阅读说明：本技术 一种耐老化的茶多酚、柚皮甙或大黄素改性锦纶母粒及其制备工艺 (Anti-aging tea polyphenol, naringin or emodin modified polyamide master batch and preparation process thereof ) 是由 黄效华 郑来久 蔡强 姜义军 甄丽 姜亚明 伏广伟 刘宇 于 2020-06-08 设计创作，主要内容包括：本发明提供一种耐老化的茶多酚、柚皮甙或大黄素改性锦纶母粒的制备工艺,包括负载剂的制备步骤；所述的负载剂的制备包括原料预处理、共混、热处理以及洗脱干燥；所述共混：将负载剂的制备原料加入搅拌釜中,在1200-1500rpm转速下搅拌8-15min,得到混合物料A；将混合物料A与远红外纳米粉体混合,得到混合物料B；将混合物料B置于28-30℃温度下超声处理28-32min,超声频率为33-38KHZ,得到共混粉体；所述热处理：将共混粉体与处理液混合,并以5-6℃/min的速率升温到99-100℃,保温热处理30-40min。本发明制备的改性锦纶母粒不仅抗菌性能好,而且耐老化性能显著。(The invention provides a preparation process of an anti-aging tea polyphenol, naringin or emodin modified polyamide mother particle, which comprises the preparation step of a loading agent; the preparation of the loading agent comprises raw material pretreatment, blending, heat treatment, elution and drying; the blending comprises the following steps: adding the preparation raw material of the loading agent into a stirring kettle, and stirring for 8-15min at the rotating speed of 1200-1500rpm to obtain a mixed material A; mixing the mixed material A with far infrared nano powder to obtain a mixed material B; subjecting the mixed material B to ultrasonic treatment at 28-30 deg.C for 28-32min at 33-38KHZ to obtain blended powder; the heat treatment comprises the following steps: mixing the blended powder with the treatment liquid, heating to 99-100 ℃ at the speed of 5-6 ℃/min, and carrying out heat preservation treatment for 30-40 min. The modified nylon master batch prepared by the invention has good antibacterial performance and obvious aging resistance.)

1. A preparation process of an anti-aging tea polyphenol, naringin or emodin modified polyamide master batch is characterized by comprising the following steps: comprises a preparation step of a loading agent; the preparation of the loading agent comprises raw material pretreatment, blending, heat treatment, elution and drying; the blending comprises the following steps: adding the preparation raw material of the loading agent into a stirring kettle, and stirring for 8-15min at the rotating speed of 1200-1500rpm to obtain a mixed material A; mixing the mixed material A with far infrared nano powder to obtain a mixed material B; subjecting the mixed material B to ultrasonic treatment at 28-30 deg.C for 28-32min at 33-38KHZ to obtain blended powder; the heat treatment comprises the following steps: mixing the blended powder with the treatment liquid, heating to 99-100 ℃ at the speed of 5-6 ℃/min, and carrying out heat preservation treatment for 30-40 min.

2. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 1, which is characterized in that:

the preparation raw materials of the loading agent comprise: montmorillonite, zeolite powder, aerogel, porous nano TiO₂Porous nano SiO₂One or more of; preferably montmorillonite, zeolite powder, aerogel and porous nano SiO₂According to the following steps of 1: 2: 0.5: 3 in a mass ratio.

3. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 1, which is characterized in that: the mass ratio of the mixed material A to the far infrared nano powder is 15-20: 1.

4. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 1, which is characterized in that: the far infrared nano powder consists of the following components in parts by weight: 10-15 parts of nano zirconia, 5-7 parts of aluminum silicate and 6-9 parts of medical stone powder; the powder fineness is 7000-.

5. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 1, which is characterized in that: the mass of the treatment liquid is 5-6 times of that of the mixed dispersion liquid;

the treating fluid is prepared by mixing sodium carbonate, sodium borate and water according to the mass ratio of 1:1.5-2: 9-10.

6. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 1, which is characterized in that: and (3) eluting and drying: washing the heat-treated filter residue by using deionized water twice; performing suction filtration again, and keeping filter residue; drying the filter residue until the water content is lower than 8%, and then placing the filter residue in a grinder to grind to 9900-10000 meshes to obtain the loading agent.

7. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 1, which is characterized in that: the preparation process also comprises the step of preparing a functional modifier; the preparation of the functional modifier comprises the following steps: mixing the tea polyphenol, naringin or emodin solution with the loading agent, stirring at the rotation speed of 30-60r/min for 30-120min to ensure that the tea polyphenol, naringin or emodin fully enter the porous material to obtain the functional modifier.

8. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 1, which is characterized in that: the preparation process further comprises the following steps of: adding the chinlon chips, the antioxidant, the dispersing agent and the functional modifier into a double-screw extruder, controlling the melting temperature to be 255-.

9. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 8, characterized in that: the mass ratio of the nylon chips to the antioxidant to the dispersant to the functional modifier is 100:4-6:5-9: 5.5-6.5.

10. The preparation process of the aging-resistant tea polyphenol, naringin or emodin modified nylon masterbatch according to claim 8, characterized in that: the antioxidant is as follows: is tert-butyl p-hydroxyanisole; the dispersing agent is as follows: the polyacrylamide, the polyoxyethylene ether and the benzyl alcohol are mixed according to the mass ratio of 6.5-7:1-1.2: 0.5-0.6.

Technical Field

The invention belongs to the technical field of fiber manufacturing, and particularly relates to an anti-aging tea polyphenol, naringin or emodin modified polyamide master batch and a preparation process thereof.

Background

The modified nylon is one kind of engineering plastic and is granular product with nylon material as base material and through altering its physical properties. The product output is modified according to the requirements of some manufacturers.

The modified nylon generally comprises reinforced nylon, toughened nylon, wear-resistant nylon, halogen-free flame-retardant nylon, conductive nylon, flame-retardant nylon and the like. 1. Thermal properties, glass transition temperature (Tg) and melting point (Tm); high Heat Distortion Temperature (HDT); high long-term use temperature (UL-746B); the application temperature range is large; the coefficient of thermal expansion is small. 2. The mechanical properties are high strength, high mechanical modulus, low creep, strong wear resistance and fatigue resistance. 3. Other, chemical resistance, electric resistance, flame resistance, weather resistance and dimensional stability are good. The product is produced by modifying according to different requirements of manufacturers, and the modified nylon roughly comprises reinforced nylon, toughened nylon, wear-resistant nylon, halogen-free flame-retardant nylon, conductive nylon, flame-retardant nylon and the like. The modified nylon has many characteristics, so the modified nylon is widely applied to automobiles, electrical equipment, mechanical parts, transportation equipment, textile, paper making machinery and the like.

The tea polyphenol is a general name of polyphenol substances in tea leaves, is white amorphous powder, and mainly comprises the following components: flavanones, anthocyanidins, flavonols, anthocyanins, phenolic acids and depside 6 compounds. Is easily soluble in water, ethanol and ethyl acetate, and is slightly soluble in oil. Naringin is mainly present in pericarp and pulp of Citrus grandis (Citrus grandis) of Rutaceae, Citrus paradisi, Citrus reticulata and Citrus aurantium, and is yellowish powder or white-like powder, and belongs to flavonoid compounds. 1 gram of the polymer was dissolved in 1000ml of water, in acetone, ethanol, hot acetic acid and hot water, and not in ether, ethane and chloroform. Emodin, loose powder in appearance, no agglomeration, orange long needle crystal, and uniform. Tea polyphenols, naringin and emodin, as biological modifiers, are now of great interest in the textile industry.

However, the research of using tea polyphenol, naringin or emodin to modify chinlon master batch is less at present. In the process research of modifying the chinlon master batch by using tea polyphenol, naringin or emodin, a great number of technical problems exist; particularly, the immobilization difficulty is high, the washing loss rate is high, the spinnability of master batches is poor, the strength of spinning fibers is poor, and the product effect is seriously influenced.

Patent CN201811455186.4 discloses a plant-derived chinlon master batch and a preparation method thereof, wherein the plant-derived chinlon master batch is mainly prepared by blending and melting a chinlon master batch and a modified sarcandra glabra extract; the mass ratio of the chinlon master batch to the modified sarcandra glabra extract is 84: 16; the invention also provides a preparation method of the cellulose fiber; the plant-derived chinlon master batch prepared by the invention has a regular shape, no continuous grains and no fragments, the grain diameter uniformity is 95.9-97.2%, and the water content is 0.81-0.89 per mill; the prepared fiber has the fiber breaking strength of 7.4-8.1cN/dtex, the elongation at break of 36.2-37.4 percent and the fiber moisture absorption rate of 11.8-12.2 percent, and has durable moisture absorption performance after being washed for many times.

Patent CN201710716647.8 discloses a preparation method of graphene nylon masterbatch and fiber, belonging to the field of materials and comprising the following steps: mixing ionic liquid and deionized water, carrying out ultrasonic treatment, then putting a graphene raw material into a solute medium, and carrying out ultrasonic treatment while stirring for 15-60 min to control the mass fraction of graphene to be 5-40 wt%; adding polyamide particles or slices, and controlling the mass ratio of the graphene to the polyamide particles or slices to be 1: 200, stirring for 2-4 h at the temperature of 40-50 ℃; centrifuging or performing suction filtration or filter pressing, and drying to obtain the graphene chinlon master batch. The invention has the beneficial effects that: the method has the advantages that the ionic liquid and the deionized water are mixed, the graphene powder is subjected to surface treatment, the obtained graphene nylon master batch and the fiber have obvious gloss, the obtained graphene nylon fiber has the conductive, electromagnetic wave resistant, anti-static and efficient far infrared shielding characteristics, and the physical and chemical properties of the common nylon fiber are greatly improved.

The above patent technology can not be used in the process of modifying polyamide master batch of tea polyphenol, naringin or emodin, but can not realize effective modifier immobilization, and the spinning performance of the master batch is greatly influenced.

Disclosure of Invention

In order to solve the problems in the prior art and further optimize the prior art, the invention provides an anti-aging tea polyphenol, naringin or emodin modified polyamide master batch and a preparation process thereof, so as to realize the following purposes: improve the nylon master batch modified by tea polyphenol, naringin or emodin, and improve the far infrared performance, the aging resistance and the antibacterial performance.

In order to solve the technical problems, the invention adopts the following technical scheme:

a preparation process of an anti-aging tea polyphenol, naringin or emodin modified polyamide mother particle comprises a preparation step of a loading agent; the preparation of the loading agent comprises raw material pretreatment, blending, heat treatment, elution and drying; the blending comprises the following steps: adding the preparation raw material of the loading agent into a stirring kettle, and stirring for 8-15min at the rotating speed of 1200-1500rpm to obtain a mixed material A; mixing the mixed material A with far infrared nano powder to obtain a mixed material B; subjecting the mixed material B to ultrasonic treatment at 28-30 deg.C for 28-32min at 33-38KHZ to obtain blended powder; the heat treatment comprises the following steps: mixing the blended powder with the treatment liquid, heating to 99-100 ℃ at the speed of 5-6 ℃/min, and carrying out heat preservation treatment for 30-40 min.

The preparation raw materials of the loading agent comprise: montmorillonite, zeolite powder, aerogel, porous nano TiO₂Porous nano SiO₂One or more of; preferably montmorillonite, zeolite powder, aerogel and porous nano SiO₂According to the following steps of 1: 2: 0.5: 3 in a mass ratio.

The mass ratio of the mixed material A to the far infrared nano powder is 15-20: 1.

The far infrared nano powder consists of the following components in parts by weight: 10-15 parts of nano zirconia, 5-7 parts of aluminum silicate and 6-9 parts of medical stone powder; the powder fineness is 7000-.

The mass of the treatment liquid is 5-6 times of that of the mixed dispersion liquid;

the treating fluid is prepared by mixing sodium carbonate, sodium borate and water according to the mass ratio of 1:1.5-2: 9-10.

And (3) eluting and drying: washing the heat-treated filter residue by using deionized water twice; performing suction filtration again, and keeping filter residue; drying the filter residue until the water content is lower than 8%, and then placing the filter residue in a grinder to grind to 9900-10000 meshes to obtain the loading agent.

The preparation process also comprises the step of preparing a functional modifier; the preparation of the functional modifier comprises the following steps: mixing the tea polyphenol, naringin or emodin solution with the loading agent, stirring at the rotation speed of 30-60r/min for 30-120min to ensure that the tea polyphenol, naringin or emodin fully enter the porous material to obtain the functional modifier.

The preparation process further comprises the following steps of: adding the chinlon chips, the antioxidant, the dispersing agent and the functional modifier into a double-screw extruder, controlling the melting temperature to be 255-.

The mass ratio of the nylon chips to the antioxidant to the dispersant to the functional modifier is 100:4-6:5-9: 5.5-6.5.

The antioxidant is as follows: is tert-butyl p-hydroxyanisole; the dispersing agent is as follows: the polyacrylamide, the polyoxyethylene ether and the benzyl alcohol are mixed according to the mass ratio of 6.5-7:1-1.2: 0.5-0.6.

By adopting the technical scheme, the invention has the beneficial effects that:

1. the modified nylon master batch prepared by the invention has the far infrared function, the far infrared emissivity is 0.88-0.89, and the far infrared radiation temperature is increased by 1.4-1.6 ℃;

2. the modified nylon master batch prepared by the invention has good aging resistance, and the mechanical property of the nylon master batch is not reduced after the nylon master batch is processed at the temperature of 50-60 ℃ for 144 h.

3. The modified nylon master batch prepared by the invention has good antibacterial effect; the bacteriostasis rate to staphylococcus aureus, escherichia coli and candida albicans is over 96 percent; the modified nylon master batch prepared by the invention has good washing resistance effect; after washing for 50 times, the bacteriostasis rate still reaches more than 95 percent.

4. The modified nylon master batch prepared by the invention has good antistatic effect, the friction voltage is 15-16V, and the surface resistivity is 6.1-6.2 × 10⁷Ω。

Detailed Description

The invention is further illustrated below with reference to specific examples.