阅读说明：本技术 一种耐高温橄榄改性锦纶纤维及其制备方法 (High-temperature-resistant olive-modified polyamide fiber and preparation method thereof ) 是由 黄效华 郑来久 王世超 黄效龙 刘潇 刘彦明 伏广伟 于 2020-06-03 设计创作，主要内容包括：本发明提供一种耐高温橄榄改性锦纶纤维,所述纤维中橄榄叶提取物含量1.0-5.0%。所述锦纶纤维的制备方法,包括：1、橄榄叶改性双层微胶囊制备；2、橄榄叶功能改性母粒制备；3、混合熔融；4纺丝及后处理步骤。本发明制备的橄榄改性锦纶纤维中含有橄榄叶提取物成份,特别是橄榄叶提取物中的橄榄苦甙和羟基酪醇,是具有天然的抗菌及防紫外线功能的天然添加剂可以提供更多的功能性,满足不同消费者的需求。(The invention provides a high-temperature-resistant olive modified polyamide fiber, wherein the content of an olive leaf extract in the fiber is 1.0-5.0%. The preparation method of the nylon fiber comprises the following steps: 1. preparing an olive leaf modified double-layer microcapsule; 2. preparing olive leaf function modified master batches; 3. mixing and melting; 4 spinning and post-processing steps. The olive modified polyamide fiber prepared by the invention contains olive leaf extract components, particularly oleuropein and hydroxytyrosol in the olive leaf extract, is a natural additive with natural antibacterial and ultraviolet-proof functions, can provide more functions, and meets the requirements of different consumers.)

1. The high-temperature-resistant olive modified polyamide fiber is characterized in that: the content of the olive leaf extract in the fiber is 1.0-5.0%.

2. The high-temperature-resistant olive-modified polyamide fiber according to claim 1, characterized in that: the preparation method of the nylon fiber comprises the following steps: 1. preparing an olive leaf modified double-layer microcapsule; 2. preparing olive leaf function modified master batches; 3. mixing and melting; 4 spinning and post-processing steps.

3. The high-temperature-resistant olive-modified polyamide fiber according to claim 2, characterized in that: the preparation steps of the olive leaf modified double-layer microcapsule comprise: (1) preparing a first reaction solution; (2) preparing a second reaction solution; (3) preparing a single-layer microcapsule solution; (4) and (4) preparing capsules.

4. The high-temperature-resistant olive-modified polyamide fiber according to claim 3, characterized in that: the first reaction liquid preparation comprises: dissolving folium Canarii albi extract in 50-60% ethanol solution for 20-30min, heating to 30-40 deg.C, adding aminopropyltrimethoxysilane, dimethyl carbonate and vegetable oil, stirring at 600-.

5. The high-temperature-resistant olive-modified polyamide fiber according to claim 4, characterized in that: the mass ratio of aminopropyl trimethoxy silane to dimethyl carbonate to vegetable oil is as follows: 2-5:1-3: 10-20; the addition amount of the aminopropyl trimethoxy silane is 10-20% of the olive leaf extract;

the vegetable oil is one or more of safflower seed oil, Indian fruit oil, tea oil, olive oil and glycerol; the addition amount of the vegetable oil is 2-3 times of the quality of the olive leaf extract.

6. The high-temperature-resistant olive-modified polyamide fiber according to claim 3, characterized in that:

the second reaction liquid continuously heats the prepared first reaction liquid to 50-60 ℃, slowly adds melamine resin and sodium alginate for dispersion at the dispersion rotation speed of 600-1200r/min for 30-40min, and then keeps the temperature for 20-30 min; finally adding one or more of azodiisoheptonitrile, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate, continuously stirring for 20-40min, and keeping the temperature for 10-20 min; the mass ratio of the melamine resin to the sodium alginate is as follows: 1:0.5-3.

7. The high-temperature-resistant olive-modified polyamide fiber according to claim 3, characterized in that: the (3) single-layer microcapsule solution preparation: cooling the prepared second reaction liquid to 20-30 ℃, adding triethylamine, adjusting the pH value to 4-6, reacting for 10-20min, and keeping the temperature for 30-50 min;

the preparation of the capsule (4): dripping the prepared single-layer microcapsule solution into a high-temperature calcium chloride solution, standing for 20-30min, performing suction filtration, and drying; the temperature of the high-temperature calcium chloride solution is 80-90 ℃.

8. The high-temperature-resistant olive-modified polyamide fiber according to claim 7, characterized in that: the high-temperature calcium chloride solution contains a forming agent; the forming agent comprises: sodium palmitate, ethylene glycol monobutyl ether, silane coupling agent; the mass ratio of the sodium palmitate, the alkyl glycoside and the silane coupling agent in the forming agent is 5-10: 1-3: 0.5-2; the silane coupling agent is one or more of gamma-methacryloxypropyl, kh-792 and Si-602.

9. The high-temperature-resistant olive-modified polyamide fiber according to claim 2, characterized in that: the preparation method of the olive leaf functional master batch comprises the steps of adding polyamide slices, an antioxidant, a dispersing agent, olive leaf modified double-layer microcapsules and a modifying agent into a double-screw extruder according to the mass parts, mixing at a high speed, and extruding and granulating; the modifier comprises: methyl benzotriazole, boron oxide, cyclopentadiene epoxy resin and sepiolite fiber; the modifier comprises methylbenzotriazole, boron oxide, cyclopentadiene epoxy resin and sepiolite fibers in a mass ratio of (5-10: 20-50: 5-20): 3-5.

10. The high-temperature-resistant olive-modified polyamide fiber according to claim 2, characterized in that: the spinning and post-processing steps comprise: the spinning temperature is 290-320 ℃, the winding speed is 2000-3000m/min, the draft multiple is 0.5-1, the side blowing wind speed is 1.2-1.4m/s, and the winding tension is 3.5-4.5 cn/dtex.

Technical Field

The invention relates to a modified nylon fiber, in particular to a high-temperature-resistant olive composite particle modified nylon fiber, and belongs to the field of nylon fibers.

Background

Chinlon 6, known as polycaprolactam and called nylon 6, is polycaprolactam fiber formed by polymerizing and spinning monomer caprolactam. It has a series of advantages of high mechanical strength, small specific weight, good toughness, wear resistance, weak acid and alkali resistance, etc., so that the nylon-6 is not only suitable for civil use, but also widely used in industry, and is one of the best fiber materials for manufacturing industrial fabrics such as nylon cord fabric, nylon canvas, etc., fishing nets, ropes, containers and military products.

With the improvement of living standard, people have more and more demands on the difference functional fabric. The preparation method of the common functional fabric mainly comprises two methods: one is that in the spinning process, functional auxiliary agent is added to prepare functional fiber, and then the fiber is obtained by spinning and weaving; another approach is to finish the functional ingredients onto the textile by post-finishing, giving the textile new functionality. From the above two methods, the first process has permanent functional performance due to the functional auxiliary agent added into the fiber during the spinning process; the fiber prepared by the second process has the functional auxiliary agent only on the surface of the fiber, so that the functionality is not durable, and therefore, many fiber manufacturers select the first production process more frequently.

In the production process for producing the modified nylon fiber by using the first process, many enterprises firstly prepare the microcapsule functional master batch, then mix the master batch with the nylon chips, and then prepare the functional nylon fiber through the steps of mixing, extruding, spinning and the like. However, in the prior art, during the preparation process of the prepared microcapsule type nylon fiber, the microcapsule generates form change under the conditions of high temperature and extrusion, and becomes flat, so that the prepared nylon fiber is unstable, and finally the industrialization of the differentiated nylon fiber is influenced. Meanwhile, with the continuous release of capsule core components, water molecules and air molecules can gradually permeate into the molecular structure of the nylon fiber, and the yellow phenomenon of the fiber can be finally caused due to oxidation after long-time storage or use.

As a metaphor for peace, calm and well-being, olive trees provide food and shelter for humans as early as the beginning of human history. It is generally believed to originate from the mediterranean coast more than 5000 years ago and was first brought to the united states in the 15 th century. There is evidence that drinking olive leaf brewed tea is a method of treating discomfort such as cough, sore throat, cystitis and fever that has traditionally been used for hundreds of years in the middle east region. Until the early 18 th century, olive leaves began to attract the attention of medical institutions. The folium Canarii albi mainly contains secoiridoid and its glycoside, flavone and its glycoside, biflavone and its glycoside, low molecular tannin, etc., and secoiridoid is the main active ingredient. Oleuropein in the olive leaves can protect skin cells from being damaged by ultraviolet rays, prevent ultraviolet rays from decomposing skin membrane lipid, promote fibroblasts to generate collagen, reduce secretion of fibroblast collagen enzyme, and prevent glycan resistant reaction of cell membranes, so that the fibroblasts are highly protected, the skin is naturally prevented from being damaged by oxidation, the skin is further prevented from being damaged by the ultraviolet rays, the skin is effectively kept tender and elastic, and the effects of strengthening and tendering the skin are achieved.

Based on this, many customers hope to produce an olive modified nylon fiber by adding the olive leaf extract into the nylon fiber so as to meet the requirements of consumers. And the fiber is not reported in the prior art.

Disclosure of Invention

Aiming at the technical problems in the prior art, the invention aims to:

1. the olive modified polyamide fiber prepared by the invention contains olive leaf extract components, particularly oleuropein and hydroxytyrosol in the olive leaf extract, is a natural additive with natural antibacterial and ultraviolet irradiation preventing functions, can provide more functionality, and meets the requirements of different consumers.

2. The nylon fiber prepared by the preparation process can solve the technical problems that the fiber is yellowed and the strength is reduced after the long-time storage or use due to the continuous release of capsule core components of the capsule.

3. In the process of preparing the olive modified polyamide fiber, the prepared olive modified microcapsule has a double-layer structure, so that the olive modified polyamide fiber has better high-temperature resistance, and does not crack, deform and crack at a high temperature.

In order to achieve the above object, the invention adopts the following technical means:

the invention provides a high-temperature-resistant olive modified polyamide fiber, wherein the content of olive leaf extract in the fiber is 1.0-5.0%;

the invention also provides a preparation process of the high-temperature-resistant olive modified polyamide fiber, which comprises the following steps: 1. preparing an olive leaf modified double-layer microcapsule; 2. preparing olive leaf function modified master batches; 3. mixing and melting; 4 spinning and post-processing steps, and specifically comprises the following preparation processes:

1. preparation of olive leaf modified double-layer microcapsule

(1) Preparing a first reaction solution:

adding the olive leaf extract into 50-60% ethanol solution for dissolving for 20-30min, heating to 30-40 ℃, adding aminopropyl trimethoxy silane, dimethyl carbonate and vegetable oil for stirring at the stirring speed of 600-;

the mass ratio of aminopropyl trimethoxy silane to dimethyl carbonate to vegetable oil is as follows: 2-5:1-3: 10-20; the addition amount of the aminopropyl trimethoxy silane is 10-20% of the olive leaf extract; the addition of aminopropyltrimethoxysilane can promote the rapid emulsification of the vegetable oil;

the vegetable oil is one or more of safflower seed oil, Indian fruit oil, tea oil, olive oil and glycerol; the addition amount of the vegetable oil is 2-3 times of the quality of the olive leaf extract;

(2) preparing a second reaction solution:

heating the prepared first reaction liquid to 50-60 ℃, slowly adding melamine resin and sodium alginate for dispersion at the dispersion rotation speed of 600-1200r/min for 30-40min, and then preserving heat for 20-30 min; finally, adding one or more of azodiisoheptonitrile, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate, continuing stirring for 20-40min, and keeping the temperature for 10-20min to obtain a second reaction solution;

the mass ratio of the melamine resin to the sodium alginate is as follows: 1: 0.5-3; the mass ratio of the melamine resin to the sodium alginate is preferably selected to enable the prepared microcapsule to have a better embedding rate.

(3) Preparation of single-layer microcapsule solution:

cooling the prepared second reaction liquid to 20-30 ℃, adding triethylamine, adjusting the pH value to 4-6, reacting for 10-20min, and keeping the temperature for 30-50min to obtain a single-layer microcapsule solution.

(4) Preparing capsules:

dripping the prepared single-layer microcapsule solution into a high-temperature calcium chloride solution, standing for 20-30min to prepare a double-layer microcapsule solution, and finally performing suction filtration and drying to obtain the olive leaf modified double-layer microcapsule;

the temperature of the high-temperature calcium chloride solution is 80-90 ℃;

the high-temperature calcium chloride solution contains a forming agent; the forming agent comprises: sodium palmitate, ethylene glycol monobutyl ether, silane coupling agent; the mass ratio of the sodium palmitate, the alkyl glycoside and the silane coupling agent in the forming agent is 5-10: 1-3: 0.5-2; the silane coupling agent is one or more of methacryloxypropyltrimethoxysilane, kh-792 and Si-602; the forming agent is helpful for the prepared microcapsule to have uniform and smooth capsule wall.

The olive leaf modified double-layer microcapsule prepared by the invention has a microscopic double-layer structure under an electron microscope, the capsule wall is smooth and uniform, the heat resistance is excellent, the thermal melting temperature is 380-; meanwhile, the particle size is properly less than or equal to 0.8 mu m, and the method is suitable for fiber production; good sphericity and dispersity, double-layer structure coating, 99.9% of embedding rate, 130.45-150.73J/g of enthalpy, and good heat storage performance.

2. Preparation of olive leaf function modified master batch

Adding the chinlon slices, the antioxidant, the dispersing agent, the olive leaf modified double-layer microcapsule and the modifying agent into a double-screw extruder according to the mass parts, mixing at a high speed, and extruding and granulating to obtain an olive leaf functional master batch;

the addition amount of the olive leaf modified double-layer microcapsule in the olive leaf function modified master batch is 10-50% of the weight of the nylon chips.

As an improvement, the weight ratio of the nylon chips, the antioxidant, the dispersant, the olive leaf modified double-layer microcapsule to the modifier is 20-100: 1-3: 3-5: 15-20: 5-10; the nylon chips are dried in vacuum before use, the drying temperature is 100-110 ℃, and the drying time is 80-110 min; the polyamide fiber slice has the transverse shrinkage of 0.2-0.4%, the longitudinal shrinkage of 0.5-0.8%, the relative viscosity of 2.4-2.8 and the amino end group content of 40-60;

the antioxidant is antioxidant T-9228, the pH value is 5-7, the content of active substances is 99.5%, and the CAS number is 154862-43-8;

the modifier comprises: methyl benzotriazole, boron oxide, cyclopentadiene epoxy resin and sepiolite fiber; the modifier comprises methylbenzotriazole, boron oxide, cyclopentadiene epoxy resin and sepiolite fibers in a mass ratio of (5-10: 20-50: 5-20): 3-5;

in a natural environment, because the molecular structure of the nylon fiber contains amide groups, water molecules and air molecules can gradually permeate into the molecular structure of the nylon fiber along with the continuous release of capsule core components of the capsule, and finally the yellowing phenomenon and the strength reduction of the fiber can be caused by the oxidation after the nylon fiber is stored or used for a long time. The modifier is added in the preparation process of the olive leaf functional modified master batch, and the main purpose of the invention is to improve the shielding performance of the prepared nylon fiber, prevent the situation that the oxidation resistance of the nylon fiber is gradually weakened due to the continuous release of capsule core components of the fiber, avoid the yellowing phenomenon of the fiber after long-time storage or use, and obviously enhance the strength of the fiber.

3. Mixing and melting

Mixing the olive leaf functional modified master batch prepared in the step 2 with the chinlon chips 6, and then heating, melting and extruding the mixture by a screw extruder to obtain a spinning melt;

the addition amount of the olive leaf function modification master batch accounts for 1-5% of the prepared nylon fiber based on the olive leaf extract;

the temperature intervals of all the zones in the screw extruder are as follows: 245 ℃ and 260 ℃; 260-2-75 ℃; 275 ℃ and 280 ℃; 275 ℃ and 270 ℃; 275 ℃ and 270 ℃.

4. Spinning and after-treatment

The spinning melt obtained in the step 3 is sprayed out through a spinneret plate through a spinning box, and then air is supplied and cooled through a spinning channel to form fiber yarns; oiling is carried out through a bundling and oiling process; finally, the process is passed; sequentially passing through a godet roller for stretching and heat setting, and finally winding to form the nylon-6 fiber;

the spinning temperature is 290-320 ℃, the winding speed is 2000-3000m/min, the draft multiple is 0.5-1, the side blowing wind speed is 1.2-1.4m/s, and the winding tension is 3.5-4.5 cn/dtex.

Because the modifier is added into the modified master batch, in order to be matched with the modifier for use, the spinning temperature needs to be increased, the winding speed needs to be reduced, the wind speed needs to be increased, and the shielding performance and the strength of the prepared nylon fiber can be improved to the maximum extent.

Due to the adoption of the technical scheme, the invention achieves the following technical effects:

1. the olive modified polyamide fiber prepared by the invention has good antibacterial performance, the antibacterial rate to staphylococcus aureus is more than or equal to 99.9%, the antibacterial rate to candida albicans is more than or equal to 97.6%, and the antibacterial rate to escherichia coli is more than or equal to 98.6%.

2. The olive leaf modified double-layer microcapsule prepared by the invention has a microscopic double-layer structure under an electron microscope, the capsule wall is smooth and uniform, the heat resistance is excellent, the thermal melting temperature is 380-; meanwhile, the particle size is properly less than or equal to 0.8 mu m, and the method is suitable for fiber production; good sphericity and dispersity, double-layer structure coating, 99.9% of embedding rate, 130.45-150.73J/g of enthalpy, and good heat storage performance.

3. The modifier is added in the preparation process of the olive leaf functional modified master batch, and the main purpose is to improve the shielding performance of the prepared nylon fiber, prevent the situation that the oxidation resistance of the nylon fiber is gradually weakened due to the continuous release of capsule core components of the fiber, avoid the yellowing phenomenon of the fiber after long-time storage or use, and obviously enhance the strength of the fiber; the olive modified polyamide fiber prepared by the invention has good physical strength and yellowing resistance, wherein the breaking strength is more than or equal to 5.7cN/dtex, the elongation at break is more than or equal to 43%, and the yellowing resistance grade is 5 grade.

Detailed Description