CN118639348B - A stain-resistant nylon 6 fiber and its preparation method - Google Patents

A stain-resistant nylon 6 fiber and its preparation method

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Publication number
CN118639348B
CN118639348B CN202410760221.2A CN202410760221A CN118639348B CN 118639348 B CN118639348 B CN 118639348B CN 202410760221 A CN202410760221 A CN 202410760221A CN 118639348 B CN118639348 B CN 118639348B
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temperature
nylon
modified
preparation
stain
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CN118639348A (en
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吴炼军
杨新华
刘园园
郭一凡
王松林
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Zhejiang Hengyi Petrochemical Co Ltd
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Zhejiang Hengyi Petrochemical Co Ltd
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    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/60—Polyamides or polyester-amides
    • C08G18/603—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • 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
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent

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

Abstract

本发明涉及尼龙纤维领域，针对后整理制备耐沾污面料耐牢度差、不环保的问题，提供一种耐沾污尼龙6纤维及其制备方法，切片由单羧基封端剂改性的改性尼龙切片、PA6‑PDMS嵌段改性切片组成。制备方法为在己内酰胺中加入单羧基封端剂，开环聚合制改性尼龙切片；在己内酰胺中加双羧基封端剂，开环聚合制备双羧基封端PA6预聚体，再和双氨基封端聚二甲基硅氧烷、二异氰酸酯原位聚合得嵌段改性切片；将改性尼龙切片、嵌段改性切片和含氨基的笼状半硅氧烷混合，熔融挤出，纺丝得耐沾污尼龙6纤维。本发明通过切片共混纺丝的方法结合了改性切片抗污功能和PA6‑PDMS嵌段改性切片疏水性能，得到永久耐沾污尼龙6纤维，且避免使用氟化物。This invention relates to the field of nylon fibers, addressing the problems of poor fastness and environmental unfriendliness in the post-processing of stain-resistant fabrics. It provides a stain-resistant nylon 6 fiber and its preparation method, comprising modified nylon chips modified with a monocarboxyl end-capping agent and PA6-PDMS block-modified chips. The preparation method involves adding a monocarboxyl end-capping agent to caprolactam and performing ring-opening polymerization to prepare modified nylon chips; adding a dicarboxyl end-capping agent to caprolactam and performing ring-opening polymerization to prepare a dicarboxyl-terminated PA6 prepolymer, which is then in-situ polymerized with diamino-terminated polydimethylsiloxane and diisocyanate to obtain block-modified chips; mixing the modified nylon chips, block-modified chips, and amino-containing cage-like semisiloxane, melt-extruding, and spinning to obtain stain-resistant nylon 6 fiber. This invention combines the stain-resistant function of modified chips and the hydrophobic properties of PA6-PDMS block-modified chips through chip blending and spinning, resulting in permanently stain-resistant nylon 6 fiber while avoiding the use of fluorides.

Description

Stain-resistant nylon 6 fiber and preparation method thereof
Technical Field
The invention relates to the field of nylon fibers, in particular to a stain-resistant nylon 6 fiber and a preparation method thereof.
Background
Along with the rapid development of social economy, the living standard of people is continuously improved, and the demands for functional fibers are gradually expanded. The nylon 6 fiber is used as a second large civil silk, and the fabric is inevitably stained with cola, soy sauce and the like in the actual use process, and the cola and the soy sauce are acidic substances, so that the fiber is difficult to clean after being dyed. The stain-resistant fabric is in a post-finishing mode in the market, but the stain-resistant effect gradually worsens along with repeated water washing, for example, the high-color-fastness stain-resistant and stain-release special tie fabric and the preparation method thereof disclosed by the patent CN102995392B are obtained by adopting master batch colored micro-cavitated fine denier Gao Fangzhen silk polyester filaments as raw materials, weaving with satin, twill, changing twill, broken twill or plain weave structures, and carrying out stain-resistant and stain-release finishing and shaping processing through alkali deweighting treatment, acid treatment and fluorocarbon alcohol auxiliary agents with carbon chains of not more than 8. Most finishes are fluoride-based and are not environmentally friendly. Therefore, the development of the nylon 6 fiber with permanent stain resistance and environmental protection has important significance.
Disclosure of Invention
The invention provides a stain-resistant nylon 6 fiber and a preparation method thereof, which are used for solving the problems of poor fastness and environmental protection of stain-resistant fabrics prepared by after-finishing, and the stain-resistant nylon 6 fiber is obtained by combining a modified slice anti-stain function and a PA6-PDMS block modified slice hydrophobic property by a slice blending spinning method, and the use of fluoride is avoided.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a stain-resistant nylon 6 fiber, the slice is composed of a modified nylon slice modified by a single carboxyl end capping agent and a PA6-PDMS block modified slice.
Preferably, the mass ratio of the modified nylon slice to the PA6-PDMS block modified slice is (90-95): 5-10.
The invention also provides a preparation method of the stain-resistant nylon 6 fiber, which comprises the following steps:
(1) Adding a monocarboxyl end capping agent into caprolactam, and preparing a modified nylon slice through ring opening polymerization;
(2) Adding a dicarboxyl end-capping agent into caprolactam, and performing ring-opening polymerization to prepare a dicarboxyl end-capped PA6 prepolymer, wherein the dicarboxyl end-capped PA6 prepolymer, the dicarboxyl end-capped polydimethylsiloxane and diisocyanate are subjected to in-situ polymerization reaction to obtain a PA6-PDMS block modified slice;
(3) Mixing the modified nylon slice prepared in the step (1), the PA6-PDMS block modified slice prepared in the step (2) and cage-shaped silsesquioxane containing amino, and carrying out melt extrusion and spinning to obtain the stain-resistant nylon 6 fiber.
The modified nylon slice is mainly prepared by introducing a blocking agent in the nylon polymerization process, and by reducing the content of amino groups at the fiber ends, the acidic dye is difficult to dye, so that cola, soy sauce and the like are difficult to adhere to nylon fibers, and the modified nylon slice has pigment resistance. The block modified nylon slice is a PA6-PDMS multiblock copolymer obtained by melt polymerization by adopting dicarboxyl end-capped low molecular weight PA6 and diamino end-capped polydimethylsiloxane as reactants and diisocyanate as a chain extender. The Si-CH 3 in the PDMS (polydimethylsiloxane) structure has hydrophobicity, and the introduction of PDMS can improve the hydrophobicity of nylon fibers.
Preferably, the monocarboxylic end-capping agent in the step (1) is benzoic acid, and the mass of the benzoic acid is 2-5% of that of caprolactam.
Preferably, in the step (1), a catalyst is also added, wherein the catalyst is at least one of sodium hydroxide, p-toluenesulfonic acid, phosphoric acid and sodium hypophosphite, and the mass of the catalyst is 500-2000 ppm of the mass of caprolactam.
Preferably, deionized water is added in the step (1), wherein the mass of the deionized water is 2-4% of that of caprolactam.
Preferably, the ring opening temperature of the step (1) is 208-225 ℃, the pressure is 0.54-0.8 MPa, the pressure maintaining ring opening time is 1-2 hours, the polymerization temperature is 250-265 ℃, the pressure is vacuumized to 0.03-0.05 MPa, and the vacuumized time is 0.5-2 hours.
Preferably, the dicarboxyl end-capping agent of step (2) is adipic acid;
preferably, deionized water is added in the step (2), wherein the mass of the deionized water is 2-4% of that of caprolactam.
Preferably, the ring opening temperature of the step (2) is 208-225 ℃, the pressure is 0.5-0.7 MPa, the pressure maintaining ring opening time is 1-2 h, the polymerization temperature is 250-260 ℃, the pressure is vacuumized to 0.07-0.08 MPa, and the vacuumizing time is 1-2 h.
Preferably, the number average molecular weight of the dicarboxyl-terminated PA6 prepolymer in the step (2) is 1000-3000 g/mol, the number average molecular weight of the diamino-terminated polydimethylsiloxane is 2000-5000 g/mol, the diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate, the feeding mole ratio of the dicarboxyl-terminated PA6 prepolymer, the diamino-terminated polydimethylsiloxane and the diisocyanate is 1:1 (1-2), deionized water is also added in the in-situ polymerization, and the mass of the deionized water is 20-30% of the total feeding mass.
Preferably, the in-situ polymerization condition in the step (2) is that after feeding, three-way discharging is carried out, the temperature is raised to 160-180 ℃, the pressure is relieved to normal pressure, and the time is 1.5-2 hours. And (3) carrying out heat preservation reaction for 1-2 h. And then heating to 240-250 ℃, and carrying out vacuum polymerization for 1-2 hours.
Preferably, the amino-containing cage-like silsesquioxane in the step (3) is one or a combination of more than two of p-aminophenyl isobutyl cage-like silsesquioxane, aminoethyl aminopropyl isobutyl cage-like silsesquioxane, aminopropyl isobutyl cage-like silsesquioxane and N-methyl aminopropyl isobutyl cage-like silsesquioxane, and the mass of the amino-containing cage-like silsesquioxane is 0.2-1% of the total mass of the slice.
Preferably, the slices in the step (3) are sequentially subjected to vacuum drying, melt extrusion, spinning, cross-air cooling, drafting, tension heat setting, winding and spooling treatment to obtain the stain-resistant nylon 6 fiber. The method comprises the following specific parameters of vacuum drying at 100-110 ℃ for 20-24 hours, melt extrusion at 230-250 ℃ in a first region of a screw extruder, 240-250 ℃ in a second region, 250-260 ℃ in a third region, spinning at 250-260 ℃ in a composite spinning box, 48 holes in a spinning assembly, side blowing cooling at 15 ℃ and relative humidity of 80%, winding speed of 3200m/min, drafting multiple of 1.9-3 times and tension heat setting at 110-130 ℃.
Therefore, the invention has the beneficial effects that (1) the modified slice anti-fouling function and the PA6-PDMS block modified slice hydrophobic property are combined by the slice blending spinning method, the preparation method of the permanent anti-fouling nylon 6 fiber is provided, the application of fluoride materials is reduced, and the development of environmental protection industry is promoted. (2) The problem that the polarity difference of two phases of PDMS and PA6 is too large and the phase separation in the polymerization process can not be effectively reacted is solved by utilizing the high reactivity of the isocyanate groups. (3) Compared with direct PDMS master batch blending, the compatibility of two phases of blending by using the PA6-PDMS slice and the modified nylon slice is improved, and the serious decrease of the breaking strength of the fiber after the PMDS content is improved is avoided. (4) The cage-shaped semi-siloxane containing amino can further improve the dispersion uniformity of PDMS in a nylon matrix, and in addition, the cage-shaped semi-siloxane containing amino has a certain hydrophobic effect, and the addition of the cage-shaped semi-siloxane containing amino is beneficial to improving the hydrophobic performance of fibers.
Detailed Description
The technical scheme of the invention is further described through specific embodiments.
In the present invention, unless otherwise specified, the materials and equipment used are commercially available or are commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified. Unless otherwise indicated, parts are parts by weight, temperatures are expressed in degrees celsius or at ambient temperature, and pressures are at or near atmospheric. The presence of reaction conditions (e.g., component concentrations, solvents required, solvent mixtures, temperatures, pressures, and other reaction ranges) and numerous variations and combinations of conditions that can be used to optimize the purity and yield of the product obtained by the process will require only reasonably routine experimentation to optimize such process conditions.
Examples
A preparation method of a stain-resistant nylon 6 fiber comprises the following steps:
1. preparation of modified Nylon chip
And adding the monocarboxyl end capping agent, caprolactam, deionized water and a catalyst into a reaction kettle for ring-opening polymerization to prepare the modified nylon slice. The monocarboxylic end-capping agent is benzoic acid, and the mass of the benzoic acid is 2-5% of that of caprolactam. The catalyst is at least one of sodium hydroxide, p-toluenesulfonic acid, phosphoric acid and sodium hypophosphite, and the mass of the catalyst is 500-2000 ppm of the mass of caprolactam. The mass of the deionized water is 2-4% of that of caprolactam.
The ring-opening reaction is carried out under the conditions that the temperature is 208-225 ℃, the pressure is 0.54-0.8 MPa, and the pressure-maintaining ring-opening time is 1-2 h. The polymerization reaction is carried out under the conditions that the temperature is 250-265 ℃, the pressure is vacuumized to 0.03-0.05 MPa, and the vacuumization time is 0.5-2 h.
2. Preparation of PA6-PDMS Block modified slice
(1) And adding the dicarboxyl end-capping agent, caprolactam and deionized water into a reaction kettle for ring-opening polymerization to prepare the dicarboxyl end-capped PA6 prepolymer.
The dicarboxyl end-capping agent is adipic acid,The mass of the deionized water is 2-4% of that of caprolactam.
The ring-opening reaction is carried out under the conditions that the temperature is 208-225 ℃, the pressure is 0.5-0.7 MPa, and the pressure-maintaining ring-opening time is 1-2 h. The polymerization reaction is carried out under the conditions that the temperature is 250-260 ℃, the pressure is vacuumized to 0.07-0.08 MPa, and the vacuumization time is 1-2 h.
(2) Adding the dicarboxyl end-capped PA6 prepolymer, the diamino end-capped polydimethylsiloxane, deionized water and diisocyanate into a reaction kettle for in-situ polymerization reaction to obtain the PA6-PDMS block modified slice.
The number average molecular weight of the dicarboxyl end-capped PA6 prepolymer is 1000-3000 g/mol. The number average molecular weight of the diamino terminated polydimethylsiloxane is 2000-5000 g/mol. The diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate, and the feeding mole ratio of the dicarboxyl-terminated PA6 prepolymer to the diamino-terminated polydimethylsiloxane to the diisocyanate is 1:1 (1-2). The mass of the deionized water is 20% -30% of the total feeding mass.
The reaction condition of the in-situ polymerization is that after feeding, three tee joints are put, the temperature is raised to 160-180 ℃, the pressure is relieved to normal pressure, and the time is 1.5-2 hours. And (3) carrying out heat preservation reaction for 1-2 h. And then heating to 240-250 ℃, and carrying out vacuum polymerization for 1-2 hours.
3. Preparation of stain-resistant nylon 6 fiber
And (3) mixing the modified nylon slice prepared in the first step, the PA6-PDMS block modified slice prepared in the second step and cage-shaped semi-siloxane containing amino, and carrying out melt extrusion and spinning to obtain the contamination-resistant nylon 6 fiber.
The modified nylon slice accounts for 90-95% of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice), and the PA6-PDMS block modified slice accounts for 5-10% of the total slice. The amino-containing cage-shaped semi-siloxane is one or the combination of more than two of p-aminophenyl isobutyl cage-shaped semi-siloxane, aminoethyl aminopropyl isobutyl cage-shaped semi-siloxane, aminopropyl isobutyl cage-shaped semi-siloxane and N-methyl aminopropyl isobutyl cage-shaped semi-siloxane, and the mass of the amino-containing cage-shaped semi-siloxane is 0.2-1% of the total slice mass.
The slices are sequentially subjected to vacuum drying treatment, melt extrusion, spinning, cross-air cooling, stretching, tension heat setting, winding and spooling treatment. The temperature is 100-110 ℃, the drying time is 20-24 hours, the conditions of melt extrusion are that the temperature of a first area of a screw extruder is 230-250 ℃, the temperature of a second area is 240-250 ℃, the temperature of a third area is 250-260 ℃, the conditions of spinning are that the temperature of a composite spinning box is 250-260 ℃, the number of spinning holes of a spinning assembly is 48 holes, the side blowing cooling temperature is 15 ℃, the relative humidity is 80%, the winding speed is 3200m/min, the draft multiple is 1.9-3 times, and the temperature of tension heat setting is 110-130 ℃.
The invention also provides a stain-resistant nylon 6 fiber prepared by the preparation method.
Example 1
A preparation method of the stain-resistant nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 2% of the mass of the caprolactam, 1500ppm of phosphoric acid and 3% of deionized water into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding deionized water accounting for 4% of the mass of the caprolactam. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 3000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:1, and adding deionized water accounting for 20% of the total feeding mass. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) The preparation of the stain-resistant nylon 6 fiber comprises the steps of putting the modified nylon slice and the block modified slice into a vacuum drum for drying, wherein the drying temperature is 100 ℃, and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 1:9, and adding aminopropyl isobutyl cage-shaped silsesquioxane accounting for 0.2% of the mass of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice). And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the stain-resistant nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 240 ℃, the temperature of a second area of the screw is 250 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 1.9 times and the temperature for tension heat setting was 130 ℃.
The linear density of the prepared stain-resistant nylon 6 fiber is 70dtex.
Example 2
A preparation method of the stain-resistant nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon chip comprises the steps of adding 3% of benzoic acid, 1500ppm of phosphoric acid, 3% of deionized water and caprolactam into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.05MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding 4% deionized water. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) Preparation of block modified slice, namely 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 5000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate are put into a polymerization reactor according to a molar ratio of 1:1:1, and then 20% of deionized water is added. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) The preparation of the stain-resistant nylon 6 fiber comprises the steps of putting the modified nylon slice and the block modified slice into a vacuum drum for drying, wherein the drying temperature is 100 ℃, and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to a ratio of 1:9, and adding 0.2% of aminopropyl isobutyl cage-shaped silsesquioxane. And putting the uniformly mixed slices into a hopper, and carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the stain-resistant nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 240 ℃, the temperature of a second area of the screw is 250 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 1.9 times and the temperature for tension heat setting was 130 ℃.
The linear density of the prepared stain-resistant nylon 6 fiber is 69dtex.
Example 3
A preparation method of the stain-resistant nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon chip comprises the steps of adding 5% of benzoic acid, 2000ppm of phosphoric acid, 3% of deionized water and caprolactam into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.05MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 16.4:1, and adding 4% deionized water. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) Preparation of block modified slice, namely 2000g/mol of dicarboxyl end-capped PA6 prepolymer, 5000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate are put into a polymerization reactor according to a mol ratio of 1:1:1, and then 20% of deionized water is added. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 240 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) The preparation of the stain-resistant nylon 6 fiber comprises the steps of putting the modified nylon slice and the block modified slice into a vacuum drum for drying, wherein the drying temperature is 100 ℃, and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to a ratio of 1:9, and adding 0.2% of aminopropyl isobutyl cage-shaped silsesquioxane. And putting the uniformly mixed slices into a hopper, and carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the stain-resistant nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 240 ℃, the temperature of a second area of the screw is 250 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 1.9 times and the temperature for tension heat setting was 130 ℃.
The linear density of the prepared stain-resistant nylon 6 fiber is 72dtex.
Example 4
A preparation method of the stain-resistant nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 2% of the mass of the caprolactam, 500ppm of sodium hypophosphite and 2% of deionized water into a polymerization reaction kettle. After three-way release, the temperature is raised to 208 ℃ and the pressure is maintained for 0.54MPa for open loop for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.03MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding deionized water accounting for 2% of the mass of the caprolactam. After three-way release, the temperature is raised to 208 ℃ and the pressure is maintained for 0.5MPa for open loop for 1h. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.07MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 2000g/mol of diamino end-capped polydimethylsiloxane and isophorone diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:2, and adding deionized water accounting for 30% of the total feeding mass. After three-way release, the temperature is raised to 160 ℃, the pressure is released to normal pressure, the time is 1.5h, and the reaction is kept for 1h. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) The preparation of the stain-resistant nylon 6 fiber comprises the steps of putting the modified nylon slice and the block modified slice into a vacuum drum for drying, wherein the drying temperature is 110 ℃, and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 5:95, and adding N-methyl aminopropyl isobutyl cage-shaped silsesquioxane accounting for 0.5% of the mass of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice). And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the stain-resistant nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 250 ℃, the temperature of a second area is 260 ℃, the temperature of a third area is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple is 3 times, and the temperature for tension heat setting is 110 ℃.
The linear density of the prepared stain-resistant nylon 6 fiber is 56dtex.
Example 5
A preparation method of the stain-resistant nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 2% of the mass of the caprolactam, p-toluenesulfonic acid of 1500ppm and deionized water of 4% into a polymerization reaction kettle. After three-way release, the temperature is raised to 215 ℃ and the pressure is maintained for 0.8MPa for open loop for 1h. After the mixture is discharged to normal pressure, the temperature is raised to 265 ℃, the mixture is vacuumized to 0.05MPa, and the mixture is vacuumized and polymerized for 0.5h.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 25.22:1, and adding deionized water accounting for 3% of the mass of the caprolactam. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.6MPa for open loop for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 1h.
(3) The preparation of the block modified slice comprises the steps of adding 3000g/mol of dicarboxyl end-capped PA6 prepolymer, 5000g/mol of diamino end-capped polydimethylsiloxane and diphenylmethane diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:1.5, and adding deionized water accounting for 25% of the total feeding mass. After three-way release, the temperature is raised to 170 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 245 ℃, and the vacuum polymerization reaction is carried out for 1.5h.
(4) The preparation of the stain-resistant nylon 6 fiber comprises the steps of putting the modified nylon slice and the block modified slice into a vacuum drum for drying, wherein the drying temperature is 105 ℃ and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 8:92, and adding p-aminophenyl isobutyl cage-shaped silsesquioxane accounting for 1% of the mass of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice). And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the stain-resistant nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 245 ℃, the temperature of a second area of the screw is 245 ℃, the temperature of a third area of the screw is 250 ℃, and the temperature of a composite spinning box body is 250 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 2.5 times and the temperature for tension heat setting was 120 ℃.
The linear density of the prepared stain-resistant nylon 6 fiber is 64dtex.
Comparative example
Comparative example 1
The difference from example 1 is that in step (1) no monocarboxylic end-capping agent benzoic acid is used. The method comprises the following steps:
the preparation method of the nylon 6 fiber comprises the following steps:
(1) Nylon chips are prepared by putting caprolactam and deionized water accounting for 3 percent of the mass of the caprolactam into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding deionized water accounting for 4% of the mass of the caprolactam. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 3000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:1, and adding deionized water accounting for 20% of the total feeding mass. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) Nylon 6 fiber is prepared through vacuum drum drying nylon slice and block modified slice at 100 deg.c for 24 hr. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 1:9, and adding aminopropyl isobutyl cage-shaped silsesquioxane accounting for 0.2% of the mass of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice). And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 250 ℃, the temperature of a second area of the screw is 255 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 2.3 times and the temperature for tension heat setting was 130 ℃.
The linear density of the prepared stain-resistant nylon 6 fiber is 70dtex.
Comparative example 2
The difference from example 1 is that the amount of benzoic acid used as the end-capping agent in step (1) is 8% and is outside the preferred range of 2-5%. Specifically, the preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 8% of the mass of the caprolactam, 1500ppm of phosphoric acid and 3% of deionized water into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
Because of the excessive benzoic acid, the modified chip viscosity was too low to spin properly.
Comparative example 3
The difference from example 1 is that the capping agent of step (1) uses the dicarboxyl capping agent terephthalic acid. The method comprises the following steps:
the preparation method of the nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, terephthalic acid accounting for 2% of the mass of the caprolactam, phosphoric acid of 1500ppm and deionized water of 3% into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding deionized water accounting for 4% of the mass of the caprolactam. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 3000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:1, and adding deionized water accounting for 20% of the total feeding mass. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) And (3) preparing the nylon 6 fiber, namely placing the modified nylon slices and the block modified slices into a vacuum drum for drying, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 1:9, and adding aminopropyl isobutyl cage-shaped silsesquioxane accounting for 0.2% of the mass of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice). And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 240 ℃, the temperature of a second area of the screw is 250 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 1.9 times and the temperature for tension heat setting was 130 ℃.
The linear density of the nylon 6 fiber obtained was 70dtex.
Comparative example 4
The difference from example 1 is that the PDMS block modified chips were not prepared and spun directly with modified nylon chips. The preparation method of the nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 2% of the mass of the caprolactam, 1500ppm of phosphoric acid and 3% of deionized water into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) And (3) preparing the nylon 6 fiber, namely placing the modified nylon slices into a vacuum drum for drying, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. And (3) putting the slices into a hopper, carrying out melt extrusion by a screw extruder, measuring by a melt pipeline and a metering pump, and spinning by a spinning assembly, cooling by lateral blowing, drafting, tension heat setting, winding and spooling to obtain the nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 250 ℃, the temperature of a second area of the screw is 255 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 2.4 times and the temperature for tension heat setting was 130 ℃.
The linear density of the nylon 6 fiber obtained was 71dtex.
Comparative example 5
The difference from example 1 is that the number average molecular weight of PDMS of step (3) is outside the preferred range. The method comprises the following steps:
the preparation method of the nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 2% of the mass of the caprolactam, 1500ppm of phosphoric acid and 3% of deionized water into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding deionized water accounting for 4% of the mass of the caprolactam. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 10000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:1, and adding deionized water accounting for 20% of the total feeding mass. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) And (3) preparing the nylon 6 fiber, namely placing the modified nylon slices and the block modified slices into a vacuum drum for drying, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 1:9, and adding aminopropyl isobutyl cage-shaped silsesquioxane accounting for 0.2% of the mass of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice). And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 240 ℃, the temperature of a second area of the screw is 250 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 1.9 times and the temperature for tension heat setting was 130 ℃.
The linear density of the nylon 6 fiber obtained was 75dtex.
Comparative example 6
The difference from example 1 is that step (3) does not use isocyanate groups as chain extender. The method comprises the following steps:
The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer and 3000g/mol of diamino end-capped polydimethylsiloxane into a polymerization reaction kettle according to a molar ratio of 1:1, and adding deionized water accounting for 20% of the total feeding mass. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
The reactivity of carboxyl and amino is not high, and the viscosity of the block modified slice is low and spinning can not be performed.
Comparative example 7
The difference from example 1 is that no amino-containing cage-like silsesquioxane was used in step (4). The method comprises the following steps:
the preparation method of the nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 2% of the mass of the caprolactam, 1500ppm of phosphoric acid and 3% of deionized water into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding deionized water accounting for 4% of the mass of the caprolactam. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 3000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:1, and adding deionized water accounting for 20% of the total feeding mass. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) And (3) preparing the nylon 6 fiber, namely placing the modified nylon slices and the block modified slices into a vacuum drum for drying, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 1:9. And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 240 ℃, the temperature of a second area of the screw is 250 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 1.9 times and the temperature for tension heat setting was 130 ℃.
The linear density of the nylon 6 fiber obtained was 72dtex.
Comparative example 8
The difference from example 1 is that the amino-containing cage-like silsesquioxane of step (4) is used in an amount of 2% and is out of the preferred range of 0.2 to 1%. The method comprises the following steps:
the preparation method of the nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 2% of the mass of the caprolactam, 1500ppm of phosphoric acid and 3% of deionized water into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding deionized water accounting for 4% of the mass of the caprolactam. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 3000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:1, and adding deionized water accounting for 20% of the total feeding mass. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) And (3) preparing the nylon 6 fiber, namely placing the modified nylon slices and the block modified slices into a vacuum drum for drying, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 1:9, and adding aminopropyl isobutyl cage-shaped silsesquioxane accounting for 2% of the mass of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice). And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 240 ℃, the temperature of a second area of the screw is 250 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 1.9 times and the temperature for tension heat setting was 130 ℃.
The linear density of the nylon 6 fiber obtained was 70dtex.
Comparative example 9
The difference from example 1 is that the amino-containing cage-like silsesquioxane of step (3) is replaced with 3-aminopropyl trimethoxysilane. The method comprises the following steps:
the preparation method of the nylon 6 fiber comprises the following steps:
(1) The preparation of the modified nylon slice comprises the steps of adding caprolactam, benzoic acid accounting for 2% of the mass of the caprolactam, 1500ppm of phosphoric acid and 3% of deionized water into a polymerization reaction kettle. After three-way release, the temperature is raised to 225 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 260 ℃, the mixture is vacuumized to 0.04MPa, and the mixture is vacuumized and polymerized for 2 hours.
(2) Preparing a dicarboxyl end-capped PA6 prepolymer, namely adding caprolactam and adipic acid into a polymerization reaction kettle according to a molar ratio of 7.56:1, and adding deionized water accounting for 4% of the mass of the caprolactam. After three-way release, the temperature is raised to 220 ℃ and the pressure is maintained for 0.7MPa for 2 hours. After the mixture is discharged to normal pressure, the temperature is raised to 250 ℃, the mixture is vacuumized to 0.08MPa, and the mixture is vacuumized and polymerized for 2 hours.
(3) The preparation of the block modified slice comprises the steps of adding 1000g/mol of dicarboxyl end-capped PA6 prepolymer, 3000g/mol of diamino end-capped polydimethylsiloxane and hexamethylene diisocyanate into a polymerization reaction kettle according to a molar ratio of 1:1:1, and adding deionized water accounting for 20% of the total feeding mass. After three-way release, the temperature is raised to 180 ℃, the pressure is released to normal pressure, the time is 2 hours, and the reaction is kept for 1 hour. Then the temperature is raised to 250 ℃, and the vacuum polymerization reaction is carried out for 1h.
(4) And (3) preparing the nylon 6 fiber, namely placing the modified nylon slices and the block modified slices into a vacuum drum for drying, wherein the drying temperature is 100 ℃ and the drying time is 24 hours. Mixing the dried modified nylon slice and the block modified slice according to the mass ratio of 1:9, and adding 3-aminopropyl trimethoxysilane accounting for 0.2% of the mass of the total slice (modified nylon Long Qiepian and PA6-PDMS block modified slice). And putting the uniformly mixed slices into a hopper, carrying out melt extrusion by a screw extruder, metering by a melt pipeline and a metering pump, and spinning by a spinning component, cooling by cross blowing, drafting, tension heat setting, winding and spooling to obtain the nylon 6 fiber. The temperature of a first area of a screw of the screw extruder is 240 ℃, the temperature of a second area of the screw is 250 ℃, the temperature of a third area of the screw is 260 ℃, and the temperature of a composite spinning box body is 260 ℃. The number of the spinneret holes of the spinneret assembly is 48 holes. The side-blown cooling temperature is 15 ℃ and the relative humidity is 80%. The winding speed is 3200m/min. The draft multiple was 1.9 times and the temperature for tension heat setting was 130 ℃.
The linear density of the nylon 6 fiber obtained was 70dtex.
Performance testing
The stain resistant nylon 6 fibers prepared in each example and comparative example were subjected to performance test by measuring the hydrophobic property of the stain resistant nylon 6 fibers by an angle measurement method using a DSAl0-MK2 type contact angle tester using GB/T30693-2014 "measurement of contact angle of Plastic film with Water". The stain resistance of the stain-resistant nylon 6 fiber is tested by adopting GB/T30159.1-2013 [ detection and evaluation of antifouling Property of textiles ] part 1, stain resistance ], and the permanent stain resistance is tested by adopting a method of evaluating the stain resistance after washing for 50 times. The results are shown in Table 1.
TABLE 1 Strength and stain resistance Properties of composite fibers of examples 1 to 4 and comparative examples 1 to 4
From the data of the examples, the fiber of the invention has better hydrophobic and anti-staining properties, and the contact angle of water and the staining grade are improved along with the increase of the PDMS content and the increase of the addition amount of the benzoic acid. Compared with the prior art, the invention has the advantages that on one hand, the fiber has permanently excellent hydrophobic and anti-fouling properties by using the form of slice blending, and on the other hand, the serious loss of the strength of the fiber and even difficult spinning caused by the increase of the content of the PDMS are avoided by using the P6-PDMS slice and the cage-shaped semi-siloxane containing amino.
Comparative example 1 does not use a monocarboxyl capping agent to reduce the slice-end amino content compared to example 1, resulting in a reduced fiber stain resistance. Comparative example 2 was too high in benzoic acid and too low in modified chip viscosity to be spun normally. Comparative example 3 is not within the preferred range because the dicarboxyl-capping agent is not effective in reducing the terminal amino content of the cut sheet, resulting in poor fiber stain resistance. Comparative example 4 was not sliced with PDMS modified blocks, the fibers did not have hydrophobicity, and the stain resistance of the fibers was reduced. The comparative example 5 has excessively large number average molecular weight of the diamino terminated PDMS and poor dispersion effect, which results in far lower silicon content in the block modified slice than expected, reduced slice viscosity and no obvious improvement of the hydrophobic property of the fiber. Comparative example 6 has low reactivity of carboxyl group and amino group, and the block modified chips have low viscosity and cannot be spun. The comparative example 7 in which the amino group-containing cage-like silsesquioxane was not used resulted in poor mixing effect of the modified chips and the block modified chips, a significant decrease in fiber breaking strength and deterioration in hydrophobic property. The excessive amount of the amino group-containing cage-like silsesquioxane of comparative example 8 resulted in an increase in cost, but the improvement in the hydrophobic effect was not significant. The polyhedral cage structure of the amino-containing cage-like silsesquioxane of comparative example 9 had a certain hydrophobic property, and the hydrophobic property of the fiber was reduced after the substitution with 3-aminopropyl trimethoxysilane.
The present invention is not limited to the preferred embodiments, and the present invention is described above in any way, but is not limited to the preferred embodiments, and any person skilled in the art will appreciate that the present invention is not limited to the embodiments described above, while the above disclosure is directed to various equivalent embodiments, which are capable of being modified or varied in several ways, any simple modification, equivalent changes and variation of the above embodiments according to the technical principles of the present invention will still fall within the scope of the present invention.

Claims (9)

1.一种耐沾污尼龙6纤维的制备方法，其特征在于，包括以下步骤：1. A method for preparing stain-resistant nylon 6 fiber, characterized by comprising the following steps: （1）在己内酰胺中加入单羧基封端剂，开环聚合制备改性尼龙切片；(1) Add a monocarboxyl end-capping agent to caprolactam and prepare modified nylon chips by ring-opening polymerization; （2）在己内酰胺中加入双羧基封端剂，开环聚合制备双羧基封端PA6预聚体；双羧基封端PA6预聚体和双氨基封端聚二甲基硅氧烷、二异氰酸酯进行原位聚合反应，得到PA6-PDMS嵌段改性切片；(2) Add a dicarboxyl end-capping agent to caprolactam and prepare a dicarboxyl-terminated PA6 prepolymer by ring-opening polymerization; the dicarboxyl-terminated PA6 prepolymer and diamino-terminated polydimethylsiloxane and diisocyanate are subjected to in-situ polymerization reaction to obtain PA6-PDMS block modified chips. （3）将改性尼龙切片、PA6-PDMS嵌段改性切片和含氨基的笼状半硅氧烷混合，熔融挤出，纺丝得耐沾污尼龙6纤维。(3) Mix modified nylon chips, PA6-PDMS block modified chips and amino-containing cage semisiloxane, melt extrude and spin to obtain stain-resistant nylon 6 fibers. 2.根据权利要求1所述的制备方法，其特征在于，改性尼龙切片和PA6-PDMS嵌段改性切片的质量比为(90-95):(5-10)。2. The preparation method according to claim 1, wherein the mass ratio of modified nylon chips to PA6-PDMS block modified chips is (90-95):(5-10). 3.根据权利要求1所述的制备方法，其特征在于，单羧基封端剂为苯甲酸，苯甲酸质量为己内酰胺质量的2~5%。3. The preparation method according to claim 1, wherein the monocarboxyl end-capping agent is benzoic acid, and the mass of benzoic acid is 2-5% of the mass of caprolactam. 4. 根据权利要求1所述的制备方法，其特征在于，步骤（1）的开环聚合条件包括：开环温度为208~225 ℃，压力为0.54~0.8 MPa，保压开环时间为1~2 h；聚合温度为250~265 ℃，压力为抽真空至0.03~0.05 MPa，抽真空时间为0.5~2 h。4. The preparation method according to claim 1, characterized in that the ring-opening polymerization conditions in step (1) include: a ring-opening temperature of 208~225 ℃, a pressure of 0.54~0.8 MPa, and a holding time of 1~2 h; a polymerization temperature of 250~265 ℃, a pressure of 0.03~0.05 MPa under vacuum, and a vacuuming time of 0.5~2 h. 5.根据权利要求1所述的制备方法，其特征在于，双羧基封端剂为己二酸。5. The preparation method according to claim 1, wherein the dicarboxylic acid end-capping agent is adipic acid. 6. 根据权利要求1所述的制备方法，其特征在于，步骤（2）的开环聚合条件包括：开环温度为208~225 ℃，压力为0.5~0.7 MPa，保压开环时间为1~2 h；聚合温度为250~260 ℃，压力为抽真空至0.07~0.08 MPa，抽真空时间为1~2 h。6. The preparation method according to claim 1, characterized in that the ring-opening polymerization conditions in step (2) include: a ring-opening temperature of 208~225 ℃, a pressure of 0.5~0.7 MPa, and a holding time of 1~2 h; a polymerization temperature of 250~260 ℃, a pressure of 0.07~0.08 MPa under vacuum, and a vacuuming time of 1~2 h. 7.根据权利要求1所述的制备方法，其特征在于，7. The preparation method according to claim 1, characterized in that, 双羧基封端PA6预聚体数均分子量为1000~3000 g/mol；The number-average molecular weight of dicarboxylated PA6 prepolymer is 1000~3000 g/mol; 双氨基封端聚二甲基硅氧烷数均分子量为2000~5000 g/mol；The number-average molecular weight of diamino-terminated polydimethylsiloxane is 2000~5000 g/mol; 二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二苯甲烷二异氰酸酯中的至少一种；The diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate; 双羧基封端PA6预聚体、双氨基封端聚二甲基硅氧烷、二异氰酸酯的投料摩尔比为1:1:(1~2)。The molar ratio of dicarboxyl-terminated PA6 prepolymer, diamino-terminated polydimethylsiloxane, and diisocyanate is 1:1:(1~2). 8.根据权利要求1所述的制备方法，其特征在于，含氨基的笼状半硅氧烷为对氨苯基异丁基笼状半硅氧烷、氨乙基氨丙基异丁基笼状半硅氧烷、氨丙基异丁基笼状半硅氧烷、N-甲基氨丙基异丁基笼状半硅氧烷中的一种或者两种以上组合；含氨基的笼状半硅氧烷质量为切片总质量的0.2~1%。8. The preparation method according to claim 1, characterized in that the amino-containing cage-like semisiloxane is one or a combination of two or more of p-aminophenyl isobutyl cage-like semisiloxane, aminoethylaminopropyl isobutyl cage-like semisiloxane, aminopropyl isobutyl cage-like semisiloxane, and N-methylaminopropyl isobutyl cage-like semisiloxane; the mass of the amino-containing cage-like semisiloxane is 0.2-1% of the total mass of the slices. 9.根据权利要求1所述的制备方法，其特征在于，步骤（3）还包括：真空干燥、侧吹风冷却、牵伸、紧张热定型、卷绕和络筒处理。9. The preparation method according to claim 1, wherein step (3) further includes: vacuum drying, side blowing cooling, stretching, tension heat setting, winding and winding treatment.
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