CN103774271A - Functional nylon-6 fiber and preparation method thereof - Google Patents

Abstract

The invention relates to a functional nylon 6 fiber and a preparation method thereof. The fiber comprises a branched nylon 6 functional masterbatch and conventional nylon 6 slices, wherein the mass percentage of the branched nylon 6 functional masterbatch is 6-10%; the preparation method thereof Including: (1) Preparation of branched nylon 6 functional masterbatch by in-situ polymerization or blending method; (2) Separate crystallization of branched nylon 6 functional masterbatch and conventional nylon 6 slices, drying and mixing, and then vacuum drying The blended chips are obtained; finally, the blended chips are melt-spun. The invention can appropriately reduce the dosage of functional additives under the premise of improving or maintaining the functionality, which not only reduces the production cost, but also increases the spinnability of the fiber.

Description

A kind of functional nylon 6 fiber and preparation method thereof

technical field

The invention belongs to the field of functional nylon fibers, in particular to a functional nylon 6 fiber and a preparation method thereof.

Background technique

Nylon 6 fiber has a series of excellent properties, but also has disadvantages, such as low modulus, poor light and heat resistance, easy aging, and poor antistatic properties. With the improvement of living standards, people are not completely satisfied with the warmth effect brought by traditional fibers, and are more pursuing functionalization, refinement, health and quality.

Compared with foreign developed countries, there are very few new nylon fiber products with independent intellectual property rights in my country at present, and fewer varieties are actually used for industrialization. Secondly, the price of nylon fiber is higher than that of polyester fiber, and fiber series products must be positioned at the high-end level. , in order to ensure the competitiveness of enterprises. Therefore, the development of new nylon 6 fiber and its products, the improvement of the differentiation rate of nylon 6 fiber and the application in high-grade chemical fiber fabrics are the inevitable trend of the development of nylon industry.

Introducing anti-ultraviolet agents, antistatic agents, antibacterial agents, etc. to prepare functional nylon 6 masterbatch and its fibers by blending or copolymerization can effectively improve the application value of fibers. The introduction of functional particles by blending can make the functional particles evenly dispersed in the fiber cross-section by adding a coupling agent, but if the particles can be maximized and dispersed on the fiber surface, the increase in the contact specific surface area can not only optimize and maximize the Play the role of functional particles, and can properly reduce the amount of particles added, with good spinning and forming processing.

Contents of the invention

The technical problem to be solved by the present invention is to provide a functional nylon 6 fiber and its preparation method, which ensures that the functional particles are maximized and stably distributed on the surface of the fiber, and can avoid a large number of functional particles gathering in the center of the fiber as far as possible and cannot be separated from the outside world such as Direct contact with human skin, etc., to maximize the functional effects of antistatic, anti-ultraviolet, antibacterial, deodorizing, flame retardant, and far infrared.

A functional nylon 6 fiber of the present invention, the fiber comprises a branched nylon 6 functional masterbatch and conventional nylon 6 chips, wherein the mass percentage of the branched nylon 6 functional masterbatch is 6-10%; the branched nylon 6 Functional masterbatch is in-situ polymerization branched chain nylon 6 functional masterbatch or blended branched chain nylon 6 functional masterbatch.

The blended branched-chain nylon 6 functional masterbatch is prepared by combining branched-chain nylon 6 slices with nano-functional additives, dispersants and coupling agents for melt blending and pelletizing; wherein the mass percentage of each component is:

The branched-chain nylon 6 chips are prepared by polymerizing caprolactam, molecular weight modifier, deionized water and isophthalic acid or pyromellitic acid under nitrogen protection. Based on the caprolactam, the mass of other components The percentage is:

Molecular weight modifier 5～7‰;

Deionized water 4~5%;

Isophthalic acid or pyromellitic acid 1-2%.

The in-situ polymerized branched nylon 6 functional masterbatch is prepared by polymerizing caprolactam, molecular weight regulator, deionized water, nano functional additives, coupling agent and isophthalic acid or pyromellitic acid under nitrogen protection , based on the caprolactam, the mass percentages of all the other components are:

The molecular weight regulator is one or more of organic acids such as adipic acid and acetic acid.

The nano-functional additive is one or more of antistatic agent, antiultraviolet agent, antibacterial agent, deodorant, flame retardant, far-infrared additive and the like.

The coupling agent is one or more of silane coupling agents and titanate coupling agents; the silane coupling agent is one or more of commercially available KH550, KH560, and KH570; the The titanate coupling agent used is one or more of commercially available NDZ-105, NDZ-133, NDZ-201, NDZ-311, NDZ-311W, and NDZ-401.

A kind of preparation method of functional nylon 6 fiber of the present invention comprises:

(1) Blending preparation of branched nylon 6 functional masterbatch:

The coupling agent, nano-functional additive and ethanol are ultrasonically oscillated for 2-3 hours, sprayed by airflow and then dried to obtain the nano-functional additive modified by the coupling agent; then the nano-functional additive modified by the coupling agent is mixed with branched chain nylon 6 After the slices are mixed and fully stirred, enter the twin-screw extruder for melt extrusion, and then pelletize to obtain the branched chain nylon 6 functional masterbatch;

or prepared by in situ polymerization:

Or in-situ polymerize caprolactam, molecular weight regulator, deionized water, nano-functional additives, coupling agent and isophthalic acid or pyromellitic acid at 250-270°C, and then pelletize the obtained polymeric melt Obtain branched chain nylon 6 functional masterbatch;

(2) Blending and spinning

The branched nylon 6 functional masterbatch and conventional nylon 6 chips are crystallized separately, dried, mixed, and then vacuum-dried to obtain blended chips; finally, the blended chips can be melt-spun.

After the granulation described in step (1), the product is extracted with pure water at 100-120°C to reduce the extractables to less than 0.5%, and finally dried to constant weight under nitrogen at 110-140°C.

The branched-chain nylon 6 functional masterbatch and conventional nylon 6 slices described in step (2) are crystallized separately, and the drying time in drying is 20 to 24 hours, and the drying temperature is 100 to 120 °C; the vacuum drying is at 100 Vacuum dry at ~120°C for 1-2 hours.

In the melt spinning described in step (2), the temperature of the screw zone is 250-270°C, the spinning speed is 4200-4400m/min, the drawing temperature of GR1 is normal temperature, the drawing temperature of GR2 is 160-185°C, and the drawing temperature is 160-185°C. The multiple is 1.1 to 2.0 times, and the aspect ratio of the spinneret hole is 2.5 to 3:1. Add a slow cooling device. The diameter of the heating sleeve is the same as the diameter of the spinneret plate, and the temperature in the slow cooling zone is 250 to 270 ° C. The heating sleeve is 5-7cm long.

The optimal choice of the present invention is the in-situ polymerization method, and the prepared branched nylon 6 masterbatch forms a spherical shape and has high fluidity and functionality. The prepared branched nylon 6 chips have a relative viscosity of 2.0-2.3 and a melting point of 218-221° C., and the branched nylon 6 has low viscosity and high fluidity.

In the present invention, in the melt spinning, the temperature of the screw zone is 250-270°C, the spinning speed is 4200-4400m/min, the drawing temperature of GR1 is normal temperature, the drawing temperature of GR2 is 160-185°C, and the draw ratio is 1.1-2.0 times , in which the aspect ratio of the spinneret hole is 2.5-3:1, the slow cooling device is added, the tube diameter of the heating sleeve is the same as that of the spinneret plate, the temperature of the slow cooling zone is 250-270°C, and the length of the heating sleeve is 5-270°C. 7cm, to ensure that the temperature difference of the tow at the filament outlet is small, so as to realize the slow cooling effect of the tow, and at the same time, the branched chain nylon 6 functional masterbatch leaves the spinneret hole and uses its high fluidity to expand on the surface of the fiber through the orifice in the slow cooling zone. A functional nylon 6 fiber was prepared.

The invention relates to a preparation method of functional nylon 6 fiber, which uses branched nylon 6, has low viscosity, and has high fluidity compared with conventional nylon 6. During the spinning process, when the polymer melt is extruded from the small hole of the spinneret, since the melt enters the small hole of the spinneret, a longitudinal velocity gradient is generated in the flow direction, and the melt undergoes tensile elastic deformation and stays in it. The time is short, and there is no time to relax. At the exit, the external force will release the effect on the molecular chain, and the stretched macromolecular chain will return to the curled state. On the other hand, the polymer is subjected to shear stress during the flow process, resulting in extrusion. The diameter of the extruded object becomes obviously larger, and extrusion swelling occurs. Branched-chain nylon 6 expands with extrusion at the spinneret. Due to the fast flow speed, it first distributes quickly to both sides, driving the functional particles to enrich on the fiber surface. In addition, a slow cooling device is added under the spinning box to ensure the stability of the particles. Distributed on the surface, the cooled fiber can achieve the effect similar to the finishing process, but it is durable. The outer layer of the fiber is branched functional nylon 6, and the inner layer is conventional nylon 6.

Compared with conventional nylon 6, the branched-chain nylon 6 used in the present invention has low viscosity and high fluidity. During the extrusion process of the spinneret of the spinning box, combined with the slow cooling process, the high-fluidity branched-chain nylon 6 drives functional particles Enriched on the surface of the fiber, the cooled fiber can meet the required requirements.

Beneficial effect:

(1) Branched chain nylon 6 has better melt fluidity than conventional nylon 6. The polymer melt is extruded from the small hole of the spinneret. With the expansion effect of melt extrusion, high fluidity nylon 6 drives the enrichment of functional particles in the The surface of the fiber, combined with the slow cooling process, ensures that the functional particles are maximized and stably distributed on the surface of the fiber, and it is possible to avoid a large number of functional particles gathering in the center of the fiber and not directly contacting the outside world such as human skin. The particles on the surface maximize the functional effects of antistatic, anti-ultraviolet, antibacterial, deodorizing, flame retardant, and far-infrared.

(2) The present invention can appropriately reduce the dosage of functional additives on the premise of improving or maintaining the functionality, which not only reduces the production cost, but also increases the spinnability of the fiber.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

A functional nylon 6 fiber, which is composed of branched nylon 6 functional masterbatch and conventional nylon 6 chips, and its mass percentage is:

Branched chain nylon 6 functional masterbatch 6%

Regular Nylon 6 Slices Surplus

In-situ polymerization is optimally selected, and the polymerized branched nylon 6 functional masterbatch is made of isophthalic acid, caprolactam, molecular weight regulator, deionized water, nano-functional additives, and coupling agent, and is prepared by polymerization reaction under nitrogen protection. Get, take described caprolactam as benchmark, its raw material component mass percent is:

Described molecular weight regulator is acetic acid;

The nano functional additive is an antistatic agent.

The coupling agent can be commercially available NDZ-105 as a titanate coupling agent.

The prepared branched nylon 6 chips have a relative viscosity of 2.3 and a melting point of 221° C., and the branched nylon 6 has low viscosity and high fluidity.

Its preparation method is:

(1) Preparation of branched nylon 6 functional masterbatch

After the caprolactam is metered, it passes through the static mixer together with the metered isophthalic acid molecular weight regulator, deionized water, functional additives, and silane coupling agent, and then enters the polymerization tower, and undergoes polymerization and ring opening. The polymerization temperature is 250°C. The polymer melt is pelletized and extracted with pure water at 100°C to reduce the extractables to less than 0.5%. The slices after extraction were dried to constant weight at 110°C by blowing nitrogen gas.

(2) Blending and spinning

Separately crystallize the branched nylon 6 functional masterbatch and conventional nylon 6 slices, dry for 20 hours at a drying temperature of 100°C, then mix them in proportion, and dry them in a vacuum drum oven for 1 hour at a drying temperature of 100°C to obtain a total mixed slice;

The blended chips are blended and spun through melt spinning equipment. The process route is: screw extruder → pre-filter → metering pump → spinning assembly → spinning → side blowing and oiling → drafting → winding, screw The zone temperature is 250-270°C, the spinning speed is 4200m/min, the GR2 drawing temperature is 160°C, the drafting ratio is 1.1 times, and the aspect ratio of the spinneret hole is 2.5:1, add slow cooling device, heating jacket The barrel diameter is the same as that of the spinneret plate, the temperature of the slow cooling zone is 250°C, and the length of the heating sleeve is 7cm, which ensures that the temperature difference of the tow at the filament exit is small, thereby realizing the effect of slow cooling of the tow, and at the same time branched chain nylon 6 The functional masterbatch leaves the spinneret hole and uses its high fluidity to expand on the surface of the fiber through the orifice in the slow cooling zone to obtain a functional nylon 6 fiber.

Example 2

A functional nylon 6 fiber, which is composed of branched nylon 6 functional masterbatch and conventional nylon 6 chips, and its mass percentage is:

Branched chain nylon 6 functional masterbatch 8%

Regular Nylon 6 Slices Surplus

In-situ polymerization is optimally selected, and the polymerized branched nylon 6 functional masterbatch is made of pyromellitic acid, caprolactam, molecular weight regulator, deionized water, nano-functional additives, and coupling agent, and is prepared by polymerization reaction under nitrogen protection. Get, take described caprolactam as benchmark, its raw material component mass percent is:

Described molecular weight regulator is acetic acid;

The nano-functional additives are antibacterial agents and far-infrared additives.

The coupling agent can be silane coupling agent KH560 and titanate coupling agent NDZ-311W.

The prepared branched nylon 6 chips have a relative viscosity of 2.2 and a melting point of 220° C., and the branched nylon 6 has low viscosity and high fluidity.

Its preparation method is:

(1) Preparation of branched nylon 6 functional masterbatch

After the caprolactam is metered, it passes through the static mixer together with the metered pyromellitic acid molecular weight regulator, deionized water, functional additives, and silane coupling agent, and then enters the polymerization tower, and undergoes polymerization and ring opening. The polymerization temperature is 260°C. The polymer melt is pelletized and extracted with pure water at 110°C to reduce the extractables to less than 0.5%. The slices after extraction were dried to constant weight at 120°C by blowing nitrogen gas.

(2) Blending and spinning

Separately crystallize the branched nylon 6 functional masterbatch and conventional nylon 6 slices, dry for 22 hours at a drying temperature of 110°C, then mix them in proportion, and dry them in a vacuum drum oven for 1.5 hours at a drying temperature of 110°C to obtain a total mixed slice;

The blended chips are blended and spun through melt spinning equipment. The process route is: screw extruder → pre-filter → metering pump → spinning assembly → spinning → side blowing and oiling → drafting → winding, screw The zone temperature is 250-270°C, the spinning speed is 4300m/min, the drawing temperature of GR1 is normal temperature, the drawing temperature of GR2 is 170°C, and the drafting ratio is 1.3 times to prepare functional nylon 6 fibers. Among them, the aspect ratio of the spinneret hole is 2.75:1, and the slow cooling device is added. The tube diameter of the heating sleeve is the same as that of the spinneret plate, and the temperature of the slow cooling zone is 260 ° C. The temperature difference of the tow is small, so that the slow cooling effect of the tow is realized. At the same time, the branched nylon 6 functional masterbatch leaves the spinneret hole in the slow cooling zone and uses its high fluidity to expand on the surface of the fiber through the orifice to enrich and obtain a functional Nylon 6 fiber.

Example 3

A functional nylon 6 fiber, which is composed of branched nylon 6 functional masterbatch and conventional nylon 6 chips, and its mass percentage is:

Branched chain nylon 6 functional masterbatch 10%

Regular Nylon 6 Slices Surplus

In-situ polymerization is optimally selected, and the polymerized branched nylon 6 functional masterbatch is made of isophthalic acid, caprolactam, molecular weight regulator, deionized water, nano-functional additives, and coupling agent, and is prepared by polymerization reaction under nitrogen protection. Get, take described caprolactam as benchmark, its raw material component mass percent is:

Described molecular weight regulator is adipic acid, acetic acid;

The nano-functional additive deodorant and far-infrared additive.

The coupling agent can be titanate coupling agent NDZ-133, NDZ-201.

The prepared branched nylon 6 chips have a relative viscosity of 2.1 and a melting point of 219° C., and the branched nylon 6 has low viscosity and high fluidity.

Its preparation method is:

(1) Preparation of branched nylon 6 functional masterbatch

After the caprolactam is metered, it passes through the static mixer together with the metered isophthalic acid molecular weight regulator, deionized water, functional additives, and silane coupling agent, and then enters the polymerization tower, and undergoes polymerization and ring opening. The polymerization temperature is 270°C. The polymer melt is pelletized and extracted with pure water at 120°C to reduce the extractables to less than 0.5%. The slices after extraction were dried to constant weight at 140°C by blowing nitrogen gas.

(2) Blending and spinning

Separately crystallize the branched nylon 6 functional masterbatch and conventional nylon 6 slices, dry for 24 hours at a drying temperature of 120°C, then mix them in proportion, and dry them in a vacuum drum oven for 2 hours at a drying temperature of 120°C to obtain a total mixed slice;

The blended chips are blended and spun through melt spinning equipment. The process route is: screw extruder → pre-filter → metering pump → spinning assembly → spinning → side blowing and oiling → drafting → winding, screw The zone temperature is 250-270°C, the spinning speed is 4400m/min, the drawing temperature of GR1 is normal temperature, the drawing temperature of GR2 is 185°C, and the draw ratio is 1.5 times. The aspect ratio of the spinneret holes is 3:1, increasing Slow cooling device, the tube diameter of the heating sleeve is the same as the diameter of the spinneret plate, the temperature of the slow cooling zone is 270°C, and the length of the heating sleeve is 5cm, so as to ensure that the temperature difference of the filament bundle at the filament outlet changes little and gradually returns to normal temperature, so as to realize the A functional nylon 6 fiber was prepared by slow cooling of the bundle.

Example 4

A functional nylon 6 fiber, which is composed of branched nylon 6 functional masterbatch and conventional nylon 6 chips, and its mass percentage is:

Branched chain nylon 6 functional masterbatch 9%

Conventional nylon 6 slice margin;

The blended branched-chain nylon 6 functional masterbatch is prepared by combining branched-chain nylon 6 slices with nano-functional additives, dispersants and coupling agents for melt blending and pelletizing; wherein the mass percentage of each component is:

The branched-chain nylon 6 chips are prepared by polymerizing caprolactam, molecular weight modifier, deionized water and isophthalic acid or pyromellitic acid under nitrogen protection. Based on the caprolactam, the mass of other components The percentage is:

Molecular weight modifier 6‰;

Deionized water 5%;

Isophthalic acid or pyromellitic acid 2%.

Described molecular weight regulator is adipic acid;

The nano-functional additives are anti-ultraviolet agents and antibacterial agents.

The coupling agent can be silane coupling agent KH550.

The prepared branched nylon 6 chips have a relative viscosity of 2.0 and a melting point of 218° C., and the branched nylon 6 has low viscosity and high fluidity.

Its preparation method is:

(1) Blending preparation of branched nylon 6 functional masterbatch

The coupling agent, nano-functional additive and ethanol are ultrasonically oscillated for 2-3 hours, sprayed by airflow and then dried to obtain the nano-functional additive modified by the coupling agent; then the nano-functional additive modified by the coupling agent is mixed with branched chain nylon 6 After the slices are mixed and fully stirred, enter the twin-screw extruder for melt extrusion, and then pelletize to obtain the branched chain nylon 6 functional masterbatch;

(2) Blending and spinning

Separately crystallize the branched nylon 6 functional masterbatch and conventional nylon 6 slices, dry for 22 hours at a drying temperature of 110°C, then mix them in proportion, and dry them in a vacuum drum oven for 1.5 hours at a drying temperature of 110°C to obtain a total mixed slice;

The blended chips are blended and spun through melt spinning equipment. The process route is: screw extruder → pre-filter → metering pump → spinning assembly → spinning → side blowing and oiling → drafting → winding, screw The zone temperature is 250-270°C, the spinning speed is 4300m/min, the drawing temperature of GR1 is normal temperature, the drawing temperature of GR2 is 170°C, and the draw ratio is 2.0 times to prepare functional nylon 6 fibers. Among them, the aspect ratio of the spinneret hole is 2.75:1, and the slow cooling device is added. The tube diameter of the heating sleeve is the same as that of the spinneret plate, and the temperature of the slow cooling zone is 260 ° C. The temperature difference of the tow is small, so that the slow cooling effect of the tow is realized. At the same time, the branched nylon 6 functional masterbatch leaves the spinneret hole in the slow cooling zone and uses its high fluidity to expand on the surface of the fiber through the orifice to enrich and obtain a functional Nylon 6 fiber.

Claims (10)

1. A functional nylon 6 fiber, the fiber comprising branched nylon 6 functional masterbatch and conventional nylon 6 slices, wherein the mass percentage of branched nylon 6 functional masterbatch is 6 to 10%; the branched nylon 6 functional The masterbatch is in-situ polymerized branched nylon 6 functional masterbatch or blended branched nylon 6 functional masterbatch. 2. A kind of functional nylon 6 fiber according to claim 1, characterized in that: said blended branched chain nylon 6 functional masterbatch is combined with branched chain nylon 6 slices and nano functional additives, dispersant and coupling agent Melt blending and pelletizing; the mass percentage of each component is: 3. a kind of functional nylon 6 fiber according to claim 2, is characterized in that: described branched chain nylon 6 slice is made of caprolactam, molecular weight modifier, deionized water and isophthalic acid or pyromellitic acid in nitrogen Prepared by polymerization under protection, based on the caprolactam, the mass percentages of the remaining components are: Molecular weight modifier 5～7‰; Deionized water 4~5%; Isophthalic acid or pyromellitic acid 1-2%. 4. a kind of functional nylon 6 fiber according to claim 1, is characterized in that: described in-situ polymerization branched chain nylon 6 functional masterbatch is made of caprolactam, molecular weight regulator, deionized water, nano functional additive, coupling Agent and isophthalic acid or pyromellitic acid are prepared by polymerization under nitrogen protection. Based on the caprolactam, the mass percentages of the remaining components are:

5. A functional nylon 6 fiber according to claim 3 or 4, characterized in that: the molecular weight regulator is one or more of adipic acid and acetic acid. 6. A kind of functional nylon 6 fiber according to claim 2 or 4, characterized in that: the nano-functional additive is an antistatic agent, an anti-ultraviolet agent, an antibacterial agent, a deodorant, a flame retardant, a far-infrared One or more of the additives. 7. A kind of functional nylon 6 fiber according to claim 2 or 4, is characterized in that: described coupling agent is one or more in silane coupling agent, titanate coupling agent; The silane coupling agent is one or more of commercially available KH550, KH560, KH570; the described titanate coupling agent is commercially available NDZ-105, NDZ-133, NDZ-201, NDZ-311, NDZ- One or more of 311W, NDZ-401. 8. the preparation method of the functional nylon 6 fiber as described in any one of claim 1-7, comprises: (1) Ultrasonic vibration of the coupling agent, nano-functional additive and ethanol for 2-3 hours, drying after spraying by airflow, to obtain the nano-functional additive modified by the coupling agent; then mix the nano-functional additive modified by the coupling agent with the Chain nylon 6 slices are mixed and fully stirred, then enter the twin-screw extruder for melt extrusion, and then pelletize to obtain branched chain nylon 6 functional masterbatch; Or in-situ polymerize caprolactam, molecular weight regulator, deionized water, nano-functional additives, coupling agent and isophthalic acid or pyromellitic acid at 250-270°C, and then pelletize the obtained polymeric melt Obtain branched chain nylon 6 functional masterbatch; (2) Separately crystallize the branched nylon 6 functional masterbatch and conventional nylon 6 slices, mix them after drying, and then dry them in vacuum to obtain blended slices; finally melt-spin the blended slices. 9. The preparation method of functional nylon 6 fiber according to claim 8, characterized in that: after the granulation described in step (1), the product is extracted with pure water at 100-120°C to reduce the extractables to less than 0.5%, and finally dried to constant weight under nitrogen at 110-140°C. 10. The preparation method of functional nylon 6 fiber according to claim 8, characterized in that: the temperature of the screw zone in the melt spinning described in step (2) is 250-270°C, and the spinning speed is 4200-4400m/ min, GR1 drafting temperature is normal temperature, GR2 drafting temperature is 160-185°C, drafting ratio is 1.1-2.0 times, and the aspect ratio of spinneret hole is 2.5-3:1, add slow cooling device and heating sleeve The tube diameter is the same as that of the spinneret plate, the temperature in the slow cooling zone is 250-270°C, and the length of the heating sleeve is 5-7cm.