阅读说明：本技术 一种具有抗菌性能的长丝的制备方法 (Preparation method of antibacterial filament ) 是由 笪俊杰 于 2018-05-31 设计创作，主要内容包括：本发明公开了一种具有抗菌性能的长丝的制备方法,包括以下步骤：将改性聚氨酯与聚乳酸分别在100-120℃真空条件下干燥,将混合物在单螺杆挤出机中混合、压缩、熔融,形成混合熔体,形成熔体细流；将熔体细流在100-110℃的冷却装置中缓慢冷却,形成纤维；将所得的纤维进入丝室,冷却固化,拉伸；将冷却后的纤维经过油辊上油,拉伸,得成品。本发明将改性聚氨酯与聚乳酸混合,制备的纺丝具有优良的力学性能。(the invention discloses a preparation method of a filament with antibacterial property, which comprises the following steps: respectively drying the modified polyurethane and the polylactic acid at the temperature of 100-120 ℃ under vacuum, and mixing, compressing and melting the mixture in a single-screw extruder to form a mixed melt, so as to form a melt trickle; slowly cooling the melt trickle in a cooling device at the temperature of 100-110 ℃ to form fibers; the obtained fiber enters a filament chamber, is cooled, solidified and stretched; and oiling the cooled fiber by an oiling roller, and stretching to obtain a finished product. The invention mixes the modified polyurethane and the polylactic acid, and the prepared spinning has excellent mechanical property.)

1. a method for preparing a filament with antibacterial property is characterized by comprising the following steps:

(1-1) respectively drying the modified polyurethane and the polylactic acid at the temperature of 100-120 ℃ under vacuum, respectively mixing the dried modified polyurethane and the polylactic acid, and then adding the mixture into a single-screw extruder;

(1-2) mixing, compressing and melting the mixture in a single-screw extruder to form a mixed melt, and controlling the temperature of the melt at 190 ℃ and 200 ℃ to form melt trickle;

(1-3) slowly cooling the melt stream in a cooling device at the temperature of 100-110 ℃ to form fibers;

(1-4) feeding the obtained fiber into a filament chamber, controlling the air supply temperature to be 20-25 ℃, the air pressure to be 300-;

And (1-5) oiling the cooled fiber by using an oiling roller, pre-stretching by using a stretching hot plate, and then performing package forming to obtain a finished product.

2. a process for producing a filament having antibacterial properties according to claim 1, wherein in step (1-1), the mass ratio of the modified polyurethane to the polylactic acid is 1-3: 1.

3. A process for producing a filament having antibacterial properties according to claim 1, characterized in that in step (1-1), the modified polyurethane is produced by the following process:

(2-1) dissolving chitosan in an acetic acid solution, and stirring for degradation to obtain chitosan molecules A;

(2-2) dissolving chitosan molecule A in the solution, homogenizing at 10000-;

And (2-3) crosslinking the chitosan microspheres and polyurethane in a glutaraldehyde solution to obtain the chitosan modified polyurethane material.

4. A process for preparing a filament having antibacterial properties according to claim 1, wherein the molecular weight of the chitosan molecule A in step (2-1) is 46-68 kDa.

5. A process for preparing a filament having antibacterial properties according to claim 1, wherein the mass ratio of the chitosan microspheres to the polyurethane in step (2-3) is 1-2: 100.

6. A process for preparing a filament having antibacterial properties as claimed in claim 1, wherein the molecular weight of the polyurethane in step (2-3) is 5000-8000 Da.

7. a process for preparing a filament having antibacterial properties according to claim 1, wherein the mass percentage of the acetic acid solution in the step (2-1) is 5 to 8%.

8. A process for preparing a filament having antibacterial properties according to claim 1, wherein the mass percentage of the glutaraldehyde solution in step (2-3) is 1.5-2%.

9. A process for producing a filament having antibacterial properties according to claim 1, wherein in step (1-1), zinc oxide particles are further included.

10. a process for producing a filament having antibacterial properties according to claim 9, characterized in that in step (1-1), the mass ratio of the modified polyurethane, polylactic acid and zinc oxide particles is 1-3:1: 0.01-0.05.

Technical Field

The invention relates to a preparation method of spinning, in particular to a preparation method of a filament with antibacterial property.

Background

The traditional synthetic fiber fabric only has the common performances of fiber materials, but has very defects of environmental protection, hygroscopicity, antibiosis, ultraviolet resistance, radiation protection and other performances, and the traditional film only has the common performances of the common film, but has defects of antibiosis, environmental protection, ultraviolet resistance, infrared transmission and other performances.

Chinese patent 'CN 201510117354' provides an antibacterial spandex fiber and a preparation method thereof, the antibacterial spandex fiber prepared by the invention has stable and uniform performance, has antibacterial property and no other special performance, and the antibacterial performance prepared by additionally added components is easy to lose in the spinning process.

Chinese patent 'CN 201410611814.9' provides a preparation method of chitosan modified spandex filament, the method comprises the steps of soaking a polyamide membrane in 1.1-1.3% glutaraldehyde solution for 3 hours, washing with deionized water after the reaction is finished, soaking in 15-20mg/mL chitosan solution at 4 ℃ for 24 hours to obtain a chitosan polyurethane membrane, washing with 2% glacial acetic acid, neutralizing with NaOH to be neutral, and washing with deionized water to obtain a chitosan grafted polyurethane membrane; and preparing spandex filament by using the obtained modified polyurethane film.

Disclosure of Invention

The purpose of the invention is as follows: the invention provides a synthetic material with antibacterial performance and a preparation method thereof, and solves the problems that the synthetic material in the prior art has poor antibacterial performance and has great influence on a spinning process.

The technical scheme is as follows: the preparation method of the filament with antibacterial property comprises the following steps: (1-1) respectively drying the modified polyurethane and the polylactic acid at the temperature of 100-120 ℃ under vacuum, respectively mixing the dried modified polyurethane and the polylactic acid, and then adding the mixture into a single-screw extruder; (1-2) mixing, compressing and melting the mixture in a single-screw extruder to form a mixed melt, and controlling the temperature of the melt at 190 ℃ and 200 ℃ to form melt trickle; (1-3) slowly cooling the melt stream in a cooling device at the temperature of 100-110 ℃ to form fibers; (1-4) feeding the obtained fiber into a filament chamber, controlling the air supply temperature to be 20-25 ℃, the air pressure to be 300-; and (1-5) oiling the cooled fiber by using an oiling roller, pre-stretching by using a stretching hot plate, and then performing package forming to obtain a finished product.

Further, in the step (1-1), the mass ratio of the modified polyurethane to the polylactic acid is 1-3: 1.

Further, in the step (1-1), the preparation method of the modified polyurethane comprises the following steps: (2-1) dissolving chitosan in an acetic acid solution, and stirring for degradation to obtain chitosan molecules A; (2-2) dissolving chitosan molecule A in the solution, homogenizing at 10000-; and (2-3) crosslinking the chitosan microspheres and polyurethane in a glutaraldehyde solution to obtain the chitosan modified polyurethane material.

In the invention, the acetic acid used in the step (2-1) hydrolyzes the chitosan, and the concentration and hydrolysis time of the acetic acid influence the degradation speed and degradation degree of the chitosan, so that the concentration of the acetic acid can be determined by integrating factors such as production cost, production period and the like.

In the present invention, the initial molecular weight of the chitosan molecule subjected to acid hydrolysis in the step (2-1) is not limited, and commercially available chitosan molecules can be used, and the molecular weight is usually about 30 to 100 ten thousand.

In the invention, in addition to the hydrolysis by acetic acid, hydrochloric acid or other hydrolysis modes such as enzymolysis and the like can be used in the step (2-1), and hydrochloric acid is also a common means and is an equivalent mode of the hydrolysis by acetic acid in the step (2-1) of the invention, but the influence of the introduction of acetate on the subsequent steps is smaller than that of the introduction of chloride ions, so the optimal mode is to use an acetic acid solution to carry out acidolysis on chitosan molecules.

In the invention, in the step (2-1), the molecular weight of the chitosan molecule A obtained after the chitosan molecule is hydrolyzed is 46-68kDa, the control of the hydrolysis end point is the measurement of viscosity, the viscosity of the chitosan solution in the range is obtained according to the calculation formula of the high molecular viscosity and the molecular weight, and when the viscosity of the hydrolyzed solution falls into the range, the reaction is stopped, and the specific calculation mode can refer to the literature, "measurement of the viscosity-average molecular mass of chitosan" or other existing literatures.

And purifying the degraded chitosan molecule A by using an alcohol precipitation or centrifugation mode.

In the invention, in the step (2-2), the chitosan microspheres can be obtained by utilizing the chitosan molecules with the molecular weight under the condition of high-speed homogenization, the homogenization temperature is between 50 and 60 ℃, the mass percent of the prepared chitosan molecule A solution is 0.01mg/ml, and 1 to 3 drops of glacial acetic acid can be dripped into the dissolved distilled water solution when the chitosan molecule A is dissolved.

In the invention, in step (2-2), the obtained chitosan microspheres can be obtained by freeze drying, or by vacuum distillation.

In the invention, in the step (2-3), the mass ratio of the chitosan microspheres to the polyurethane is 1-2:100, the mass ratio of the chitosan microspheres to the polyurethane needs to be strictly controlled between 1-2:100, and the ratio of the microspheres is too much, so that the viscosity in the subsequent spinning process cannot be controlled, and the spinning assembly can be blocked; the ratio of the microspheres is low, so that the antibacterial effect cannot be achieved on one hand, and the Tg temperature of the material is reduced on the other hand.

In the invention, the CAS number of polyurethane is 30322-28-2, and the molecular weight of the polyurethane is 5000-8000 Da.

Preferably, the mass percentage of the acetic acid solution in the step (2-1) is 5-8%.

In the present invention, the concentration of glutaraldehyde is selected in relation to the molecular weight of polyurethane and the particle size of microspheres, and preferably, the mass percentage of the glutaraldehyde solution in step (2-3) is 1.5-2%.

In the step (1-1) of the invention, zinc oxide particles are also included, so that the material further has a deodorizing function.

further, in the step (1-1), the mass ratio of the modified polyurethane to the polylactic acid to the zinc oxide particles is 1-3:1: 0.01-0.05.

Has the advantages that: (1) in the invention, chitosan macromolecules are firstly degraded by acid, the degraded chitosan molecules are prepared into microspheres with the particle size of 1-3 mu m, and then the chitosan microspheres are crosslinked with polyurethane, so that the modified polyurethane has an antibacterial function; (2) the invention changes the molecular weight of chitosan and reduces the influence of the molecular viscosity of chitosan on the spinning process of the composite material; (3) the invention mixes the modified polyurethane and the polylactic acid, and the prepared spinning has excellent mechanical property; (4) according to the invention, zinc oxide is added in the spinning, so that the toughness of the spinning is increased, and the deodorization function of the spinning is increased.

Detailed Description

firstly, the source of raw materials

and (3) chitosan: the average molecular weight is 30-50 ten thousand;

Polyurethane: the average molecular weight is 8000 Da;

Polylactic acid: the average molecular weight is 1-2 ten thousand;

Zinc oxide was purchased from Shijiazhuang Ruitou chemical science and technology Co., Ltd;

The remaining materials were obtained commercially.

Second, sample preparation

2.1 preparation of modified polyurethane

Dissolving chitosan in 6% acetic acid solution, placing on a magnetic stirrer, and stirring and degrading for 4.5h at normal temperature to obtain chitosan molecule A; dissolving chitosan molecule A in distilled water, dropwise adding a little glacial acetic acid to dissolve the chitosan molecule A in the distilled water to prepare a chitosan molecule A solution with the concentration of 0.01mg/ml, homogenizing at the rotating speed of 11000rpm, and freeze-drying to obtain chitosan microspheres; and (2) crosslinking 1.5g of chitosan microspheres and polyurethane in a 1.5-2% glutaraldehyde solution according to the mass ratio of 1.5:100 to obtain the chitosan modified polyurethane material.

2.2 preparation of the spun yarn