CN117820853A - Flame-retardant master batch for nylon 66 fibers and preparation method and application thereof - Google Patents

Flame-retardant master batch for nylon 66 fibers and preparation method and application thereof Download PDF

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Publication number
CN117820853A
CN117820853A CN202311611992.7A CN202311611992A CN117820853A CN 117820853 A CN117820853 A CN 117820853A CN 202311611992 A CN202311611992 A CN 202311611992A CN 117820853 A CN117820853 A CN 117820853A
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nylon
flame
powder
fiber
retardant
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赵亮
赵丽丽
厉勇
戎智宗
苏家凯
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Shandong Nanshan Zhishang Technology Co ltd
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Shandong Nanshan Zhishang Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a flame-retardant master batch for nylon 66 fibers, a preparation method and application thereof, and the flame-retardant master batch has good flame retardance and spinnability and can be used for manufacturing nylon 66 fibers with good flame retardance and mechanical properties. The flame-retardant master batch is prepared from melamine polyphosphate, tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate, graphene powder, a wetting dispersant, a lubricant, a coupling agent and an antioxidant serving as raw materials through a series of processes of wetting, dispersing, grinding, mixing, extruding and the like. The flame-retardant nylon master batch prepared by the invention contains graphene with small sheets, and has good mechanical properties due to the good mechanical properties. The flame-retardant nylon master batch prepared by the invention has good spinnability. The method is applied to the field of nylon 66 fibers.

Description

Flame-retardant master batch for nylon 66 fibers and preparation method and application thereof
Technical Field
The invention relates to the field of nylon fibers, in particular to a flame-retardant masterbatch for nylon 66 fibers, and a preparation method and application thereof.
Background
The nylon, the terylene and the acrylon are three main types applied to the civil fiber field, and play an important role in promoting the development history of fibers. Nylon 6 and nylon 66 are most widely used, accounting for about 98% of the total nylon yield. With the continuous expansion and improvement of the application field of nylon 66 fibers, the nylon 66 flame-retardant fibers are increasingly focused by technicians, and particularly in the aspect of application to security teams, the flame-retardant function of the fibers is increasingly important.
Flame retardants have a long history of development and are used in the fields of plastics and rubber, but the use of flame retardants in the field of nylon 66 fibers is a new subject. At present, two technical paths are mainly adopted, namely, a flame retardant is added into nylon 66 for reaction, namely, bulk polymerization is modified, and although the flame retardant is well dispersed in a liquid phase system of the bulk polymerization, the flame retardant has certain negative effects on the reaction of the bulk polymerization, such as the polymerization reaction rate, the molecular weight distribution and the like, and besides, the technical means can bear huge pressure in the aspect of industrial production and amplification; the invention patent with publication number CN117050519A discloses a preparation method of a flame-retardant nylon 66 composite material, which comprises the steps of adding nylon 66, LDHs/rGO flame retardant, antioxidant, toughening agent and lubricant into a mixer for high-speed mixing, extruding, granulating and drying by a double-screw extruder to obtain the flame-retardant nylon 66 material, wherein the flame retardant is powder, the nylon 66 is sliced into particles, the appearance sizes of the two materials are greatly different, uniformity is difficult to achieve in the mixing process, and the nylon 66 fiber prepared by the method has poor spinnability. Therefore, development of the flame-retardant master batch effectively applied to the field of nylon 66 flame-retardant fibers has important research significance.
Disclosure of Invention
The invention aims to overcome the defects of poor spinnability and poor mechanical property in the production of the existing nylon 66 flame-retardant fiber and the defects of the prior art, and provides a flame-retardant master batch applicable to the field of the nylon 66 flame-retardant fiber, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the flame-retardant master batch for the nylon 66 fiber comprises the following components in percentage by weight:
melamine polyphosphate: 6.0 to 40.0 percent;
tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate: 3.0 to 20.0 percent;
graphene powder: 0.01 to 0.1 percent;
wetting dispersant: 0.05 to 2.0 percent
And (3) a lubricant: 0.05 to 2.0 percent;
coupling agent: 0.1 to 3.0 percent;
antioxidant: 0.1 to 3.0 percent;
the balance of nylon 66 powder.
Furthermore, the original particle size of the melamine polyphosphate powder is less than or equal to 1.0 and um.
Further, the powder primary particle size of the tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate is less than or equal to 1.0 um.
Further, the number of layers of the graphene powder is 1.0-10.0 layers.
Further, the original particle size of the nylon 66 powder is less than or equal to 250.0 and um.
The invention also discloses a preparation method of the flame-retardant master batch for nylon 66 fibers, wherein the preparation method of the flame-retardant master batch comprises the following steps:
(1) Pretreatment of melamine polyphosphate: firstly, adding a proper amount of mixed solution of ethyl acetate and dimethylbenzene into a stirring barrel at a constant speed, and then adding a proper amount of wetting dispersant and coupling agent at a low stirring speed of 30-60 rpm. After stirring for 1 hour, adding the melamine polyphosphate powder material, and after the addition, adjusting the temperature of the stirrer to 300-1000 rpm, and stirring for 1-3 hours. And (3) grinding the prepared melamine polyphosphate powder slurry by a ball mill for 1-4 hours, and finishing grinding when the fineness of the slurry is less than or equal to 1.0 um. The ground slurry is filtered, dried and crushed, and when the fineness of the powder is less than or equal to 1.0um, the crushing is finished, and the vacuum packaging is carried out.
(2) Pretreatment of tetrakis (2, 6-dimethylphenyl) 1, 3-phenylene phosphate: adding a proper amount of mixed solution of ethyl acetate and dimethylbenzene into a stirring barrel, and then adding a proper amount of wetting dispersant and coupling agent at a low stirring speed of 30-60 rpm. After stirring for 1 hour, adding the tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate powder material, and after the addition, adjusting the speed of a stirrer to 100-500 rpm and stirring for 1-3 hours. The prepared slurry of the tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate is ground by a ball mill for 1 to 4 hours, and when the fineness of the slurry is less than or equal to 1.0um, the grinding is finished. The ground slurry is filtered, dried and crushed, and when the fineness of the powder is less than or equal to 1.0um, the crushing is finished, and the vacuum packaging is carried out.
(3) Mixing materials: adding a proper amount of nylon 66 powder into a high-speed mixer, then sequentially adding treated melamine polyphosphate and tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate, and adding a proper amount of wetting dispersant, lubricant, coupling agent and antioxidant at a low stirring speed of 30-60 rpm. After the material is fed, the speed in the high-speed mixer is adjusted to 100-500 rpm, and the material is stirred for 1-3 hours. Obtaining the mixed material.
(4) Preparation of flame-retardant master batches: and (3) adding the mixed materials in the step (III) into a 35# double-screw extruder, conveying, mixing, dissolving and extruding the materials under the conditions that the rotating speed of the screw is 30-150 rpm and the temperature of a heating zone of the screw is 100-320 ℃, and cutting the strip-shaped materials from the screw extruder by a cutting machine to obtain flame-retardant master batches.
In addition, the invention also discloses application of the flame-retardant master batch for the nylon 66 fiber, the flame-retardant master batch for the nylon 66 fiber has good spinnability, and the flame-retardant master batch for the nylon 66 fiber and corresponding nylon 66 powder are mixed with each other, so that the nylon 66 fiber with good flame retardant property can be obtained in a melt spinning mode.
The invention has the advantages that:
the invention solves the problem that the powder flame retardant material is easy to generate agglomeration phenomenon when dispersed in nylon 66. The main technical means are two, one is to pretreat the powder flame retardant material, and from the perspective of using raw materials, the generation of powder agglomerates is prevented. The second technical means is that when the flame retardant powder is mixed with nylon 66, the flame retardant powder is mixed with nylon 66 in a slice shape, which is different from the existing flame retardant powder, so that the difficult problem of uneven mixing caused by oversized appearance size of materials in the mixing process is avoided.
The flame-retardant nylon master batch prepared by the invention contains graphene with small sheets, and has good mechanical properties due to the good mechanical properties. The flame-retardant nylon master batch prepared by the invention has good spinnability.
Detailed Description
The present invention is further illustrated below in conjunction with preparation examples, examples and application examples, which are provided to illustrate the present invention and are not intended to limit the scope of the present invention.
Preparation example 1
Pretreatment of melamine polyphosphate: (laboratory stage)
Preparing a mixed solution according to the weight ratio of ethyl acetate to dimethylbenzene of 1:3, and adding the prepared mixed solution of 1000g of ethyl acetate and dimethylbenzene into a 2000ml glass beaker; then 10.0g of hyperdispersant BYK-164 was added at a low stirring speed of 50rpm and stirring was continued for 1 hour. 110g of melamine polyphosphate powder material was then added at a stirring speed of 120rpm, and after the addition was completed, the speed of the stirrer was adjusted to 800rpm and stirred for 1.5 hours. And (3) grinding the prepared melamine polyphosphate powder slurry by a ball mill for 2-3 hours, and finishing grinding when the fineness of the slurry is less than or equal to 1.0 um. The milled slurry was then filtered and vacuum dried at 95 c for 8 hours.
Crushing the dried material by using a crusher, and when the fineness of the powder is less than or equal to 1.0um, finishing crushing, and carrying out vacuum packaging to obtain the pretreated melamine polyphosphate.
Preparation example 2
Pretreatment of tetrakis (2, 6-dimethylphenyl) 1, 3-phenylene phosphate: (laboratory stage)
Preparing a mixed solution according to the weight ratio of ethyl acetate to dimethylbenzene of 1:3, and adding the prepared mixed solution of 1000g of ethyl acetate and dimethylbenzene into a 2000ml glass beaker; then 10.0g of hyperdispersant BYK-164 was added at a low stirring speed of 50rpm and stirring was continued for 1 hour. 100g of the powder material of tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate was then added at a stirring speed of 120rpm, and after the addition was completed, the speed of the stirrer was adjusted to 200rpm and stirred for 2.0 hours. The prepared slurry of the tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate is ground by a ball mill for 3.0 hours, and when the fineness of the slurry is less than or equal to 1.0um, the grinding is finished. The milled slurry was then filtered and vacuum dried at 95 c for 10 hours.
Crushing the dried material by using a crusher, and when the fineness of the powder is less than or equal to 1.0um, finishing crushing, and carrying out vacuum packaging to obtain pretreated tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate.
Preparation example 3
Pretreatment of melamine polyphosphate: (Process amplification stage)
Preparing a mixed solution according to the weight ratio of ethyl acetate to dimethylbenzene of 1:3, and adding the prepared mixed solution of ethyl acetate and dimethylbenzene with the weight of 10.0kg into a 50L stirring kettle; 100g of hyperdispersant BYK-164 was then added at a low stirring speed of 60rpm and stirring continued for 1 hour. Then 1100g of melamine polyphosphate powder material was added at a stirring speed of 120rpm, and after the addition was completed, the stirrer was adjusted to 800rpm and stirred for 1.5 hours. And (3) grinding the prepared melamine polyphosphate powder slurry by a ball mill for 2-3 hours, and finishing grinding when the fineness of the slurry is less than or equal to 1.0 um. The milled slurry was then filtered and vacuum dried at 95 c for 8 hours.
Crushing the dried material by using a crusher, and when the fineness of the powder is less than or equal to 1.0um, finishing crushing, and carrying out vacuum packaging to obtain the pretreated melamine polyphosphate.
Preparation example 4
Pretreatment of tetrakis (2, 6-dimethylphenyl) 1, 3-phenylene phosphate: (Process amplification stage)
Preparing a mixed solution according to the weight ratio of ethyl acetate to dimethylbenzene of 1:3, and adding the prepared mixed solution of ethyl acetate and dimethylbenzene with the weight of 10.0kg into a 50L stirring kettle; 100g of hyperdispersant BYK-164 was then added at a low stirring speed of 60rpm and stirring continued for 1 hour. 1000g of the tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate powder material was then added at a stirring speed of 120rpm, and after the addition was completed, the speed of the stirrer was adjusted to 600rpm and stirred for 2.0 hours. The prepared slurry of the tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate is ground by a ball mill for 3.0 hours, and when the fineness of the slurry is less than or equal to 1.0um, the grinding is finished. The milled slurry was then filtered and vacuum dried at 95 c for 10 hours.
Crushing the dried material by using a crusher, and when the fineness of the powder is less than or equal to 1.0um, finishing crushing, and carrying out vacuum packaging to obtain pretreated tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate.
Example 1
Preparation of nylon 66 flame-retardant master batch:
mixing materials: adding 5600g of nylon 66 powder into a high-speed mixer, then respectively adding 150g of high-temperature lubricant (PETS), 100g of titanate coupling agent, 100g of antioxidant (B225) and 8g of graphene powder at a low stirring speed of 15rpm, and stirring for 30 minutes at 30rpm after the addition of the auxiliary agent is completed; 3000g of treated melamine polyphosphate was then added in a stopped state, after the addition was completed, the machine was capped and its sealing performance was checked. The speed in the high-speed mixer is adjusted to 200rpm, stirring is carried out for 1 hour, then the speed in the mixer is increased to 1500rpm, stirring is carried out for 1 hour, then the machine is stopped, and the mixed materials are discharged from a discharge hole.
Extruding and granulating the mixed materials by a 35# double-screw extruder, wherein the specific operation is as follows:
the temperatures of thirteen heating areas of the twin screw are set as follows: 110 ℃, 238 ℃, 280 ℃, 300 ℃, 320 ℃, 322 ℃, 325 ℃,316 ℃, 330 ℃ when the temperature of each heating area of the screw reaches a set value, starting the water pump and the oil pump of the double screw, after 5 minutes of operation, starting the double screw, setting the rotating speed to 80 rpm, and slowly pouring the mixed materials into a charging hole. When the mixed materials pass through the double screws, the materials are heated, the flame retardant is uniformly dispersed in the melted PA66 melt under the mixing and shearing of the screws and the help of the addition agent, and then the mixture is extruded by a die at the head of the double screws and enters a water tank for cooling. The cooled material strip continuously enters a granulator and is cut into master batches with the length of 2.5 mm. The package mark is: nylon 66 flame retardant masterbatch a.
Example 2
Preparation of nylon 66 flame-retardant master batch:
mixing materials: adding 5600g of nylon 66 powder into a high-speed mixer, then respectively adding 150g of high-temperature lubricant (PETS), 100g of titanate coupling agent, 100g of antioxidant (B225) and 8g of graphene powder at a low stirring speed of 15rpm, and stirring for 30 minutes at 30rpm after the addition of the auxiliary agent is completed; 3000g of treated tetrakis (2, 6-dimethylphenyl) 1, 3-phenylene phosphate was then added while the machine was stopped, and after the addition, the machine was capped and its sealing properties were checked. The speed in the high-speed mixer is adjusted to 200rpm, stirring is carried out for 1 hour, then the speed in the mixer is increased to 1500rpm, stirring is carried out for 1 hour, then the machine is stopped, and the mixed materials are discharged from a discharge hole.
Extruding and granulating the mixed materials by a 35# double-screw extruder, wherein the specific operation is as follows:
the temperatures of thirteen heating areas of the twin screw are set as follows: 110 ℃, 238 ℃, 280 ℃, 300 ℃, 320 ℃, 322 ℃, 325 ℃,316 ℃, 330 ℃ when the temperature of each heating area of the screw reaches a set value, starting the water pump and the oil pump of the double screw, after 5 minutes of operation, starting the double screw, setting the rotating speed to 80 rpm, and slowly pouring the mixed materials into a charging hole. When the mixed materials pass through the double screws, the materials are heated, the flame retardant is uniformly dispersed in the melted PA66 melt under the mixing and shearing of the screws and the help of the addition agent, and then the mixture is extruded by a die at the head of the double screws and enters a water tank for cooling. The cooled material strip continuously enters a granulator and is cut into master batches with the length of 2.5 mm. The package mark is: nylon 66 flame retardant masterbatch B.
Example 3
Preparation of nylon 66 flame-retardant master batch:
mixing materials: adding 5600g of nylon 66 powder into a high-speed mixer, then respectively adding 150g of high-temperature lubricant (PETS), 100g of titanate coupling agent, 100g of antioxidant (B225) and 8g of graphene powder at a low stirring speed of 15rpm, and stirring for 30 minutes at 30rpm after the addition of the auxiliary agent is completed; then 1500g of treated melamine polyphosphate and 1500g of tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate were added in sequence in a stopped state, the machine was capped after the addition was completed, and the sealing performance was checked. The speed in the high-speed mixer is adjusted to 200rpm, stirring is carried out for 1 hour, then the speed in the mixer is increased to 1500rpm, stirring is carried out for 1 hour, then the machine is stopped, and the mixed materials are discharged from a discharge hole.
Extruding and granulating the mixed materials by a 35# double-screw extruder, wherein the specific operation is as follows:
the temperatures of thirteen heating areas of the twin screw are set as follows: 110 ℃, 238 ℃, 280 ℃, 300 ℃, 320 ℃, 322 ℃, 325 ℃,316 ℃, 330 ℃ when the temperature of each heating area of the screw reaches a set value, starting the water pump and the oil pump of the double screw, after 5 minutes of operation, starting the double screw, setting the rotating speed to 80 rpm, and slowly pouring the mixed materials into a charging hole. When the mixed materials pass through the double screws, the materials are heated, the flame retardant is uniformly dispersed in the melted PA66 melt under the mixing and shearing of the screws and the help of the addition agent, and then the mixture is extruded by a die at the head of the double screws and enters a water tank for cooling. The cooled material strip continuously enters a granulator and is cut into master batches with the length of 2.5 mm. The package mark is: nylon 66 flame retardant masterbatch C.
Application example
Preparing materials before spinning:
(1) Comparative example LOT-0 preparation:
weighing 210kg of nylon 66 powder (DuPont of the supplier in U.S.) and uniformly adding into a dryer in three batches, drying at 80 ℃ for 2.0 hours, and vacuum packaging the dried slices for spinning, wherein the label is LOT-0.
(2) Application example LOT preparation:
140kg of nylon 66 powder (DuPont, USA) and 70kg of nylon 66 flame retardant masterbatch A were weighed into a double cone drum mixer and mixed for one hour at 50 rpm. And then evenly dividing into three batches, adding the three batches into a dryer, drying at the drying temperature of 80 ℃ for 2.0 hours, and vacuum packaging the dried slices for spinning, wherein the label is LOT-A.
(3) Batch LOT preparation for application example LOT-B:
140kg of nylon 66 powder (DuPont, USA) and 70kg of nylon 66 flame retardant masterbatch B were weighed into a double cone drum mixer and mixed for one hour at 50 rpm. And then evenly dividing into three batches, adding the three batches into a dryer, drying at the drying temperature of 80 ℃ for 2.0 hours, and vacuum packaging the dried slices for spinning, wherein the label is LOT-B.
(4) Application example LOT preparation:
140kg of nylon 66 powder (DuPont, USA) and 70kg of nylon 66 flame retardant masterbatch C were weighed into a double cone drum mixer and mixed for one hour at 50 rpm. And then evenly dividing into three batches, adding the three batches into a dryer, drying at the drying temperature of 80 ℃ for 2.0 hours, and vacuum packaging the dried slices for spinning, wherein the label is LOT-C.
Preparation before spinning: the four batches of LOT-0 and LOT-A, LOT-B, LOT-C prepared above were subjected to an on-line spinning experiment, wherein the three batches of LOT-A, LOT-B, LOT-C were samples of their corresponding flame retardant applications. Where LOT-0 is its corresponding blank comparative sample.
The spinning process comprises the following steps: the prepared powder for spinning is firstly sucked into a hopper above a screw feeding hole by a vacuum system. The melt extrusion equipment used was an SJ-60 x 30 high torque single screw compounding extruder, the screw diameter was 60mm, the twin screw aspect ratio was 30:1, a total of 7 heating zones. The temperature of each heating area of the twin screw is increased to the set temperature, powder enters from a charging port, plasticization and dissolution are carried out in the single screw, and after passing through a filter, the dissolved material is metered by a metering pump and then sprayed out by a spinneret plate in a spinning component. Then cooling and forming under the action of lateral blowing, then drawing and heat setting through a heating roller, then networking through a network device, and finally winding on a winding machine to form a spinning cake. The relevant main process parameters are respectively described as follows:
the aspect ratio of the twin screws was 30:1, a total of 7 heating areas, the heating temperatures are respectively: 265 ℃, 275 ℃, 280 ℃, 287 ℃, 289 ℃, 293 ℃, 294 ℃; the stainless steel filter screen of the filter is 400 meshes, and the specification of the spinneret plate is as follows: 34 orifices, each orifice having a diameter of 0.23mm and an aspect ratio (L/D) of 2.0; the temperature of the air blown out by the side blowing is 23 ℃, the air speed is 0.40m/s, the temperatures of the 1 st drafting heat roller and the 2 nd drafting heat roller are 89 ℃ and 125 ℃, the speeds of the 1 st drafting heat roller and the 2 nd drafting heat roller are 3371 m/min and 5056 m/min, and the speed of the winding machine is 4950 m/min.
The four batches of LOT-0 and LOT-A, LOT-B, LOT-C are subjected to spinning experiments through the process, and Fiber samples obtained correspondingly are Fiber-0 and Fiber-A, fiber-B, fiber-C.
Detection method and experimental data
(1) Comparative operation performance of Fiber-0 and Fiber-A, fiber-B, fiber-C mechanical properties
According to the national standard GB/T6502-2008 chemical Fiber filament sampling method, fiber-0 and Fiber-A, fiber-B, fiber-C fibers are randomly sampled, 5 filament cakes are extracted from each group of fibers, and according to the national standard GB/T14344-2008 chemical Fiber filament tensile property test method, the test results of the Fiber mechanical properties of Fiber-0 and Fiber-A, fiber-B, fiber-C are shown in Table 1.
It can be seen that by comparing experimental data of mechanical properties of Fiber-0 and Fiber-A, fiber-B, fiber-C, although a larger proportion of nylon 66 flame retardant masterbatch is added, the mechanical properties of Fiber-A, fiber-B, fiber-C are not significantly reduced compared with the Fiber-0 Fiber added without flame retardant.
The defect of great strength discount caused by adding the flame retardant which is a non-polymer body substance into nylon 66 fibers is avoided by adding the graphene powder, the strength reduction percentage is controlled within 4%, and the fiber reinforcement effect is achieved.
(2) Fiber-0, fiber-A, fiber-B, fiber-C flame retardant performance comparison:
fiber-0 and Fiber-A, fiber-B, fiber-C were tested according to national standard GB/T8924-2005 oxygen index method of Fiber reinforced plastics Combustion test method and UL94 vertical Combustion method, respectively, and the test results are shown in Table 2.
From the above test results, it can be seen that the three groups of fibers including Fiber-A, fiber-B, fiber-C are obtained by respectively performing spinning experiments on the nylon 66 flame retardant masterbatch A, the flame retardant masterbatch B and the flame retardant masterbatch C, and comparing experiments are performed on the fibers with the blank spinning Fiber-0 fibers without the flame retardant masterbatch, and oxygen index and UL94 flame retardant performance tests are performed respectively, so as to obtain the flame retardant Fiber: when melamine polyphosphate or tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate flame retardant is added, the fiber has a flame retardant effect, and the UL94 test of the fiber can reach the V1 grade; more preferably, when melamine polyphosphate and tetrakis (2, 6-dimethylphenyl) 1, 3-phenylene phosphate flame retardant are used in combination 1: when the proportion of the components is mixed in proportion, the flame retardant effect is greatly increased, the oxygen index is increased to about 36 from the LOI value of 28-29 in the test of the oxygen index, the V0 level is reached from the V1 level in the test of the UL94, and the flame retardant property of the nylon 66 fiber is greatly improved.
The test examples of the present invention are merely illustrative of the present application and not limiting, and those skilled in the art, after reading the present specification, may make no innovative modifications and conditional changes to the examples, but are protected by the patent laws within the scope of the appended claims.

Claims (7)

1. The flame-retardant master batch for the nylon 66 fiber is characterized in that: the components are calculated according to the weight percentage:
melamine polyphosphate: 6.0 to 40.0 percent;
tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate: 3.0 to 20.0 percent;
graphene powder: 0.01 to 0.1 percent;
wetting dispersant: 0.05 to 2.0 percent
And (3) a lubricant: 0.05 to 2.0 percent;
coupling agent: 0.1 to 3.0 percent;
antioxidant: 0.1 to 3.0 percent;
the balance of nylon 66 powder.
2. The flame retardant masterbatch for nylon 66 fiber according to claim 1, wherein: the original particle size of the melamine polyphosphate powder is less than or equal to 1.0 and um.
3. The flame retardant masterbatch for nylon 66 fiber according to claim 1, wherein: the original particle size of the powder of the tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate is less than or equal to 1.0 um.
4. The flame retardant masterbatch for nylon 66 fiber according to claim 1, wherein: the number of layers of the graphene powder is 1.0-10.0.
5. The flame retardant masterbatch for nylon 66 fiber according to claim 1, wherein: the original particle size of the nylon 66 powder is less than or equal to 250.0 and um.
6. The method for preparing the flame-retardant masterbatch for nylon 66 fiber according to any one of claims 1-5, characterized in that: the preparation method of the flame-retardant master batch comprises the following steps:
pretreatment of melamine polyphosphate and ammonium polyphosphate:
(1) Pretreatment of melamine polyphosphate: firstly, adding a proper amount of mixed solution of ethyl acetate and dimethylbenzene into a stirring barrel at a constant speed, and then adding a proper amount of wetting dispersant and coupling agent at a low stirring speed of 30-60 rpm; after stirring for 1 hour, adding the melamine polyphosphate powder material, and after the addition, adjusting the degree of a stirrer to 300-1000 rpm, and stirring for 1-3 hours; grinding the prepared melamine polyphosphate powder slurry by a ball mill for 1-4 hours, and finishing grinding when the fineness of the slurry is less than or equal to 1.0 um; filtering, drying and crushing the ground slurry, and vacuum packaging when the fineness of the powder is less than or equal to 1.0 um;
(2) Pretreatment of tetrakis (2, 6-dimethylphenyl) 1, 3-phenylene phosphate: firstly, adding a proper amount of mixed solution of ethyl acetate and dimethylbenzene into a stirring barrel, and then adding a proper amount of wetting dispersant and coupling agent at a low stirring speed of 30-60 rpm; after stirring for 1 hour, adding a 1, 3-phenylene phosphoric acid tetra (2, 6-dimethylphenyl) ester powder material, and after the addition, adjusting the speed of a stirrer to 100-500 rpm, and stirring for 1-3 hours; grinding the prepared slurry of the tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate by a ball mill for 1-4 hours, and finishing grinding when the fineness of the slurry is less than or equal to 1.0 um; filtering, drying and crushing the ground slurry, and vacuum packaging when the fineness of the powder is less than or equal to 1.0 um;
(3) Mixing materials: adding a proper amount of nylon 66 powder into a high-speed mixer, then sequentially adding treated melamine polyphosphate and tetra (2, 6-dimethylphenyl) 1, 3-phenylene phosphate, and adding a proper amount of wetting dispersant, lubricant, coupling agent and antioxidant at a low stirring speed of 30-60 rpm; after the material is fed, the speed in the high-speed mixer is adjusted to 100-500 rpm, and the materials are stirred for 1-3 hours; obtaining a mixed material;
(4) Preparation of flame-retardant master batches: and (3) adding the mixed materials in the step (III) into a 35# double-screw extruder, conveying, mixing, dissolving and extruding the materials under the conditions that the rotating speed of the screw is 30-150 rpm and the temperature of a heating zone of the screw is 100-320 ℃, and cutting the strip-shaped materials from the screw extruder by a cutting machine to obtain flame-retardant master batches.
7. Use of a flame retardant masterbatch for nylon 66 fibers according to any one of claims 1-5, characterized in that: the flame-retardant master batch for the nylon 66 fiber has good spinnability, and the flame-retardant master batch for the nylon 66 fiber and corresponding nylon 66 powder are mixed with each other, so that the nylon 66 fiber with good flame retardant property can be obtained in a melt spinning mode.
CN202311611992.7A 2023-11-29 2023-11-29 Flame-retardant master batch for nylon 66 fibers and preparation method and application thereof Pending CN117820853A (en)

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