishing, absorbing moisture or losing their soft and fluffy effects after washing; some ester-based quaternary ammonium salts have poor resistance to yellowing, making the finished fabrics prone to yellowing and affecting their appearance; and some ester-based quaternary ammonium salts are too ionic, which can easily reduce the stability of the softener composition when in contact with negatively charged cellulose, making it difficult for the ester-based quaternary ammonium salts to exert their fabric finishing effect, and resulting in poor finishing effect on cotton fabrics. Especially in commercial hotels or other public places, the fabrics that need finishing are basically white cellulose cotton towels. At the same time, the finishing efficiency requirements are very high. They need to be washed and then dried at high temperature (≥100℃) instead of air-dried at room temperature with general-purpose softeners. Under high temperature conditions, cationic surfactants or amino-containing silane coupling agents are very prone to discoloration, causing the finished towels to turn yellow and seriously affecting their appearance.

[0005] Against this backdrop, it is necessary to improve the molecular structure of cationic surfactants. Based on a cationic surfactant with a special structure, this invention prepares a finishing softener specifically for cellulose-based cotton towels that is resistant to washing and high-temperature conditions, does not easily change color, and the treated fabric has better softness. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to address the problem of yellowing that easily occurs in cellulose-based cotton towels during high-temperature washing and high-temperature drying, and to further improve the softness of fabrics treated with finishing softeners.

[0007] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention is as follows:

[0008] Firstly, a cationic surfactant having the following structural formula: or ;

[0009] Wherein, R1 is a straight-chain hydrocarbon group, branched hydrocarbon group, or cyclic hydrocarbon group with 9 to 29 carbon atoms, preferably, R1 is a straight-chain hydrocarbon group, branched hydrocarbon group, or cyclic hydrocarbon group with 9 to 19 carbon atoms; R2 is a straight-chain hydrocarbon group, branched hydrocarbon group, or cyclic hydrocarbon group with 1 to 6 carbon atoms, preferably, R2 is a straight-chain hydrocarbon group, branched hydrocarbon group, or cyclic hydrocarbon group with 1 to 4 carbon atoms; R3 is any one of methyl, ethyl, n-propyl, or isopropyl, preferably, R3 is any one of methyl or ethyl; X is a halogen atom, preferably, X is selected from Cl, Br, or I atoms.

[0010] Secondly, the preparation method of the above-mentioned cationic surfactant includes: using alkyl diethanolamine as raw material, first reacting it with C10~C30 fatty acids to obtain an esterified product, and then reacting the esterified product with β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to obtain a cationic surfactant.

[0011] The synthetic route for the esterification reaction is as follows:

[0012] ;

[0013] The synthetic route for the ring-opening reaction is as follows:

[0014] ;

[0015] Preferably, the molar ratio of C10~C30 fatty acids to alkyl diethanolamine in the esterification reaction is (2.0~2.4):1;

[0016] Further preferred, the molar ratio of C10~C30 fatty acids to alkyl diethanolamine in the esterification reaction is (2.1~2.3):1;

[0017] Preferably, the esterification reaction uses an esterification catalyst, and the esterification catalyst is preferably p-toluenesulfonic acid;

[0018] Preferably, the temperature of the esterification reaction is controlled at 120~200℃;

[0019] Further optimization involves controlling the esterification reaction temperature at 160~200℃;

[0020] Preferably, the esterification reaction ends and cooling begins when the acid value of the reaction system is below 20 mgKOH / g;

[0021] Further optimization involves stopping the esterification reaction and starting cooling when the acid value of the reaction system is below 15 mgKOH / g.

[0022] Preferably, unreacted fatty acids are removed by vacuum distillation after the esterification reaction is completed;

[0023] Preferably, the ring-opening reaction temperature is controlled at 60~100℃;

[0024] Further optimization involves controlling the ring-opening reaction temperature at 60~90℃;

[0025] Further optimization involves controlling the ring-opening reaction temperature at 60~80℃.

[0026] Preferably, the molar ratio of β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to alkyl diethanolamine is (1.0~1.2):1; more preferably, the molar ratio of β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to alkyl diethanolamine is (1.0~1.1):1.

[0027] Preferably, the ring-opening reaction uses an aqueous solution of a quaternary ammonium salt and HX as a catalyst, wherein the quaternary ammonium salt is preferably any one of tetraalkylammonium chloride or tetraalkylammonium bromide, and the HX is preferably any one of HCl, HBr or HI;

[0028] Preferably, an inert gas or nitrogen is continuously introduced during the esterification and ring-opening reactions.

[0029] Thirdly, the hydrolysis product of the aforementioned cationic surfactant is obtained by reacting the cationic surfactant with water molecules to remove at least one molecule of R3OH, and the hydrolysis product includes at least one Si-OH group.

[0030] Fourthly, the condensation product of the cationic surfactant mentioned above is obtained by condensation reaction of the Si-OH of the hydrolysis product of the cationic surfactant and the Si-OR3 group of the cationic surfactant, while removing at least one molecule of R3OH, and the condensation product obtained includes at least one Si-O-Si bond.

[0031] Alternatively, the condensation product is obtained by combining the Si-OH groups of the hydrolysis products of the above-mentioned cationic surfactants, while removing at least one molecule of R3OH, and the resulting condensation product includes at least one Si-O-Si bond.

[0032] Fifthly, the use of the aforementioned cationic surfactants, hydrolysis products of cationic surfactants, and condensation products of cationic surfactants in the preparation of fabric softeners.

[0033] Sixthly, a softener composition comprising: deionized water, an alcohol solvent, an organic ester of orthosilicate, an imidazoline surfactant, a metal ion salt, an organic antibacterial agent, and the aforementioned cationic surfactant, a hydrolysis product of a cationic surfactant, or a condensation product of a cationic surfactant.

[0034] Preferably, the organic ester of orthosilicate is selected from methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, or the corresponding polymers;

[0035] Preferably, the alcohol solvent is selected from any one or a combination of two of ethanol and isopropanol;

[0036] Preferably, the imidazoline surfactant is selected from hydrocarbon hydroxyethyl imidazoline, wherein the hydrocarbon hydroxyethyl imidazoline is preferably any one or a combination of two of oleic acid hydroxyethyl imidazoline and stearic acid hydroxyethyl imidazoline;

[0037] Metal ion salts are used to neutralize the negative charge on the fiber surface and stabilize cationic surfactants. The preferred metal ion in the metal ion salt is Ca. 2+ Or Mg 2+ ;

[0038] Preferably, the metal ion salt is selected from any one or a combination of two of calcium chloride and magnesium chloride.

[0039] Organic antibacterial agents are used to inhibit the growth of microorganisms such as bacteria and mold, and to prevent odors from appearing in fabric softener compositions. The preferred organic antibacterial agent is dimethyloldimethylhydantoin.

[0040] Further, the composition of the softener composition, by weight, is as follows: 70-80 parts deionized water, 5-20 parts alcohol solvent, 1-5 parts organic ester of orthosilicate, 1-5 parts imidazoline surfactant, 0.05-0.5 parts metal ion salt, 0.05-0.5 parts organic antibacterial agent, and 5-20 parts of the above-mentioned cationic surfactant, hydrolysis product of cationic surfactant, or condensation product of cationic surfactant.

[0041] Seventhly, the use of the softener compositions described above in fabric finishing.

[0042] Preferably, the fabric is a cotton fabric.

[0043] The beneficial effects of this invention are as follows: a novel cationic surfactant structure is designed and synthesized, and cycloalkyl and siloxy groups (Si-OR) are introduced using β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane. Due to the increased internal stress caused by ring strain, the epoxy groups on the cycloalkane are more likely to undergo nucleophilic substitution reactions with N atoms at lower temperatures to open the ring.

[0044] Meanwhile, the introduction of cycloalkyl groups increases the steric hindrance around the N atom and hydroxyl group, which improves the anti-yellowing properties of surfactants and softeners through the steric hindrance effect, and reduces the degree of hydrolysis-condensation reaction of cationic surfactants, thereby improving the stability of surfactants at high temperatures.

[0045] On the other hand, introducing Si-OR siloxy groups that can undergo hydrolysis and condensation reactions into cationic surfactants can condense with the hydroxyl groups of cellulose molecules, adsorb more firmly onto the cellulose surface of the fabric through chemical bonding, and exert its effect, giving the fabric better softness after treatment. Attached Figure Description

[0046] Figure 1 X-ray diffraction (XRD) images of white cotton fabric treated with the softener composition of Example 5 and white cotton fabric not treated with the softener composition.

[0047] Figure 2 The images show surface morphology analysis (SEM) of white cotton fabric treated with the softener composition of Example 5 and white cotton fabric not treated with the softener composition. Detailed Implementation

[0048] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0049] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0050] Unless otherwise specified, the experimental conditions used in the examples are generally in accordance with conventional conditions in the art or the conditions recommended by the reagent company. Unless otherwise specified, the materials and reagents used in the examples can be purchased commercially.

[0051] Example 1

[0052] Lauric acid (C12) and N-methyldiethanolamine (MDEA) were used as initial raw materials, with a molar ratio of 2.25:1. p-Toluenesulfonic acid was used as a catalyst for the esterification reaction, with the amount of p-toluenesulfonic acid added being 0.8% of the total reactant mass. Lauric acid was added to a four-necked flask equipped with a condenser and stirrer. The mixture was heated to 100°C under nitrogen protection to melt the lauric acid. P-Toluenesulfonic acid was then added under continuous stirring and nitrogen purging, and MDEA was added dropwise using a dropping funnel. Simultaneously, the reaction system was heated to 180°C. After 0.5 hours, the MDEA was added dropwise, and the reaction was maintained at 180°C. The reaction was stopped when the acid value of the system fell below 15 mgKOH / g. The mixture was then cooled to 120°C, and unreacted fatty acids were removed by vacuum distillation at a vacuum degree of 0.2 torr.

[0053] When the reaction product was cooled to 70℃, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (JH-O186, Jianghan New Materials) was added, wherein the molar ratio of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to MDEA was 1.05:1. At the same time, 0.1% of tetrabutylammonium chloride and 0.5% of 0.5 mol / L hydrochloric acid aqueous solution of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane by total mass were added as catalysts for the ring-opening reaction. During the reaction, the mixture was continuously stirred and nitrogen gas was introduced for protection, and the temperature of the reaction system was maintained at 70℃. After the reaction was continued for 1 hour, the temperature was lowered to end the reaction.

[0054] The product prepared in Example 1 was characterized, and the results of its synthetic resonance 1H spectrum were as follows: 1H-NMR (400MHz,CDCl3): δ0.87 (6H, dd, J = 7.00, 7.00 Hz), 0.94-1.08 (2H, 1.01 (dd, J =6.80, 6.80 Hz), 1.01 (dd, J = 6.80, 6.80 Hz)), 1.14-1.41 (37H, 1.23 (dddd, J= 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz),1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00,7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00,7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd,J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz),1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.25 (dddd, J = 7.67, 7.67, 7.00,7.00 Hz), 1.25 (dddd, J = 7.67, 7.67, 7.00, 7.00 Hz), 1.26 (dddd, J = 7.00,7.00, 7.00, 7.00 Hz), 1.26 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.28 (qdd,J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.30 (dd, J =7.11, 7.11 Hz), 1.34 (ddd, J = 6.80, 6.80, 5.24 Hz), 1.34 (ddd, J = 6.80,6.80, 5.24 Hz)), 1.44-1.81 (9H, 1.53 (dddd, J = 15.77, 10.26, 2.79, 2.79 Hz),1.55 (dddd, J = 7.67, 7.67, 7.40, 7.40 Hz), 1.55 (dddd, J = 7.67, 7.67, 7.40, 7.40 Hz), 1.59 (dddd, J = 15.77, 2.79, 2.79, 2.79 Hz), 1.63 (dddddd, J =5.24, 5.24, 2.79, 2.79, 2.79, 2.79 Hz), 1.71 (ddd, J = 12.89, 2.79, 2.79 Hz),1.73 (ddd, J = 12.89, 2.79, 2.79 Hz)), 1.82-2.04 (2H, 1.90 (dddd, J = 12.26,2.79, 2.79, 2.79 Hz), 1.95 (dddd, J = 12.26, 10.26, 10.26, 2.79 Hz)), 2.18-2.31 (4H, 2.25 (dd, J = 7.40, 7.40 Hz), 2.25 (dd, J = 7.40, 7.40 Hz)), 2.99(9H, s), 3.16-3.31 (2H, 3.23 (q, J = 7.11 Hz), 3.23 (q, J = 7.11 Hz)), 3.47-3.60 (4H, 3.53 (dd, J = 5.77, 5.77 Hz), 3.53 (dd, J = 5.77, 5.77 Hz)), 4.11(1H, ddd, J = 2.79, 2.79, 2.79 Hz), 4.36-4.55 (5H, 4.43 (ddd, J = 10.26,2.79, 2.79 Hz), 4.48 (dd, J = 5.77, 5.77 Hz), 4.48 (dd, J = 5.77, 5.77 Hz)). .

[0055] Example 2

[0056] Myristic acid (C14) and N-methyldiethanolamine (MDEA) were used as the initial raw materials, with a molar ratio of 2.2:1. Subsequently, the molar ratio of the epoxidized silane coupling agent β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to MDEA was controlled to be 1.1:1, and the rest of the reaction was the same as in Example 1.

[0057] The product prepared in Example 2 was characterized, and the results of its synthesis resonance 1H spectrum were as follows: 1H-NMR (400MHz,CDCl3):

[0058] δ0.86 (6H, dd, J = 7.00, 7.00 Hz), 0.94-1.08 (2H, 1.01 (dd, J = 6.80,6.80 Hz), 1.01 (dd, J = 6.80, 6.80 Hz)), 1.14-1.41 (45H, 1.23 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00,7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00,7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.25 (dddd, J =7.67, 7.67, 7.00, 7.00 Hz), 1.25 (dddd, J = 7.67, 7.67, 7.00, 7.00 Hz), 1.26(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.26 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00Hz), 1.30 (dd, J = 7.11, 7.11 Hz), 1.34 (ddd, J = 6.80, 6.80, 5.24 Hz), 1.34(ddd, J = 6.80, 6.80, 5.24 Hz)), 1.44-1.81 (9H, 1.53 (dddd, J = 15.77, 10.26,2.79, 2.79 Hz), 1.55 (dddd, J = 7.67, 7.67, 7.40, 7.40 Hz), 1.55 (dddd, J =7.67, 7.67, 7.40, 7.40 Hz), 1.59 (dddd, J = 15.77, 2.79, 2.79, 2.79 Hz), 1.63(dddddd, J = 5.24, 5.24, 2.79, 2.79, 2.79, 2.79 Hz), 1.71 (ddd, J = 12.89,2.79, 2.79 Hz), 1.73 (ddd, J = 12.89, 2.79, 2.79 Hz)), 1.82-2.04 (2H, 1.90(dddd, J = 12.26, 2.79, 2.79, 2.79 Hz), 1.95 (dddd, J = 12.26, 10.26, 10.26,2.79 Hz)), 2.18-2.31 (4H, 2.25 (dd, J = 7.40, 7.40 Hz), 2.25 (dd, J = 7.40,7.40 Hz)), 2.99 (9H, s), 3.16-3.31 (2H, 3.23 (q, J = 7.11 Hz), 3.23 (q, J =7.11 Hz)), 3.47-3.60 (4H, 3.53 (dd, J = 5.77, 5.77 Hz), 3.53 (dd, J = 5.77,5.77 Hz)), 4.11 (1H, ddd, J = 2.79, 2.79, 2.79 Hz), 4.36-4.55 (5H, 4.43 (ddd,J = 10.26, 2.79, 2.79 Hz), 4.48 (dd, J = 5.77, 5.77 Hz), 4.48 (dd, J = 5.77,5.77 Hz)).

[0059] Example 3

[0060] Palmitic acid (C16) and N-methyldiethanolamine (MDEA) were used as the initial raw materials, with a molar ratio of 2.15:1. Subsequently, the molar ratio of the epoxidized silane coupling agent β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to MDEA was controlled to be 1.05:1, and the rest of the reaction was the same as in Example 1.

[0061] The product prepared in Example 3 was characterized, and the results of its synthesis resonance 1H spectrum were as follows: 1 H-NMR (400MHz, CDCl3):

[0062] δ0.85 (6H, dd, J = 7.00, 7.00 Hz), 0.94-1.08 (2H, 1.01 (dd, J = 6.80,6.80 Hz), 1.01 (dd, J = 6.80, 6.80 Hz)), 1.14-1.41 (53H, 1.23 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00,7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00,7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.25 (dddd, J = 7.67, 7.67, 7.00, 7.00 Hz), 1.25 (dddd, J = 7.67, 7.67,7.00, 7.00 Hz), 1.26 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.26 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J= 7.00, 7.00, 7.00 Hz), 1.30 (dd, J = 7.11, 7.11 Hz), 1.34 (ddd, J = 6.80,6.80, 5.24 Hz), 1.34 (ddd, J = 6.80, 6.80, 5.24 Hz)), 1.44-1.81 (9H, 1.53(dddd, J = 15.77, 10.26, 2.79, 2.79 Hz), 1.55 (dddd, J = 7.67, 7.67, 7.40,7.40 Hz), 1.55 (dddd, J = 7.67, 7.67, 7.40, 7.40 Hz), 1.59 (dddd, J = 15.77,2.79, 2.79, 2.79 Hz), 1.63 (dddddd, J = 5.24, 5.24, 2.79, 2.79, 2.79, 2.79Hz), 1.71 (ddd, J = 12.89, 2.79, 2.79 Hz), 1.73 (ddd, J = 12.89, 2.79, 2.79Hz)), 1.82-2.04 (2H, 1.90 (dddd, J = 12.26, 2.79, 2.79, 2.79 Hz), 1.95 (dddd,J = 12.26, 10.26, 10.26, 2.79 Hz)), 2.18-2.31 (4H, 2.25 (dd, J = 7.40, 7.40Hz), 2.25 (dd, J = 7.40, 7.40 Hz)), 2.99 (9H, s), 3.16-3.31 (2H, 3.23 (q, J =7.11 Hz), 3.23 (q, J = 7.11 Hz)), 3.47-3.60 (4H, 3.53 (dd, J = 5.77, 5.77Hz), 3.53 (dd, J = 5.77, 5.77 Hz)), 4.11 (1H, ddd, J = 2.79, 2.79, 2.79 Hz),4.36-4.55 (5H, 4.43 (ddd, J = 10.26, 2.79, 2.79 Hz), 4.48 (dd, J = 5.77, 5.77Hz), 4.48 (dd, J = 5.77, 5.77 Hz)). .

[0063] Example 4

[0064] Stearic acid (C18) and N-methyldiethanolamine (MDEA) were used as the initial raw materials, with a molar ratio of 2.1:1. Subsequently, the molar ratio of the epoxide coupling agent β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to MDEA was controlled to be 1.1:1, and the rest of the reaction was the same as in Example 1.

[0065] The product prepared in Example 4 was characterized, and the results of its synthesis resonance 1H spectrum were as follows: 1 H-NMR (400MHz, CDCl3):

[0066] δ0.86 (6H, dd, J = 7.00, 7.00 Hz), 0.94-1.08 (2H, 1.01 (dd, J = 6.80,6.80 Hz), 1.01 (dd, J = 6.80, 6.80 Hz)), 1.14-1.41 (61H, 1.23 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00,7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00,7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23(dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.23 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.23 (dddd, J = 7.00, 7.00,7.00, 7.00 Hz), 1.24 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.24 (dddd, J =7.00, 7.00, 7.00, 7.00 Hz), 1.25 (dddd, J = 7.67, 7.67, 7.00, 7.00 Hz), 1.25(dddd, J = 7.67, 7.67, 7.00, 7.00 Hz), 1.26 (dddd, J = 7.00, 7.00, 7.00, 7.00Hz), 1.26 (dddd, J = 7.00, 7.00, 7.00, 7.00 Hz), 1.28 (qdd, J = 7.00, 7.00,7.00 Hz), 1.28 (qdd, J = 7.00, 7.00, 7.00 Hz), 1.30 (dd, J = 7.11, 7.11 Hz),1.34 (ddd, J = 6.80, 6.80, 5.24 Hz), 1.34 (ddd, J = 6.80, 6.80, 5.24 Hz)),1.44-1.81 (9H, 1.53 (dddd, J = 15.77, 10.26, 2.79, 2.79 Hz), 1.55 (dddd, J =7.67, 7.67, 7.40, 7.40 Hz), 1.55 (dddd, J = 7.67, 7.67, 7.40, 7.40 Hz), 1.59(dddd, J = 15.77, 2.79, 2.79, 2.79 Hz), 1.63 (dddddd, J = 5.24, 5.24, 2.79,2.79, 2.79, 2.79 Hz), 1.71 (ddd, J = 12.89, 2.79, 2.79 Hz), 1.73 (ddd, J =12.89, 2.79, 2.79 Hz)), 1.82-2.04 (2H, 1.90 (dddd, J = 12.26, 2.79, 2.79,2.79 Hz), 1.95 (dddd, J = 12.26, 10.26, 10.26, 2.79 Hz)), 2.18-2.31 (4H, 2.25(dd, J = 7.40, 7.40 Hz), 2.25 (dd, J = 7.40, 7.40 Hz)), 2.99 (9H, s), 3.16-3.31 (2H, 3.23 (q, J = 7.11 Hz), 3.23 (q, J = 7.11 Hz)), 3.47-3.60 (4H, 3.53(dd, J = 5.77, 5.77 Hz), 3.53 (dd, J = 5.77, 5.77 Hz)), 4.11 (1H, ddd, J =2.79, 2.79, 2.79 Hz), 4.36-4.55 (5H, 4.43 (ddd, J = 10.26, 2.79, 2.79 Hz), 4.48 (dd, J = 5.77, 5.77 Hz), 4.48 (dd, J = 5.77, 5.77 Hz)). .

[0067] Example 5

[0068] The proportions of the softener composition, by mass, are as follows: 10 parts of the cationic surfactant prepared in Example 1, 2 parts of oleic acid-based hydroxyethyl imidazoline, 10 parts of ethanol, 0.1 parts of calcium chloride, 75.8 parts of deionized water, 2 parts of JH-T28 (Jianghan New Materials, tetraethyl orthosilicate), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0069] Example 6

[0070] The proportions of the softener composition, by mass, are as follows: 11 parts of the cationic surfactant prepared in Example 1, 2 parts of stearyl hydroxyethyl imidazoline, 10 parts of ethanol, 0.1 parts of calcium chloride, 73.8 parts of deionized water, 3 parts of JH-T32 (Jianghan New Materials, tetraethyl orthosilicate oligomer, average degree of polymerization 1-2), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0071] Example 7

[0072] The proportions of the softener composition, by mass, are as follows: 10 parts of the cationic surfactant prepared in Example 2, 2 parts of oleic acid-based hydroxyethyl imidazoline, 10 parts of isopropanol, 0.1 parts of calcium chloride, 75.8 parts of deionized water, 2 parts of JH-T28 (Jianghan New Materials, tetraethyl orthosilicate), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0073] Example 8

[0074] The proportions of the softener composition, by mass, are as follows: 11 parts of the cationic surfactant prepared in Example 2, 2 parts of stearyl hydroxyethyl imidazoline, 10 parts of isopropanol, 0.1 parts of calcium chloride, 73.8 parts of deionized water, 3 parts of JH-T40 (Jianghan New Materials, tetraethyl orthosilicate oligomer, average degree of polymerization 4-5), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0075] Example 9

[0076] The proportions of the softener composition, by mass, are as follows: 10 parts of the cationic surfactant prepared in Example 3, 2 parts of oleic acid-based hydroxyethyl imidazoline, 10 parts of ethanol, 0.1 parts of calcium chloride, 75.8 parts of deionized water, 2 parts of JH-T28 (Jianghan New Materials, tetraethyl orthosilicate), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0077] Example 10

[0078] The proportions of the softener composition, by mass, are as follows: 11 parts of the cationic surfactant prepared in Example 3, 2 parts of stearyl hydroxyethyl imidazoline, 10 parts of ethanol, 0.1 parts of calcium chloride, 73.8 parts of deionized water, 3 parts of JH-T32 (Jianghan New Materials, tetraethyl orthosilicate oligomer, average degree of polymerization 1-2), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0079] Example 11

[0080] The proportions of the softener composition, by mass, are as follows: 10 parts of the cationic surfactant prepared in Example 4, 2 parts of oleic acid-based hydroxyethyl imidazoline, 10 parts of ethanol, 0.1 parts of calcium chloride, 75.8 parts of deionized water, 2 parts of JH-T28 (Jianghan New Materials, tetraethyl orthosilicate), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0081] Example 12

[0082] The proportions of the softener composition, by mass, are as follows: 11 parts of the cationic surfactant prepared in Example 4, 2 parts of stearyl hydroxyethyl imidazoline, 10 parts of ethanol, 0.1 parts of calcium chloride, 73.8 parts of deionized water, 3 parts of JH-T40 (Jianghan New Materials, tetraethyl orthosilicate oligomer, average degree of polymerization 4-5), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0083] Comparative Example 1

[0084] Stearic acid (C18) and N-methyldiethanolamine (MDEA) were used as the initial raw materials, with a molar ratio of 2.1:1. Subsequently, the molar ratio of the epoxidized silane coupling agent γ-glycidoxypropyltrimethoxysilane to MDEA was controlled to be 1.1:1, and the remaining reactions were the same as in Example 1.

[0085] Comparative Example 2

[0086] The proportions of the softener composition, by mass, are as follows: 10 parts of the cationic surfactant prepared in Comparative Example 1, 2 parts of oleic acid-based hydroxyethyl imidazoline, 10 parts of ethanol, 0.1 parts of calcium chloride, 75.8 parts of deionized water, 2 parts of JH-T28 (Jianghan New Materials, tetraethyl orthosilicate), and 0.1 parts of the antibacterial agent dimethyloldimethylhydantoin.

[0087] Weigh the formulations of Examples 5-12 and Comparative Example 2 according to the material proportions, stir and dissolve them at room temperature and pressure to obtain the corresponding softener compositions.

[0088] Low-temperature stability test of softener: The softener composition products prepared in Examples 5-12 and Comparative Example 2 were placed in a refrigerator at (-5±2)℃ for 24 hours, taken out and left to stand at room temperature for 1 hour to allow them to return to room temperature. The presence of crystallization or precipitation was then observed.

[0089] High-temperature stability test of softener: The softener composition products prepared in Examples 5-12 and Comparative Example 2 were placed in an oven at (40±2)℃ for 24 hours. They were then taken out and immediately observed for precipitation, layering or turbidity.

[0090] Fabric finishing test

[0091] Pretreatment: Cut the white cotton fabric into a certain size, first wash it in soapy water for 15 minutes, and then let it air dry naturally for later use.

[0092] The pretreated white cotton fabric was cut into 120×120 mm square pieces. The white cotton fabric was then immersed in the softener compositions of Examples 5-12 and Comparative Example 2 at a mass ratio of 1:25 (fabric to softener composition). After immersion in a water bath at (50±2)℃ for 30 min, the fabric was removed, fixed, and placed in a 100℃ oven for 15 min. The dried fabric pieces were then removed and allowed to rehydrate at room temperature for at least 24 h.

[0093] Whiteness value test: Randomly select points on the white cotton fabric and measure its reflectance with a digital whiteness meter. Record the measurement results and take the average value as the whiteness value of the sample.

[0094] Softness test: The bending stiffness (stiffness) of the treated fabric is tested using an automatic fabric stiffness tester. The change in bending stiffness is used to judge the improvement in fabric softness.

[0095] Dynamic friction coefficient test: Using a fabric style tester, referring to the standard FJ 552.2-1985, the dynamic friction coefficient (μS) of the fabric is determined. The specific operation is as follows: the treated white cotton greige fabric sample is cut into two different lengths of 30×77mm and 30×28mm respectively. The longer sample is fixed on the worktable of the style tester, and the shorter sample is placed on the starting position of the longer sample with the same fabric surface direction for testing.

[0096] Fabric wrinkle recovery angle test: Referring to the standard GB / T3819-1997, the recovery angle of the fabric is determined using a laser fabric wrinkle elasticity meter with a vertical method. After the fabric is folded under pressure, a crease will appear. After the pressure is released, the sample will recover along the crease, generating an angle. The angle of recovery is measured to assess the crease recovery ability of the fabric.

[0097] X-ray diffraction (XRD) analysis: XRD was performed on white cotton fabric treated with the softener composition of Example 5 and white cotton fabric not treated with the softener composition to analyze the changes in the crystalline morphology of cotton fibers before and after treatment.

[0098] Surface morphology analysis (SEM): After drying, samples of white cotton fabric treated with the softener composition of Example 5 and white cotton fabric not treated with the softener composition were taken, glued to a metal test bench with conductive adhesive, vacuum sputtered with gold, and the morphological characteristics of the samples were observed using a scanning electron microscope.

[0099] The stability, whiteness value, and softness test results of the softener compositions prepared in Examples 5-12 and Comparative Example 2 are listed in Table 1.

[0100] Table 1

[0101]

[0102] The evaluation of fabric softness involves multiple aspects. Fabric surface properties (coefficient of kinetic friction) reflect the "smoothness" of the fabric's feel; fabric bending properties (bending stiffness) reflect the "crispness" of the fabric's feel; and fabric wrinkle recovery angle reflects the "straightness" of the fabric's feel. The smoother, crisper, and straighter the fabric feels, the higher its softness, and the better the effect of the corresponding softener composition. Analysis of the test data in Table 1 shows that the softener compositions of Examples 5-12 all exhibited good stability. Under baking and drying conditions, the fabrics treated with Examples 5-12 showed significantly higher whiteness and wrinkle recovery angle, while the bending stiffness and coefficient of kinetic friction were lower. This indicates that the fabrics treated with the softener compositions of Examples 5-12, using the cationic surfactant prepared in Examples 1-4 as the key component, have better softness and stronger resistance to yellowing.

[0103] Comparative Example 2 used the cationic surfactant prepared in Comparative Example 1. Its nitrogen element had less steric hindrance than the cationic surfactants prepared in Examples 1-4, resulting in lower anti-yellowing performance. Furthermore, the corresponding Si-OR groups were more prone to hydrolysis-condensation reactions in alkaline aqueous solutions, forming condensation products with low water solubility. Consequently, the softener composition of Comparative Example 2 showed turbidity and bottom sedimentation after being placed in an oven at (40±2)℃ or (-5±2)℃ for 24 hours. In addition, the fabric treated with the softener composition of Comparative Example 2 exhibited higher bending stiffness, a higher coefficient of dynamic friction, and a lower wrinkle recovery angle. The test results indicate that the softener composition of Comparative Example 2 reduced the softening effect on the treated fabric.

[0104] The changes in the crystal morphology of cotton fibers before and after treatment with the softener composition in Example 5 are listed below. Figure 1 From Figure 1 As can be seen, the X-ray diffraction curves of cotton fibers before and after treatment with the finishing agent are basically similar, and the diffraction peaks do not change significantly. Obvious diffraction peaks are observed at 14.7°, 16.9°, 22.5°, and 34.1°, thus confirming it as cellulose crystal form I. This indicates that treating cotton fibers with the softener composition of Example 5 does not alter the basic crystal structure within the cotton fibers.

[0105] The changes in surface morphology of cotton fibers before and after treatment with the softener composition in Example 5 are listed below. Figure 2 From Figure 2 As can be seen, the surface of the untreated cotton fabric is significantly rougher, with microstructures such as barbs, burrs, and wrinkles. After treatment with the softener composition of Example 5, the surface of the cotton fibers is smoother and flatter, and the microstructures such as barbs, burrs, and wrinkles are significantly reduced. This is because the cationic surfactant adsorbs onto the surface of the cotton fibers through electrostatic interaction and Si-OC chemical bonding, filling the surface wrinkles of the cotton fibers and reducing friction between the cotton fibers, thereby giving the fabric a fluffy and soft feel.

[0106] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of them. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention. Although the specific embodiments of the present invention have been described above, they are not intended to limit the protection scope of the present invention. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art without creative effort based on the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A cationic surfactant, characterized in that, The structural formulas of cationic surfactants include: or R1 is a straight-chain hydrocarbon group, branched hydrocarbon group, or cyclic hydrocarbon group with 9 to 29 carbon atoms; R2 is a straight-chain hydrocarbon group, branched hydrocarbon group, or cyclic hydrocarbon group with 1 to 6 carbon atoms; R3 is any one of methyl, ethyl, n-propyl, or isopropyl; X is a halogen atom.

2. A method for preparing a cationic surfactant, characterized in that, Using alkyl diethanolamine as a raw material, it is first esterified with C10~C30 fatty acids under esterification catalyst conditions to obtain esterified products. The esterified products are then reacted with β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane under quaternary ammonium salt catalyst and HX conditions to obtain cationic surfactants. Wherein, R1 is a straight-chain hydrocarbon group, branched hydrocarbon group, or cyclic hydrocarbon group with 9 to 29 carbon atoms; R2 is a straight-chain alkyl group, branched alkyl group, or cyclic alkyl group with 1 to 6 carbon atoms; R3 is any one of methyl, ethyl, n-propyl, or isopropyl; X is a halogen atom; The synthetic route for esterification is as follows: ； The synthetic route for the ring-opening reaction is as follows: 。 3. The method for preparing the cationic surfactant according to claim 2, characterized in that, The molar ratio of C10~C30 fatty acids to alkyl diethanolamine in the esterification reaction is (2.0~2.4):1; And / or, the esterification reaction uses an esterification catalyst, said esterification catalyst being p-toluenesulfonic acid; And / or, the temperature of the esterification reaction is controlled at 120~200℃; And / or, when the acid value of the reaction system is below 20 mgKOH / g, the esterification reaction ends and cooling begins; And / or, after the esterification reaction is completed, unreacted fatty acids are removed by vacuum distillation; And / or, the ring-opening reaction temperature is controlled at 60~100℃; And / or, the molar ratio of β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to alkyl diethanolamine is (1.0~1.2):1; And / or, the ring-opening reaction uses an aqueous solution of a quaternary ammonium salt and HX as a catalyst, wherein the quaternary ammonium salt is any one of tetraalkylammonium chloride or tetraalkylammonium bromide, and the HX is any one of HCl, HBr or HI; And / or, an inert gas is continuously introduced during esterification and ring-opening reactions.

4. The hydrolysis product of the cationic surfactant as described in claim 1, characterized in that, The hydrolysis product obtained by reacting a cationic surfactant with water molecules to remove at least one molecule of R3OH includes at least one Si-OH group.

5. The condensation product of the cationic surfactant as described in claim 1, characterized in that, The product is obtained by condensation reaction of Si-OH from the hydrolysis product of a cationic surfactant and Si-OR3 group of the cationic surfactant, while removing at least one molecule of R3OH. The condensation product contains at least one Si-O-Si bond. Alternatively, the condensation product is obtained by combining the Si-OH groups of the hydrolysis products of the above-mentioned cationic surfactants, while removing at least one molecule of R3OH, and the resulting condensation product includes at least one Si-O-Si bond.

6. The use of a cationic surfactant, a hydrolysis product of a cationic surfactant, and a condensation product of a cationic surfactant as described in any one of claims 1, 4, and 5, characterized in that, Uses of cationic surfactants, their hydrolysis products, and their condensation products in the preparation of fabric softeners.

7. A fabric softener composition, characterized in that, include: Deionized water, alcohol solvents, organic esters of orthosilicate, imidazoline surfactants, metal ion salts, organic antibacterial agents, and the cationic surfactants, hydrolysis products of cationic surfactants, or condensation products of cationic surfactants as described in any one of claims 1, 4, and 5; The organic ester of orthosilicate is selected from methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or the corresponding polymer; The alcohol solvent is selected from any one or a combination of two of ethanol and isopropanol; Imidazolino surfactants are selected from hydrocarbon-hydroxyethyl imidazolines; The metal ion in a metal ion salt is selected from Ca. 2+ Or Mg 2+ ; The organic antibacterial agent is selected from dihydroxymethyldimethylhydantoin.

8. The softener composition according to claim 7, characterized in that, The metal ion salt is selected from any one or a combination of two of calcium chloride and magnesium chloride.

9. The softener composition according to claim 7, characterized in that, The composition of the softener is as follows (parts by weight): 70-80 parts deionized water, 5-20 parts alcohol solvent, 1-5 parts organic ester of orthosilicate, 1-5 parts imidazoline surfactant, 0.05-0.5 parts metal ion salt, 0.05-0.5 parts organic antibacterial agent, and 5-20 parts of the cationic surfactant, hydrolysis product of cationic surfactant, or condensation product of cationic surfactant as described in any one of claims 1, 4, and 5.

10. Use of a softener composition according to any one of claims 7-9, characterized in that, Use of softener compositions in fabric finishing.

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