Amphoteric macromolecular deodorization finishing agent as well as preparation method and application thereof

Abstract

The invention belongs to the field of textile finishing agents, and discloses an amphoteric macromolecular deodorization finishing agent as well as a preparation method and application thereof. The preparation method comprises the following steps: carrying out a ring-opening reaction on epoxy silane and a taurine monomer to obtain an active intermediate, and adding a cyclic silane monomer to copolymerize the active intermediate and the cyclic monomer to obtain the self-curing amphoteric long-acting macromolecular deodorization finishing agent with good safety performance. The problems that a micromolecular deodorant is not resistant to washing and migrates to a human body are solved, and the obtained amphoteric macromolecular deodorization finishing agent can be applied to the field of deodorization finishing of high-end cotton and linen textiles.

Description

Technical Field

[0001] The present invention relates to the field of textile finishing agents, in particular to an amphoteric macromolecular deodorizing finishing agent and a preparation method and application thereof. Background Art

[0002] Currently, human odors are primarily caused by bacteria breaking down secretions from the skin, which results in the release of organic gases. Generally speaking, deodorization and anti-odor treatment are synonymous, and fabrics treated with these treatments are considered functional hygiene textiles. Antimicrobial treatment differs from deodorization in that deodorization removes existing odors, while antimicrobial deodorization achieves this through antibacterial measures, preventing the growth of malodorous substances. The deodorizing properties of textiles remove odors not only from microbial decomposition of oils and sweat, but also from animal excrement and the volatilization of substances produced by the decay of dead animals.

[0003] In fact, textiles, especially cotton and wool fabrics, have a certain adsorption and deodorizing effect on odors due to their inherent porous structure. In the 1990s, some experts even suggested wearing fabrics to mask body odor. Today, deodorization research has matured, and deodorization can be achieved through chemical reactions, physical methods, or photocatalytic reactions.

[0004] Chemical deodorization uses redox reactions, neutralization reactions, addition reactions, condensation reactions, ion exchange reactions, and other methods to cause a chemical reaction between malodorous substances and deodorants to produce odorless substances, thereby eliminating odors. Commonly used deodorants include flavonoid compounds, tea dry distillation extracts, acid-base buffers, cyclodextrins, and transition metal ions. For example, cellulose can be made into hydroxymethylcellulose zinc, which can form salts with low-level fatty acids, form complexes with ammonia or trimethylamine, and react with hydrogen sulfide to form zinc sulfide, thereby removing odorous substances. This product also has excellent deodorizing properties, high safety, and antibacterial properties. Chemical deodorization is very effective and thorough, and once the odor is removed, it is difficult to restore. It is also easy to process and can be carried out using conventional dyeing and finishing equipment. It is currently the mainstream deodorization method.

[0005] Physical deodorization is currently one of the main deodorization methods. It is relatively low-cost and primarily involves incorporating substances such as activated carbon into fibers to enhance the fabric's adsorption capacity, or relying on the fabric's inherent adsorption properties to absorb odors. The primary mechanism of action is the van der Waals force between molecules. However, physical deodorization methods suffer from poor washability and low deodorization efficiency. They often experience low deodorization rates or even odor re-release due to saturation. Furthermore, physical deodorization methods typically require the use of inorganic powder particles, which, when applied to the fabric, can reduce the fabric's feel, have poor stability and durability, and can also cause "dust" during wear.

[0006] Photocatalytic deodorization involves applying a photocatalyst to fabrics and utilizing the photocatalytic reaction to degrade odorous substances into non-toxic and odorless substances, thereby eliminating odors. Due to their excellent durability, stability, safety, and reliability, these deodorants can be added to synthetic fibers and used as functional additives to finish textiles into functional textiles. Available photocatalysts include TiO2, ZnO, WO3, etc., which are relatively effective, with TiO2 being the most commonly used. However, photocatalytic titanium dioxide requires the assistance of ultraviolet light to complete its deodorization effect, and its application scenarios are also greatly limited. Furthermore, nano-titanium dioxide must be added to the spinning solution and spun before it can be used. Therefore, this method can currently only be used for some synthetic fibers and is difficult to apply to natural fibers and regenerated fibers.

[0007] In summary, chemical deodorization is currently a relatively effective and low-cost deodorization method suitable for industrial deployment. However, traditional chemical deodorizing agents lack durability, particularly in terms of wash and soap fastness. Furthermore, some transition metal deodorizing agents are often heavy metals, which can cause irritation and allergies to humans if left on fabrics. Summary of the Invention

[0008] The purpose of the present invention is to overcome the shortcomings of the above-mentioned background technology and provide an amphoteric macromolecular deodorizing finishing agent, its preparation method, and application. This application utilizes the acid-base neutralization principle to incorporate amphoteric small molecule deodorizing structures such as taurine and amino acids into polydimethylsiloxane by synthesizing specific monomers and polymerizing them. While retaining the deodorizing properties, the polymer's film-forming properties and the reaction characteristics of Si-OH with hydroxyl groups on the fiber are utilized to firmly fix the deodorizing structure to the fabric surface, forming a durable deodorizing property. Furthermore, after finishing, the fabric's moisture absorption and wearing comfort can be further improved.

[0009] To achieve the purpose of the present invention, the amphoteric macromolecular deodorizing finishing agent of the present invention is a polymer structure, and the microstructure of the polymer contains both amphoteric deodorizing segments and soft dimethyl polysiloxane segments, and the structure is as follows:

[0010]

[0011] Wherein, m is an integer of 5-20, and n is an integer of 5-20.

[0012] Furthermore, the present invention also provides a method for preparing the aforementioned amphiphilic macromolecular deodorizing finishing agent, wherein the preparation method comprises the following steps: a ring-opening reaction of epoxysilane with a taurine monomer to obtain an active intermediate, and then adding a cyclic silane monomer to copolymerize the active intermediate and the cyclic monomer.

[0013] Furthermore, in some embodiments of the present invention, the preparation method of the amphoteric macromolecular deodorizing finishing agent comprises the following steps:

[0014] (1) adding taurine monomer and γ-(2,3-epoxypropoxy)propyltrimethoxysilane to a reaction vessel, adding a solvent, reacting for 1 to 10 hours, and then rotating drying to obtain an active intermediate;

[0015] (2) The cyclic monomer and the active intermediate obtained in step (1) are placed in a reaction vessel, and then the temperature is increased, water is added, and a hydrolysis polymerization reaction is carried out for 1 to 6 hours to obtain an amphoteric macromolecular deodorizing finishing agent.

[0016] Furthermore, in some embodiments of the present invention, the taurine monomer is any one of taurine and N-methyltaurine, or a combination of the two.

[0017] Furthermore, in some embodiments of the present invention, the cyclic monomer is any one or more of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, and decamethylcyclopentasiloxane.

[0018] Furthermore, in some embodiments of the present invention, the solvent in step (1) is any one or more of water, N,N-dimethylformamide, and tetrahydrofuran.

[0019] Furthermore, in some embodiments of the present invention, the molar ratio of taurine monomer to γ-(2,3-epoxypropoxy)propyltrimethoxysilane in step (1) is 10:1 to 1:10.

[0020] Furthermore, in some embodiments of the present invention, the reaction temperature in step (1) is 40-100°C.

[0021] Furthermore, in some embodiments of the present invention, the molar ratio of the cyclic monomer in step (2) to the active intermediate obtained in step (1) is 10:1 to 1:10.

[0022] Furthermore, in some embodiments of the present invention, the molar ratio of the cyclic monomer + the reactive monomer to the molar ratio of water in step (2) is 1:3 to 3:1.

[0023] Furthermore, in some embodiments of the present invention, the temperature is raised to 60-120°C in step (2).

[0024] In another aspect, the present invention further provides an application of the aforementioned amphoteric macromolecular deodorizing finishing agent, wherein the application is to use the amphoteric macromolecular deodorizing finishing agent in the field of deodorizing finishing of cotton and linen textiles.

[0025] Compared with the prior art, the advantages of the present invention are as follows:

[0026] (1) The amphoteric macromolecular deodorizing finishing agent of the present invention can deodorize the fabric after being applied to the fabric, and does not contain any soluble substances, is highly safe, and has excellent deodorizing performance. In addition, the cotton and linen fabrics treated with the finishing agent of the present invention have excellent softness and hydrophilicity.

[0027] (2) The present invention utilizes the film-forming function of the macromolecular finishing agent. The resulting finishing agent can produce a wrapping effect on the fiber surface and has extremely strong water-washing resistance, thereby avoiding the problem that conventional deodorizing agents are not water-resistant and migrate to the human body to cause allergies.

[0028] (3) The amphoteric macromolecular deodorizing finishing agent of the present invention does not contain any heavy metal elements and organic solvents, is safe and environmentally friendly, and does not contain emulsifiers. It can self-emulsify in water to form a stable emulsion, has little irritation to the human body, and is easy to use. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of the synthesis route of the amphoteric macromolecular deodorizing finishing agent of the present invention;

[0030] Figure 2 The amphoteric macromolecular deodorizing finishing agent obtained in each embodiment of the present invention is 1 H-NMR spectrum;

[0031] Figure 3 FT-IR spectra of the amphoteric macromolecular deodorizing finishing agents obtained in various embodiments of the present invention;

[0032] Figure 4 This is a third-party test report on the deodorizing performance of the amphoteric macromolecular deodorizing finishing agent obtained in Example 2 of the present invention. DETAILED DESCRIPTION

[0033] In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and examples. Additional aspects and advantages of the present invention will be partially given in the following description, partially become apparent from the following description, or be understood through practice of the present invention. It should be understood that the following description is only intended to explain the present invention and is not intended to limit the present invention.

[0034] As used herein, the terms "comprises," "including," "having," "containing" or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a listed element is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0035] When amount, concentration or other value or parameter is represented with range, preferred range or the range that a series of upper preferred value and lower preferred value limit are expressed, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value and any range lower limit or preferred value, no matter whether this range is disclosed separately.For example, when disclosing scope "1 to 5", described scope should be interpreted as including scope "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5" etc.When numerical range is described in this article, unless otherwise stated, otherwise this scope is intended to include its end value and all integers and fractions within this range.

[0036] The singular includes plural references unless the context clearly dictates otherwise. "Optional" or "either" means that the subsequently described event or incident can or cannot occur, and that the description includes instances where the event occurs and instances where it does not.

[0037] The indefinite articles "a" and "an" before the elements or components of the present invention do not limit the quantity requirement (i.e. the number of times they appear). Therefore, "a" or "an" should be interpreted as including one or at least one, and elements or components in the singular also include plural forms, unless the quantity clearly refers to only the singular form.

[0038] In addition, the terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples" described below mean that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic descriptions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the technical features involved in the various embodiments of the present invention may be combined with each other as long as they do not conflict with each other.

[0039] The raw materials, instruments, equipment and reagents used in the present invention are all commercial products available for selection and can be purchased from the market.

[0040] Example 1

[0041] Step 1: Add taurine monomer (taurine) and γ-(2,3-epoxypropoxy)propyltrimethoxysilane to the system, add solvent (water), react at 40°C for 1 hour, and then rotary dry to obtain an active intermediate. The molar ratio of taurine monomer to γ-(2,3-epoxypropoxy)propyltrimethoxysilane is 10:1.

[0042] Step 2: Weigh the cyclic monomer (octamethylcyclotetrasiloxane) and the reactive intermediate from Step 1 in the correct proportions into a container. The temperature is then raised to 60°C, and deionized water is added. A hydrolysis polymerization reaction is carried out for 1 hour to produce an amphoteric macromolecular deodorizing finishing agent. The molar ratio of octamethylcyclotetrasiloxane to the reactive intermediate is 10:1, and the molar ratio of water to (cyclic monomer + reactive monomer) is 3:1. In the polymer, m = 20, and n = 5.

[0043] Example 2

[0044] Step 1: Add taurine monomer (N-methyltaurine) and γ-(2,3-epoxypropyloxy)propyltrimethoxysilane to the system, add solvent (tetrahydrofuran), react at 100°C for 10 hours, and then rotary dry to obtain an active intermediate. The molar ratio of taurine monomer to γ-(2,3-epoxypropyloxy)propyltrimethoxysilane is 1:10.

[0045] Step 2: Weigh the cyclic monomer (decamethylcyclopentasiloxane) and the active intermediate from Step 1 in the correct proportions and place them into a container. The temperature is then raised to 100°C, and water is added for a hydrolysis polymerization reaction for 6 hours to produce an amphoteric macromolecular deodorizing finish. The molar ratio of octamethylcyclotetrasiloxane to the active intermediate is 1:10, and the molar ratio of water to (cyclic monomer + active monomer) is 1:3. In the polymer, m = 5, and n = 20.

[0046] Example 3

[0047] Step 1: Add taurine monomer (taurine) and γ-(2,3-epoxypropyloxy)propyltrimethoxysilane to the system, add solvent (N,N-dimethylformamide), react at 60°C for 3 hours, and then rotary dry to obtain an active intermediate. The molar ratio of taurine monomer to γ-(2,3-epoxypropyloxy)propyltrimethoxysilane is 10:3.

[0048] Step 2: Weigh the cyclic monomer (hexamethylcyclotrisiloxane) and the active intermediate from Step 1 in the correct proportions into a container. The mixture is then heated to 120°C and water is added. A hydrolysis polymerization reaction occurs for 3 hours to produce an amphoteric macromolecular deodorizing finish. The molar ratio of octamethylcyclotetrasiloxane to the active intermediate is 10:5, and the molar ratio of water to (cyclic monomer + active monomer) is 3:2. In the polymer, m = 10, and n = 5.

[0049] Example 4

[0050] Step 1: Add taurine monomer (N-methyltaurine) and γ-(2,3-epoxypropyloxy)propyltrimethoxysilane to the system, add solvent (tetrahydrofuran), react at 60°C for 5 hours, and then rotary dry to obtain an active intermediate. The molar ratio of taurine monomer to γ-(2,3-epoxypropyloxy)propyltrimethoxysilane is 10:5.

[0051] Step 2: Weigh the cyclic monomer (octamethylcyclotetrasiloxane) and the active intermediate from Step 1 in the correct proportions into a container. The temperature is then raised to 80°C, and water is added. A hydrolysis polymerization reaction occurs for 4 hours to produce an amphoteric macromolecular deodorizing finish. The molar ratio of octamethylcyclotetrasiloxane to the active intermediate is 10:10, and the molar ratio of water to (cyclic monomer + active monomer) is 3:3. In the polymer, m = 10, and n = 10.

[0052] Example 5

[0053] Step 1: Add taurine monomer (N-methyltaurine) and γ-(2,3-epoxypropyloxy)propyltrimethoxysilane to the system, add solvent (water), react at 90°C for 8 hours, and then rotary dry to obtain an active intermediate. The molar ratio of taurine monomer to γ-(2,3-epoxypropyloxy)propyltrimethoxysilane is 1:3.

[0054] Step 2: Weigh the cyclic monomer (hexamethylcyclotrisiloxane) and the active intermediate from Step 1 in the correct proportions into a container. The temperature is then raised to 90°C, and water is added. A hydrolysis polymerization reaction is carried out for 5 hours to produce an amphoteric macromolecular deodorizing finish. The molar ratio of octamethylcyclotetrasiloxane to the active intermediate is 1:3, and the molar ratio of water to (cyclic monomer + active monomer) is 1:2. In the polymer, m = 5, and n = 10.

[0055] Example 6

[0056] Step 1: Add taurine monomer (taurine) and γ-(2,3-epoxypropyloxy)propyltrimethoxysilane to the system, add solvent (N,N-dimethylformamide), react at 80°C for 7 hours, and then rotary dry to obtain an active intermediate. The molar ratio of taurine monomer to γ-(2,3-epoxypropyloxy)propyltrimethoxysilane is 1:6.

[0057] Step 2: Weigh the cyclic monomer (decamethylcyclopentasiloxane) and the active intermediate from Step 1 in the correct proportions into a container. The mixture is then heated to 70°C and water is added. A hydrolysis polymerization reaction is carried out for 4 hours to produce an amphoteric macromolecular deodorizing finish. The molar ratio of octamethylcyclotetrasiloxane to the active intermediate is 1:6, and the molar ratio of water to (cyclic monomer + active monomer) is 1:2. In the polymer, m = 5 and n = 15.

[0058] The following table compares the performance of the amphoteric macromolecular deodorizing finishing agent obtained in the present invention with commercially available deodorizing products.

[0059] Table 1 Performance comparison of the amphoteric macromolecular deodorizing finishing agent obtained in the present invention and commercially available deodorizing products

[0060]

[0061] Note: The deodorizing finishing method is to use ramie plain woven fabric, the finishing agent dosage is 5% owf, two dipping and two padding, the padding rate is 100%, the pre-baking temperature is 80℃, the pre-baking time is 5min, the baking temperature is 140℃, and the baking time is 1.5min. The deodorizing test adopts the GB / T33610.2-2017 method, and the feel test adopts the subjective evaluation method of 5 people, and the average value is taken.

[0062] It will be easily understood by those skilled in the art that the above description is merely an embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An amphoteric macromolecular deodorizing finishing agent, characterized in that: The amphoteric macromolecular deodorizing finishing agent is a polymer structure. The microstructure of the polymer contains both amphoteric deodorizing segments and soft dimethyl polysiloxane segments. The structure is as follows: Wherein, m is an integer of 5-20, and n is an integer of 5-20.

2. A method for preparing an amphoteric macromolecular deodorizing finishing agent, characterized in that: The preparation method comprises the following steps: epoxy silane and taurine monomers undergo a ring-opening reaction to obtain an active intermediate, and then a cyclic silane monomer is added to copolymerize the active intermediate and the cyclic monomer.

3. The method for preparing the amphoteric macromolecular deodorizing finishing agent according to claim 2, characterized in that: The preparation method of the amphoteric macromolecular deodorizing finishing agent comprises the following steps: (1) adding taurine monomer and γ-(2,3-epoxypropoxy)propyltrimethoxysilane into a reaction vessel, adding a solvent, and rotating drying after the reaction to obtain an active intermediate; (2) The cyclic monomer and the active intermediate obtained in step (1) are put into a reaction vessel, and then the temperature is increased and water is added to carry out a hydrolysis polymerization reaction to obtain an amphoteric macromolecular deodorizing finishing agent.

4. The method for preparing the amphoteric macromolecular deodorizing finishing agent according to claim 2 or 3, characterized in that: The taurine monomer is any one of taurine and N-methyltaurine, or a combination of the two.

5. The method for preparing the amphoteric macromolecular deodorizing finishing agent according to claim 2 or 3, characterized in that: The cyclic monomer is any one or more of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, and decamethylcyclopentasiloxane.

6. The method for preparing the amphoteric macromolecular deodorizing finishing agent according to claim 3, characterized in that: The reaction temperature in step (1) is 40-100° C.; preferably, the reaction in step (1) lasts for 1-10 hours.

7. The method for preparing the amphoteric macromolecular deodorizing finishing agent according to claim 2, characterized in that: The solvent in step (1) is any one or more of water, N,N-dimethylformamide, and tetrahydrofuran; preferably, the molar ratio of taurine monomer and γ-(2,3-epoxypropoxy)propyltrimethoxysilane in step (1) is 10:1 to 1:

10.

8. The method for preparing the amphoteric macromolecular deodorizing finishing agent according to claim 2, characterized in that: The molar ratio of the cyclic monomer in step (2) to the active intermediate obtained in step (1) is 10:1 to 1:10; preferably, the molar ratio of the cyclic monomer + active monomer to the molar ratio of water in step (2) is 1:3 to 3:

1.

9. The method for preparing the amphoteric macromolecular deodorizing finishing agent according to claim 2, characterized in that: The temperature in step (2) is raised to 60-120° C.; preferably, the hydrolysis polymerization reaction in step (2) is carried out for 1 to 6 hours.

10. The use of the amphoteric macromolecular deodorizing finishing agent according to claim 1, characterized in that: The application is to use the amphoteric macromolecular deodorizing finishing agent in the field of deodorizing finishing of cotton and linen textiles.

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