Cationic surface active agent and anti-yellowing fabric softener composition and preparation method thereof

Abstract

The invention relates to a cationic surfactant and a preparation method and application thereof, and a softener composition and a preparation method and application thereof. Firstly, a cationic surface active agent with a novel structure is designed and synthesized, cycloalkyl and siloxy are introduced by using beta-(3, 4-epoxy cyclohexyl) ethyl trialkoxysilane, an epoxy gene on cycloalkane is a reason for increasing molecular internal stress by ring tension, a nucleophilic substitution reaction is easily carried out at a lower temperature to generate a ring-opening reaction, and the molecular internal stress is increased by using an epoxy gene on the cycloalkane; therefore, the steric hindrance around N atoms is increased, and the anti-yellowing performance and the stability of the surfactant at high temperature are improved through the steric hindrance effect. Besides, Si-OR groups capable of being hydrolyzed and condensed are introduced into the cationic surface active agent and can be condensed with hydroxyl groups of cellulose molecules, the Si-OR groups can be more firmly adsorbed on the surface of cellulose through the chemical bond effect, the effect of the Si-OR groups is exerted, and the treated fabric has better softening performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional finishing agents for textiles, and in particular relates to a cationic surfactant, a preparation method and application thereof, and a softener composition, a preparation method and application thereof. Background Art

[0002] The surfactants in fabric softeners play a significant role in improving the feel and softness of fabrics. Researching and developing new softeners is an effective way to increase the added value of textiles. Softeners are generally categorized into silicone and non-silicone types, with the latter primarily being cationic.

[0003] Cationic softeners are inherently positively charged and are very suitable for use as softeners in fabric finishing. The di-long-chain alkyl dimethyl quaternary ammonium salts developed in the early 1950s were once the largest type of cationic surfactants in terms of production volume. However, they have drawbacks such as poor biodegradability, environmental pollution, poor hygroscopicity of treated fabrics, and a greasy feel. Since di-long-chain alkyl dimethyl quaternary ammonium salts were banned in Europe, the United States and other countries and regions in the 1990s, ester-based quaternary ammonium salts, especially di-long-chain alkyl ester-based quaternary ammonium salts, have made great progress as substitutes for di-long-chain alkyl dimethyl quaternary ammonium salts.

[0004] At present, ester-based quaternary ammonium salts have generally replaced di-long-chain alkyl dialkyl quaternary ammonium salts as the most important fabric softener on the market. Ester-based quaternary ammonium salts have better biodegradability and hydrolytic stability. However, the problems are that some ester-based quaternary ammonium salts have poor water resistance after finishing, and lose their softness and fluffy effects after being left to absorb moisture or after washing; some ester-based quaternary ammonium salts have poor yellowing resistance, and the finished fabrics easily turn yellow, affecting their appearance; some ester-based quaternary ammonium salts have too strong ionicity, and the softener composition is easily stabilized after contact with cellulose with a negative charge on the surface, making it difficult for the ester-based quaternary ammonium salts to exert their fabric finishing effect, and the finishing effect on pure cotton fabrics is poor. Especially for application scenarios in commercial hotels or other public places, the fabrics that need to be finished are basically white cellulose cotton towel fabrics. 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 drying at room temperature with general softeners. Under high temperature conditions, cationic surfactants or amino-containing silane coupling agents are very likely to change color, causing the finished towels to turn yellow, seriously affecting the appearance.

[0005] In this context, it is necessary to improve the molecular structure of cationic surfactants. The present invention is based on a cationic surfactant with a special structure to prepare a post-finishing softener specifically for cellulose-based cotton towel fabrics that is resistant to water washing and high-temperature conditions and not prone to color change. The treated fabrics also have better softness. Summary of the Invention

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

[0007] In order to achieve the above technical objectives, the technical solutions adopted by the present invention are as follows:

[0008] In the first aspect, a cationic surfactant, the structural formula of which comprises: or ;

[0009] wherein R1 is a straight-chain hydrocarbon group, a branched-chain hydrocarbon group or a cyclic hydrocarbon group of 9 to 29 carbon atoms, preferably, R1 is a straight-chain hydrocarbon group, a branched-chain hydrocarbon group or a cyclic hydrocarbon group of 9 to 19 carbon atoms; R2 is a straight-chain hydrocarbon group, a branched-chain hydrocarbon group or a cyclic hydrocarbon group of 1 to 6 carbon atoms, preferably, R2 is a straight-chain hydrocarbon group, a branched-chain hydrocarbon group or a cyclic hydrocarbon group of 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 atom

[0010] In a second aspect, the preparation method of the cationic surfactant described above comprises: using alkyldiethanolamine as a raw material, first performing an esterification reaction with a C10-C30 fatty acid to obtain an esterification product, and then performing a ring-opening reaction of the esterification product with β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to obtain a cationic surfactant;

[0011] Among them, the synthetic route of esterification reaction is:

[0012] ;

[0013] The synthetic route of the ring-opening reaction is:

[0014] ;

[0015] Preferably, the molar ratio of C10-C30 fatty acid to alkyldiethanolamine in the esterification reaction is (2.0-2.4):1;

[0016] More preferably, the molar ratio of C10-C30 fatty acid to alkyldiethanolamine 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°C;

[0019] More preferably, the temperature of the esterification reaction is controlled at 160-200°C;

[0020] Preferably, when the acid value of the reaction system is lower than 20 mgKOH / g, the esterification reaction is terminated and the temperature is lowered;

[0021] More preferably, when the acid value of the reaction system is lower than 15 mgKOH / g, the esterification reaction is terminated and the temperature is lowered;

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

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

[0024] More preferably, the ring-opening reaction temperature is controlled at 60-90°C;

[0025] More preferably, the ring-opening reaction temperature is controlled at 60-80°C.

[0026] Preferably, the molar ratio of β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to alkyldiethanolamine is (1.0-1.2):1; more preferably, the molar ratio of β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to alkyldiethanolamine 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, 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 reaction and the ring-opening reaction.

[0029] In a third aspect, the hydrolysis product of the cationic surfactant described above is obtained by reacting the cationic surfactant with water molecules to remove at least one molecule of R3OH, and the resulting hydrolysis product includes at least one Si-OH group.

[0030] In a fourth aspect, the condensation product of the cationic surfactant described above is obtained by condensing the Si-OH group of the cationic surfactant hydrolyzate with the Si-OR3 group of the cationic surfactant, while removing at least one molecule of R3OH, and the resulting condensation product includes at least one Si-O-Si bond;

[0031] Alternatively, the Si-OH groups of the hydrolyzed products of the cationic surfactants are condensed with each other, and at least one molecule of R3OH is removed, so that the obtained condensation product includes at least one Si-O-Si bond.

[0032] In a fifth aspect, the cationic surfactants, the hydrolyzates of the cationic surfactants and the condensation products of the cationic surfactants described above are used in the preparation of fabric softeners.

[0033] In a sixth aspect, a softener composition comprises: deionized water, an alcohol solvent, an organic orthosilicate, an imidazoline surfactant, a metal ion salt, an organic antibacterial agent, and the cationic surfactant, the hydrolyzate of the cationic surfactant, or the condensation product of the cationic surfactant mentioned above.

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

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

[0036] Preferably, the imidazoline surfactant is selected from alkyl hydroxyethyl imidazoline, wherein the alkyl hydroxyethyl imidazoline is preferably any one of oleyl hydroxyethyl imidazoline and stearyl hydroxyethyl imidazoline or a combination of two thereof;

[0037] Metal ion salts are used to neutralize the negative charge on the fiber surface and stabilize cationic surfactants. The metal ions of the metal ion salts are preferably Ca 2+ or Mg 2+ ;

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

[0039] The organic antimicrobial agent is used to inhibit the growth of microorganisms such as bacteria and molds and prevent the softener composition from having odor. The organic antimicrobial agent is preferably dimethyloldimethylhydantoin.

[0040] Furthermore, the softener composition comprises the following components in parts by mass: 70-80 parts of deionized water, 5-20 parts of an alcohol solvent, 1-5 parts of an organic orthosilicate, 1-5 parts of an imidazoline surfactant, 0.05-0.5 parts of a metal ion salt, 0.05-0.5 parts of an organic antibacterial agent, and 5-20 parts of the above-mentioned cationic surfactant, hydrolyzate of a cationic surfactant, or condensation product of a cationic surfactant.

[0041] In a seventh aspect, the softener composition described above is used in fabric finishing.

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

[0043] The beneficial effects of the present invention are: designing and synthesizing a cationic surfactant with a novel structure, using β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to introduce cycloalkyl and siloxy groups Si-OR, and the epoxy groups on the cycloalkane are easy to undergo nucleophilic substitution reaction with nitrogen atoms at a lower temperature to cause ring opening due to the increase in internal molecular stress caused by ring tension.

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

[0045] On the other hand, the introduction of Si-OR siloxy groups that can undergo hydrolysis and condensation reactions into cationic surfactants can undergo condensation reactions with the hydroxyl groups of cellulose molecules, and through chemical bonds, they can be more firmly adsorbed on the cellulose surface of the fabric and exert their effects, making the fabric softer after treatment. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0047] Figure 2 Surface morphology analysis (SEM) images of white cotton grey fabric treated with the softener composition of Example 5 and white cotton grey fabric not treated with the softener composition. DETAILED DESCRIPTION

[0048] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

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

[0050] If the specific experimental conditions are not specified in the examples, they are usually based on conventional conditions in the field or conditions recommended by the reagent company; the materials, reagents, etc. used in the examples can be purchased through commercial channels unless otherwise specified.

[0051] Example 1

[0052] Lauric acid (C12) and N-methyldiethanolamine (MDEA) were used as the starting materials in a molar ratio of 2.25:1. p-Toluenesulfonic acid was used as a catalyst for the esterification reaction, accounting for 0.8% of the total reactant mass. The lauric acid was added to a four-necked flask equipped with a condenser and stirrer. The flask was heated to 100°C under nitrogen. After the lauric acid was melted, p-Toluenesulfonic acid was added under continuous stirring and nitrogen purging. MDEA was then added dropwise using a dropping funnel. The reaction system was then heated to 180°C. After 0.5 h, the MDEA addition was complete. The reaction was then maintained at 180°C. The reaction was terminated when the acid value (measured as below 15 mgKOH / g) was detected. The unreacted fatty acid was then removed by vacuum distillation at 0.2 torr, followed by cooling to 120°C.

[0053] When the reaction product was cooled to 70°C, 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 the total mass of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane by tetrabutylammonium chloride and 0.5% of the total mass of 0.5 mol / L hydrochloric acid aqueous solution were added as ring-opening reaction catalysts. During the reaction, stirring was continued and nitrogen was introduced for protection. The temperature of the reaction system was maintained at 70°C. After the reaction was continued for 1 hour, the temperature was lowered to terminate the reaction.

[0054] The product prepared in Example 1 was characterized, and the test results of its synthetic resonance hydrogen spectrum were 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 initial raw materials in a molar ratio of 2.2:1. The molar ratio of the epoxysilane coupling agent β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to MDEA was subsequently controlled to be 1.1:1. The remaining reactions were the same as in Example 1.

[0057] The product prepared in Example 2 was characterized, and the test results of its synthetic resonance hydrogen spectrum were 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 initial raw materials in a molar ratio of 2.15:1. The molar ratio of the epoxysilane coupling agent β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to MDEA was subsequently controlled to be 1.05:1. The remaining reactions were the same as in Example 1.

[0061] The product prepared in Example 3 was characterized, and the test results of its synthetic resonance hydrogen spectrum were 1 H-NMR (400 MHz, 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 initial raw materials in a molar ratio of 2.1:1. The molar ratio of the epoxysilane coupling agent β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to MDEA was subsequently controlled to be 1.1:1. The remaining reactions were the same as in Example 1.

[0065] The product prepared in Example 4 was characterized, and the test results of its synthetic resonance hydrogen spectrum were 1 H-NMR (400 MHz, 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, in parts by mass: 10 parts of the cationic surfactant prepared in Example 1, 2 parts of oleyl 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, ethyl orthosilicate), and 0.1 parts of dihydroxymethyldimethylhydantoin, an antibacterial agent.

[0069] Example 6

[0070] The proportions of the softener composition, in parts by mass: 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, ethyl orthosilicate oligomer, average degree of polymerization 1-2), and 0.1 parts of dihydroxymethyldimethylhydantoin, an antibacterial agent.

[0071] Example 7

[0072] The proportions of the softener composition, in parts by mass: 10 parts of the cationic surfactant prepared in Example 2, 2 parts of oleyl hydroxyethyl imidazoline, 10 parts of isopropyl alcohol, 0.1 parts of calcium chloride, 75.8 parts of deionized water, 2 parts of JH-T28 (Jianghan New Materials, ethyl orthosilicate), and 0.1 parts of dihydroxymethyl dimethyl hydantoin, an antibacterial agent.

[0073] Example 8

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

[0075] Example 9

[0076] The proportions of the softener composition, in parts by mass: 10 parts of the cationic surfactant prepared in Example 3, 2 parts of oleyl 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, ethyl orthosilicate), and 0.1 parts of dihydroxymethyl dimethyl hydantoin, an antibacterial agent.

[0077] Example 10

[0078] The proportions of the softener composition, in parts by mass: 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, ethyl orthosilicate oligomer, average degree of polymerization 1-2), and 0.1 parts of dihydroxymethyldimethylhydantoin, an antibacterial agent.

[0079] Example 11

[0080] The proportions of the softener composition, in parts by mass: 10 parts of the cationic surfactant prepared in Example 4, 2 parts of oleyl 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, ethyl orthosilicate), and 0.1 parts of dihydroxymethyldimethylhydantoin, an antibacterial agent.

[0081] Example 12

[0082] The proportions of the softener composition, in parts by mass: 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, ethyl orthosilicate oligomer, average degree of polymerization 4-5), and 0.1 parts of dihydroxymethyldimethylhydantoin, an antibacterial agent.

[0083] Comparative Example 1

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

[0085] Comparative Example 2

[0086] The proportions of the softener composition, in parts by mass: 10 parts of the cationic surfactant prepared in Comparative Example 1, 2 parts of oleyl 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, ethyl orthosilicate), and 0.1 parts of dihydroxymethyl dimethyl hydantoin, an antibacterial agent.

[0087] The formulations of Examples 5-12 and Comparative Example 2 were weighed according to the material proportions, stirred and dissolved at room temperature and pressure to obtain the corresponding softener compositions.

[0088] Low-temperature stability test of softeners: The softener compositions prepared in Examples 5-12 and Comparative Example 2 were placed in a refrigerator at (-5±2)°C for 24 hours, then taken out and allowed to stand at room temperature for 1 hour. When the samples were allowed to return to room temperature, the presence of crystallization or precipitation was observed.

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

[0090] Fabric finishing tests

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

[0092] Cut the pretreated white cotton fabric into 120×120 mm square pieces. Soak the fabric in the softener compositions of Examples 5-12 and Comparative Example 2 at a fabric-to-softener composition mass ratio of 1:25. After soaking in a (50±2)°C waterbath for 30 minutes, remove the fabric, secure it in place, and dry it in a 100°C oven for 15 minutes. Remove the dried fabric and allow it to recover moisture at room temperature for at least 24 hours.

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

[0094] Softness test: Use an automatic fabric stiffness tester to test the bending stiffness (stiffness) of the treated fabric, and use the change in bending stiffness to judge the improvement in fabric softness.

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

[0096] Fabric Wrinkle Recovery Angle Test: Based on GB / T3819-1997, a laser fabric wrinkle elasticity tester uses the vertical method to measure the fabric's recovery angle. When a fabric is folded under pressure, a crease forms. After the pressure is removed, the sample recovers along the crease, creating an angle. This recovery angle is used to measure the fabric's crease recovery ability.

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

[0098] Surface morphology analysis (SEM): After drying, samples of the white cotton fabric treated with the softener composition of Example 5 and the untreated white cotton fabric were adhered to a metal laboratory table with conductive adhesive and vacuum-sprayed with gold. The morphological characteristics of the samples were observed using a scanning electron microscope.

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

[0100] Table 1

[0101]

[0102] Evaluation of fabric softening performance includes multiple aspects, including fabric surface properties (dynamic friction coefficient) to reflect the fabric's smoothness, fabric bending properties (bending stiffness) to reflect the fabric's smoothness, and fabric wrinkle recovery angle to reflect the fabric's firmness. The smoother, smoother, and stiffer the fabric's hand, the higher the fabric's softening performance and the better the softener composition's effectiveness. Analysis of the test data in Table 1 shows that the softener compositions of Examples 5-12 exhibited no stability issues. Under baking and drying conditions, the softener compositions of Examples 5-12 achieved significantly higher whiteness and wrinkle recovery angles, while lower bending stiffness and dynamic friction coefficients. This indicates that the softener compositions of Examples 5-12, which utilize the cationic surfactants prepared in Examples 1-4 as key components, exhibit superior softening properties and enhanced resistance to yellowing.

[0103] Comparative Example 2 used the cationic surfactant prepared in Comparative Example 1. The steric hindrance of its N element was inferior to that of the cationic surfactants prepared in Examples 1-4, resulting in lower anti-yellowing performance. Furthermore, the corresponding Si-OR groups were more susceptible to hydrolysis-condensation reactions in alkaline aqueous solutions, forming condensation products with low solubility in water. This resulted in turbidity and precipitation at the bottom of the softener composition in Comparative Example 2 after being placed in an oven at (40±2)°C or (-5±2)°C for 24 hours. Furthermore, the fabric treated with the softener composition in Comparative Example 2 exhibited higher bending stiffness and dynamic friction coefficient, and a lower wrinkle recovery angle. The test results indicate that the softening effect of the softener composition in Comparative Example 2 on the treated fabric was somewhat reduced.

[0104] The changes in the crystalline morphology of cotton fibers before and after treatment with the softener composition of Example 5 are listed in Figure 1 In, from Figure 1 It can be seen that the X-ray diffraction curves of the cotton fibers before and after treatment with the finishing agent are essentially similar, with no significant changes in the diffraction peaks. Distinct diffraction peaks are present at 14.7°, 16.9°, 22.5°, and 34.1°, confirming the cellulose as Form I. This indicates that treatment of the cotton fibers with the softener composition of Example 5 does not alter the basic crystal structure within the cotton fibers.

[0105] The surface morphology changes of cotton fibers before and after treatment with the softener composition of Example 5 are shown in Figure 2 In, from Figure 2 As can be seen, the surface of the untreated cotton fabric was noticeably rougher, with barbs, burrs, and wrinkles. After treatment with the softener composition of Example 5, the cotton fiber surface became smoother and flatter, with significantly fewer barbs, burrs, and wrinkles. This is because the cationic surfactant adsorbs onto the cotton fiber surface through electrostatic interaction and Si-OC chemical bonds, filling the surface wrinkles and reducing friction between the fibers, thus giving the fabric a fluffy and soft feel.

[0106] Finally, it should be noted that the above is only 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 aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for parts thereof. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention. Although the above describes the specific embodiments of the present invention, it is not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that, based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection 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-chain hydrocarbon group or cyclic hydrocarbon group of 9 to 29 carbon atoms; R2 is a straight-chain hydrocarbon group, branched-chain hydrocarbon group or cyclic hydrocarbon group of 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 as claimed in claim 1, characterized in that: Using alkyldiethanolamine as raw material, it first undergoes an esterification reaction with C10~C30 fatty acids to obtain an esterification product, and the esterification product then undergoes a ring-opening reaction with β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to obtain a cationic surfactant; The synthetic route of the esterification reaction is: ； The synthetic route of the ring-opening reaction is: 。 3. The method for preparing a cationic surfactant according to claim 2, wherein: The molar ratio of C10-C30 fatty acid to alkyldiethanolamine in the esterification reaction is (2.0-2.4):1; and / or, an esterification catalyst is used in the esterification reaction, wherein the esterification catalyst is preferably p-toluenesulfonic acid; and / or, the temperature of the esterification reaction is controlled at 120-200° C.; and / or, when the acid value of the reaction system is lower than 20 mgKOH / g, the esterification reaction is terminated and the temperature is lowered; and / or, removing unreacted fatty acids by distillation under reduced pressure after the esterification reaction is completed; and / or, the ring-opening reaction temperature is controlled at 60-100°C; and / or, the molar ratio of β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane to alkyldiethanolamine 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, 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; And / or, an inert gas or nitrogen is continuously introduced during the esterification reaction and the ring-opening reaction.

4. The hydrolyzate of the cationic surfactant according to claim 1, wherein At least one molecule of R3OH is removed by the reaction of the cationic surfactant with water molecules, and the resulting hydrolysis product includes at least one Si-OH group.

5. The condensation product of a cationic surfactant according to claim 1, wherein The condensation reaction is carried out by condensing Si-OH groups of a cationic surfactant hydrolyzate with Si-OR3 groups of a cationic surfactant, while removing at least one molecule of R3OH, and the resulting condensation product includes at least one Si-O-Si bond; Alternatively, the Si-OH groups of the hydrolyzed products of the cationic surfactants are condensed with each other, and at least one molecule of R3OH is removed, so that the obtained condensation product includes at least one Si-O-Si bond.

6. Use of the cationic surfactant, the hydrolyzate of a cationic surfactant and the condensation product of a cationic surfactant according to any one of claims 1, 4 and 5, characterized in that: Use of cationic surfactants, hydrolyzates of cationic surfactants and condensation products of cationic surfactants in the preparation of fabric softeners.

7. A softener composition, characterized in that include: Deionized water, alcohol solvent, organic orthosilicate, imidazoline surfactant, metal ion salt, organic antibacterial agent and the cationic surfactant, cationic surfactant hydrolyzate or cationic surfactant condensation product according to any one of claims 1, 4 and 5; Wherein, the organic orthosilicate is selected from any one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or corresponding polymers; The alcohol solvent is selected from: any one of ethanol and isopropanol or a combination of the two; The imidazoline surfactant is selected from alkyl hydroxyethyl imidazoline; The metal ion of the metal ion salt is selected from Ca 2+ or Mg 2+ ; The organic antimicrobial agent is selected from dimethylol dimethyl hydantoin.

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

9. The softener composition according to claim 7, characterized in that The softener composition comprises the following components in parts by mass: 70-80 parts of deionized water, 5-20 parts of an alcohol solvent, 1-5 parts of an organic orthosilicate, 1-5 parts of an imidazoline surfactant, 0.05-0.5 parts of a metal ion salt, 0.05-0.5 parts of an organic antibacterial agent, and 5-20 parts of the cationic surfactant, the hydrolyzate of a cationic surfactant, or the condensation product of a cationic surfactant according to any one of claims 1, 4, and 5.

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

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