阅读说明：本技术 一种抗菌除臭氨纶的制备方法 (Preparation method of antibacterial and deodorant spandex ) 是由 毛植森 杨晓印 孔懿阳 杨从登 于 2019-10-30 设计创作，主要内容包括：本发明涉及一种抗菌除臭氨纶及其制备方法,在氨纶原液中加入抗菌除臭剂,经搅拌熟化,干法纺丝得到抗菌除臭氨纶,其中,抗菌除臭剂占氨纶原液中固含量的0.2～2％。所述的抗菌除臭剂是指一种聚环氧氯丙烷季铵盐化学接枝改性海泡石。该抗菌除臭剂能在氨纶原液中均匀分散,加入抗菌除臭剂后对生产设备更换周期无影响。在保持氨纶原有高弹性、高强度的基础上,赋予氨纶优异的抗菌除臭功能。用该方法制备的抗菌除臭剂在氨纶原液中能够分散良好,稳定存在,不团聚,制备的抗菌除臭氨纶与已公开的抗菌氨纶相比,氨纶纤维具有良好的均一性、抗菌性、除臭性能,耐水洗性能优异。(The invention relates to an antibacterial and deodorant spandex and a preparation method thereof, wherein an antibacterial deodorant is added into a spandex stock solution, and the antibacterial and deodorant spandex is obtained through stirring, curing and dry spinning, wherein the antibacterial deodorant accounts for 0.2-2% of the solid content in the spandex stock solution. The antibacterial deodorant is sepiolite chemically grafted and modified by polyepichlorohydrin quaternary ammonium salt. The antibacterial deodorant can be uniformly dispersed in the spandex stock solution, and the replacement period of production equipment is not affected after the antibacterial deodorant is added. The spandex is endowed with excellent antibacterial and deodorizing functions on the basis of keeping the original high elasticity and high strength of the spandex. The antibacterial deodorant prepared by the method can be well dispersed in the spandex stock solution, stably exists and does not agglomerate, and compared with the disclosed antibacterial spandex, the prepared antibacterial deodorant spandex has good uniformity, antibacterial property, deodorant performance and excellent water washing resistance.)

1. A preparation method of antibacterial and deodorant spandex is characterized in that an antibacterial deodorant is added into a spandex stock solution, and the antibacterial and deodorant spandex is obtained through stirring, curing and dry spinning, wherein the antibacterial deodorant accounts for 0.2-2% of the solid content in the spandex stock solution.

2. The method for preparing antibacterial deodorant spandex according to claim 1, characterized in that the antibacterial deodorant is a polyepichlorohydrin quaternary ammonium salt chemical graft modified sepiolite.

3. The method for preparing antibacterial deodorizing spandex according to claim 1 or 2, characterized in that the method for preparing the antibacterial deodorizing agent is as follows:

Step 1, introducing nitrogen into a reactor for protection, adding a solvent, hydroxyl-terminated polyepichlorohydrin and tertiary amine into the reactor, wherein the molar ratio of nitrogen atoms in the tertiary amine to chlorine atoms in the hydroxyl-terminated polyepichlorohydrin is 1: 2-1: 10, refluxing for 5-10 h at 60-100 ℃, and then removing the solvent to obtain hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt;

Step 2, adding N, N-dimethylacetamide, hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4, 4-diphenylmethane diisocyanate into a reactor, uniformly mixing according to the molar ratio of 1: 2-4, and carrying out prepolymerization for 1.5-3.5 h at the temperature of 40-60 ℃ to obtain an isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution with the mass fraction of 30-40%;

And 3, uniformly mixing the sepiolite treated by the inorganic acid and N, N-dimethylacetamide according to the solid-liquid mass ratio of 1: 10, grinding for 2-6 h, then mixing the ground sepiolite with 30-40% by mass of isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution, wherein the mass ratio of the ground sepiolite to the isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution is 1: 30-1: 200, carrying out chemical grafting reaction for 2-4 h at 40-60 ℃, filtering, leaching with N, N-dimethylacetamide, and drying to obtain the granular antibacterial deodorant.

4. The method for preparing antibacterial deodorant spandex according to claim 3, characterized in that the particle size range of the antibacterial deodorant is 1nm to 1000 nm.

5. The method for preparing antibacterial and deodorant spandex according to claim 3, characterized in that the number average molecular weight of the hydroxyl-terminated polyepichlorohydrin used in the step 1 is 500-1000.

6. The method for preparing antibacterial deodorizing spandex according to claim 3, characterized in that the tertiary amine used in the step 1 has the following structural formula:

Wherein R is₁is a C12-18 linear alkyl group, R₂The carbon-containing linear alkyl group has 1-18 carbon atoms.

7. the method for preparing antibacterial and deodorant spandex according to claim 3, characterized in that the solvent added to the reactor in step 1 is one of acetone, n-propanol, ethanol, methanol or isopropanol.

Technical Field

The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a preparation method of antibacterial and deodorant spandex. The method can effectively solve the problem of poor compatibility of the existing inorganic antibacterial agent and the spandex stock solution, has simple preparation process, has no influence on the replacement period of production equipment, and the prepared spandex has good performance uniformity and excellent antibacterial property and deodorization property.

Background

Spandex has the characteristics of high breaking strength, high elongation at break and high resilience, is widely used in the fields of underwear, sportswear, silk stockings, woven belts, paper diapers, medical and sanitary articles and the like, and has more and more attention to antibacterial property and deodorization performance because the products are in direct contact with human skin. Researches show that polyurethane macromolecular chains in spandex have no antibacterial property and deodorization property, and under a proper environmental condition, some bacteria harmful to human bodies can be propagated and metabolized on common spandex fibers, so that the micro-ecological dynamic balance of normal skin of the human bodies is destroyed, and the health of the human bodies is damaged. A large part of body odor is from ammonia, acetic acid and isovaleric acid formed by decomposing and metabolizing sweat or lipid secretion substances by odor bacteria such as staphylococcus epidermidis and corynebacteria. The antibacterial treatment of the fiber can effectively prevent body odor caused by bacteria, besides infectious diseases and skin diseases. Meanwhile, the other source of the body odor is ammonia gas, acetic acid, isovaleric acid, 2-nonenal and the like generated by the metabolism of the human body, so that the antibacterial and deodorizing functions are closely related, and the fiber has the two functions and has practical application significance.

In the case of chemical fibers, imparting antimicrobial properties is accomplished primarily by adding antimicrobial agents to the fibers. The antibacterial agent mainly comprises inorganic antibacterial agent, organic antibacterial agent, and small amount of natural antibacterial agent. Among inorganic antibacterial agents, silver ions are most widely used, but are not easily dispersed and are expensive. Among the organic antibacterial agents, quaternary ammonium salts are widely used, but have the problems of easy loss and poor washing resistance.

To impart a deodorizing function to chemical fibers, mainly by adding a deodorant to the fibers, the following 3 types of deodorants are often used: 1) the aromatic substances can cover odor or dilute odor, so that people can not feel odor, and the aromatic substances mainly comprise roses, lily of the valley, sweet osmanthus, turpentine, lemon oil and the like; 2) the chemical deodorant can react with odor molecules to generate odorless substances, and mainly comprises a metal salt inorganic deodorant which mainly comprises nano titanium dioxide and nano zinc oxide; 3) the physical adsorbent adopts substances with large specific surface area and large pores and strong adsorption capacity to adsorb malodorous substances, mainly comprises activated carbon, silica gel, zeolite, activated clay, diatomite and the like, but has the defect of easy agglomeration.

According to the published report, the preparation method of the antibacterial and deodorant spandex mainly comprises a blending method and a skin-core structure composite spinning method.

According to the report of patent CN102618962B, firstly adding silver nitrate into DMAC (dimethylacetamide) and stirring, stirring for 3 hours at 70 ℃ to obtain yellow silver sol, adding silver nanoparticles serving as an antibacterial agent into spandex spinning stock solution, wherein the addition amount is 0.01-1%, and performing dry spinning to obtain the antibacterial spandex. However, the silver nitrate is used for preparing the nano silver, a reducing agent and a protective agent are required to be added, otherwise, the generated nano silver is easy to agglomerate. According to the report of patent CN107513776A, in the process of melt spinning, TPU slices and silver-based inorganic antibacterial agents are heated and mixed in a screw machine, and then the antibacterial spandex is obtained through melt spinning.

the antibacterial and deodorant spandex prepared by the skin-core structure composite spinning method is prepared by coating a functional material on a skin layer or a core layer and preparing a skin-core assembly with a special structure. According to the report of patent CN 103194819B, the health spandex is composed of a skin layer and a core layer, wherein the core layer melt spinning body comprises bamboo charcoal powder, polyhexamethylene biguanide hydrochloride, perfume and fiber-forming polymer. And respectively extruding the core layer melt spinning body and the skin layer spinning solution from a hollow needle and an extrusion hole of the spinneret plate assembly by adopting a spinneret plate assembly to prepare the antibacterial odor-removing health-care spandex.

According to the information analysis reported in the publication, the following three main problems exist in the whole process of preparing the antibacterial spandex by the blending method: firstly, the nano silver is an inorganic particle with large specific surface area, is in a high-energy unstable state, has poor interface compatibility with polyurethane macromolecular chains in spandex, is very easy to agglomerate, is not modified or not treated in place, is easy to cause the blockage of a stock solution filter, has overhigh pipeline pressure, seriously causes the tripping accident of production equipment and causes great economic loss to production. Secondly, the nano silver or inorganic antibacterial agent which is not subjected to modification treatment is not uniformly dispersed in the spandex stock solution, so that the spandex index fluctuation is large, and the usage of spandex products in the subsequent process is influenced. Third, the reported antibacterial spandex basically only relates to the function of killing some common harmful bacteria in human body, but has no effect on eliminating main peculiar smell molecules (ammonia gas, acetic acid, isovaleric acid, 2-nonenal and the like) of human body, generally speaking, in the micro-ecological environment of human skin, especially the feet, armpits and other parts are easy to propagate bacteria due to a large amount of secreted organic matters and sweat, and are also easy to generate peculiar smell micromolecules, so in the development of antibacterial deodorizing textiles, the antibacterial property and the deodorizing property must be organically combined and have synergistic effect, and a good use effect can be achieved. The preparation process of the skin-core composite spinning method is complicated, the whole spinning system is completely different from the existing dry spinning process, the content of inorganic materials contained in the core layer is obviously higher, the production equipment is easy to block, the yarns are broken in the spinning process, the physical property indexes such as elongation and the like of spandex yarns can be seriously influenced, meanwhile, the core layer is coated with the antibacterial and deodorant effective substance, and the actual antibacterial and deodorant effect on spandex can be greatly reduced.

The antibacterial deodorant with a special structure is synthesized, so that the antibacterial deodorant and the water-washing-resistant property can be endowed to spandex, and meanwhile, the antibacterial deodorant is uniformly dispersed in spandex stock solution, is not easy to agglomerate, is simple in preparation process, and does not have negative influence on the replacement cycle of production equipment.

Disclosure of Invention

The technical problem is as follows: the invention aims to solve the technical problem of providing a preparation method of antibacterial deodorizing spandex, wherein an antibacterial deodorant prepared by the method can be well dispersed in a spandex stock solution, stably exists and does not agglomerate, and compared with the disclosed antibacterial spandex, the prepared antibacterial deodorizing spandex has good uniformity, antibacterial property, deodorizing performance and excellent water washing resistance.

The technical scheme is as follows: the preparation method of the antibacterial and deodorant spandex comprises the steps of adding an antibacterial deodorant into a spandex stock solution, stirring and curing, and carrying out dry spinning to obtain the antibacterial and deodorant spandex, wherein the antibacterial deodorant accounts for 0.2-2% of the solid content in the spandex stock solution.

The antibacterial deodorant is sepiolite chemically grafted and modified by polyepichlorohydrin quaternary ammonium salt.

The preparation method of the antibacterial deodorant comprises the following steps:

Step 1, introducing nitrogen into a reactor for protection, adding a solvent, hydroxyl-terminated polyepichlorohydrin and tertiary amine into the reactor, wherein the molar ratio of nitrogen atoms in the tertiary amine to chlorine atoms in the hydroxyl-terminated polyepichlorohydrin is 1: 2-1: 10, refluxing for 5-10 h at 60-100 ℃, and then removing the solvent to obtain hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt;

step 2, adding N, N-dimethylacetamide, hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4, 4-diphenylmethane diisocyanate into a reactor, uniformly mixing according to the molar ratio of 1: 2-4, and carrying out prepolymerization for 1.5-3.5 h at the temperature of 40-60 ℃ to obtain an isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution with the mass fraction of 30-40%;

And 3, uniformly mixing the sepiolite treated by the inorganic acid and N, N-dimethylacetamide according to the solid-liquid mass ratio of 1: 10, grinding for 2-6 h, then mixing the ground sepiolite with 30-40% by mass of isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution, wherein the mass ratio of the ground sepiolite to the isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution is 1: 30-1: 200, carrying out chemical grafting reaction for 2-4 h at 40-60 ℃, filtering, leaching with N, N-dimethylacetamide, and drying to obtain the granular antibacterial deodorant.

The grain size range of the antibacterial deodorant is 1 nm-1000 nm.

the number average molecular weight of the hydroxyl-terminated polyepichlorohydrin used in the step 1 is 500-1000.

The tertiary amine used in step 1 has the following structural formula:

Wherein R is₁Is a linear alkyl group having a carbon number of 12 to 18,R₂The carbon-containing linear alkyl group has 1-18 carbon atoms.

Step 1 the solvent added into the reactor in step 1 is one of acetone, n-propanol, ethanol, methanol or isopropanol.

Has the advantages that: according to the antibacterial and deodorant spandex prepared by the invention, an antibacterial and deodorant material is synthesized and added into a spandex stock solution, and on one hand, the surface of the material structure contains organic long-chain macromolecules which are similar to the polyurethane macromolecule structure serving as a spandex main component and have good compatibility, so that the antibacterial and deodorant agent can be ensured to have good stable dispersity when added into the spandex stock solution, and the replacement period of a stock solution filter and a spinning assembly can be ensured not to be shortened. On the other hand, the side chain of the organic long-chain macromolecule on the surface of the antibacterial deodorizing material has a plurality of quaternary ammonium salt groups, so that the antibacterial deodorizing material has excellent antibacterial property, and the inorganic part is sepiolite, is fibrous, has the characteristics of extremely high porosity and large specific surface area, and has excellent performance of adsorbing peculiar smell micromolecules, so that the antibacterial deodorizing spandex prepared by the method has good uniformity and antibacterial property compared with the disclosed antibacterial spandex, and is endowed with excellent deodorizing performance.

Detailed Description

The preparation method of the antibacterial and deodorant spandex comprises the following steps:

(1) Preparing the antibacterial deodorant.

(2) Preparing a spinning solution.

(3) Preparing the antibacterial deodorizing spandex.

The specific preparation method of the antibacterial deodorant comprises the following steps:

step 1, introducing nitrogen into a reactor for protection, adding a solvent, hydroxyl-terminated polyepichlorohydrin and tertiary amine into the reactor, wherein the molar ratio of nitrogen atoms in the tertiary amine to chlorine atoms in the hydroxyl-terminated polyepichlorohydrin is 1: 2-1: 10, refluxing for 5-10 h at 60-100 ℃, and then removing the solvent to obtain the hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt.

and 2, adding N, N-dimethylacetamide, hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4, 4-diphenylmethane diisocyanate into the reactor, uniformly mixing according to the molar ratio of 1: 2-4, and carrying out prepolymerization for 1.5-3.5 h at the temperature of 40-60 ℃ to obtain an isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution with the mass fraction of 30-40%.

And 3, uniformly mixing the sepiolite treated by the inorganic acid and N, N-dimethylacetamide according to the solid-liquid mass ratio of 1: 10, grinding for 3 hours, then mixing the ground sepiolite with 30-40% by mass of isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution, wherein the mass ratio of the ground sepiolite to the isocyanate-terminated polyepichlorohydrin quaternary ammonium salt solution is 1: 30-1: 200, carrying out chemical grafting reaction for 2 hours at 40-60 ℃, filtering, leaching with N, N-dimethylacetamide, and drying to obtain the antibacterial deodorant.

the specific preparation method of the spinning solution comprises the following steps:

Adding a solvent into a first reactor, mixing 4, 4-diphenylmethane diisocyanate and polytetrahydrofuran ether glycol according to a molar ratio of 1.5: 1-1.8: 1, carrying out prepolymerization at 40-50 ℃ for 2h, then transferring into a second reactor, slowly dropwise adding a chain extender solution into the second reactor, transferring into a curing tank after dropwise adding for 1.5-2.5 h, adding an antibacterial deodorant and other auxiliary materials, and curing for 24h to prepare a spinning stock solution with a mass fraction of 30-37 (wt)%, wherein the viscosity of the spinning stock solution is 3000-6000P (40 ℃).

(3) the method for preparing the antibacterial deodorizing spandex comprises the following steps:

and (2) precisely metering and extruding the spandex stock solution containing the antibacterial deodorant into a spinning assembly through a gear pump, allowing the spandex stock solution to flow out of a spinneret plate, heating filament yarns in a channel through hot air, carrying out flash evaporation volatilization on a solvent, solidifying the filament yarns into filament yarns, and oiling and winding the filament yarns to obtain the antibacterial deodorant spandex.

The detection method of the antibacterial performance and the deodorization performance refers to the following standards:

(1) and (3) detecting the antibacterial performance: FZ/T73023-2006

Note: washing with water for 20 times

(2) And (3) detection of deodorization performance: GB/T33610.2-2017

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.