CN111304775A - Tea polyphenol modified polyester filament yarn and preparation method thereof - Google Patents

Tea polyphenol modified polyester filament yarn and preparation method thereof Download PDF

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CN111304775A
CN111304775A CN202010250887.5A CN202010250887A CN111304775A CN 111304775 A CN111304775 A CN 111304775A CN 202010250887 A CN202010250887 A CN 202010250887A CN 111304775 A CN111304775 A CN 111304775A
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tea polyphenol
polyester filament
modified polyester
filament yarn
mixing
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Inventor
黄效华
覃小红
伏广伟
马咏梅
姜义军
甄丽
王丙伟
刘彦明
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Bestee Material Qingdao 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
    • 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
    • D01F6/92—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 polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/04—Melting filament-forming substances
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • 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
    • 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
    • D01F1/103—Agents inhibiting growth of microorganisms

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention provides a tea polyphenol modified polyester filament, wherein the mass content of tea polyphenol is 0.1-5%, the mass content of monofilament fiber is 0.1-0.5dpf, the breaking strength is 8.2-9.9cN/dtex, and the breaking elongation is 11.2-18.0%2‑SiO2Adding polyvinylpyrrolidone 5-8% and polyvinylpyrrolidone 2-5% into the microsphere and tea polyphenols, mixing, and adding tetracyanodimethylbenzeneQuinone and deionized water are stirred and converted into ultrasonic waves for ultrasonic treatment, wherein the ultrasonic frequency is 45-50KHz, the ultrasonic power is 1500-2000W, and the ultrasonic time is 8-18 min; the modified polyester filament yarn has the advantages of antibacterial action, lasting antibacterial effect, high preparation efficiency and good spinning quality.

Description

Tea polyphenol modified polyester filament yarn and preparation method thereof
Technical Field
The invention belongs to the technical field of polyester modification, relates to a tea polyphenol modified polyester filament yarn, and particularly relates to a tea polyphenol modified polyester filament yarn and a preparation method thereof.
Background
Tea Polyphenols (Tea Polyphenols) is a general term for Polyphenols in Tea, and comprises flavanols, anthocyanins, flavonoids, flavonols, phenolic acids, etc. Among them, flavanols (catechins) are most important. Tea polyphenol is also called tea tannin or tea tannin, is one of main components forming the color, the aroma and the taste of tea, and is also one of main components with health care functions in the tea. The IT tea contains abundant tea polyphenols (known as Camellia sinensis). Research shows that active substances such as tea polyphenol and the like have the effects of detoxification and radiation resistance, can effectively prevent radioactive substances from invading bone marrow, can quickly discharge strontium 90 and cobalt 60 out of the body, and is praised as 'radiation killer' by the health and medical community.
The polyester fiber is an important variety in synthetic fiber, the trade name is polyester fiber, and the polyester filament is a filament with the length of more than kilometer. With the development of science and technology and the demand of people for high-quality life, new requirements are also put forward on the performance of the polyester filament yarns, for example, the polyester filament yarns are required to have certain antibacterial property and larger specific surface area, so that the function of super-strong water absorption is realized.
The Chinese patent with publication number CN107326469A provides a polyester filament fiber, the key point formula of which is that PET slices, delustering agent, graphene, heavy metal compound, epoxy resin, boride, maleic anhydride grafted polypropylene, peroxide cumene and other substances are adopted to form a formula to modify the polyester filament, thus effectively improving the strength of the polyester fiber and prolonging the service life of the polyester fiber, but because the inorganic substances are added, the strength is suddenly reduced along with the fineness, and the single filament fiber can not be made into the fiber with the single filament fiber below 0.5 dtex.
The patent application number 2014102266118 discloses a bright ultra-fine denier flat polyester filament with large length-width ratio and a preparation method thereof, in particular to a method for cooling by using air among spinneret holes in the fiber spinning process, which improves the spinning efficiency on the basis of ensuring the spinning uniformity. However, it has no antibacterial property and fails to solve the technical problem of the decrease in strength after the addition of the antibacterial substance.
Disclosure of Invention
The invention provides a tea polyphenol modified polyester filament yarn and a preparation method thereof, aiming at solving the technical problems of the existing tea polyphenol modified polyester filament yarn, and realizing the following purposes:
(1) the tea polyphenol modified polyester filament yarn has an antibacterial effect;
(2) the tea polyphenol modified polyester filament yarn has a lasting antibacterial effect, and the reduction range of the antibacterial effect is small through an exposure test;
(3) the tea polyphenol modified polyester filament yarn has excellent mechanical properties;
(4) the preparation method of the tea polyphenol modified polyester filament yarn has the advantages of high spinning efficiency and high spinning quality.
In order to solve the technical problems, the following technical scheme is adopted:
a tea polyphenol modified polyester filament yarn contains tea polyphenol 0.1-5 wt%.
The following are the preferable technical scheme and the implementation mode of the technical scheme of the invention:
the tea polyphenol modified polyester filament has 0.1-0.5dpf of monofilament fiber, the breaking strength of 8.2-9.9cN/dtex and the breaking elongation of 11.2-18.0%.
The preparation method of the tea polyphenol modified polyester filament yarn comprises the following steps: preparing a functional modifier containing tea polyphenol, preparing a functional master batch containing tea polyphenol, mixing and melting, falling film evaporation and spinning.
The preparation of the functional modifier containing tea polyphenol is carried out to porous nano TiO2-SiO2Adding 5-8% polyvinylpyrrolidone into the microsphere, and mixing uniformly to obtain A; adding 2-5% polyvinylpyrrolidone into tea polyphenols, and mixing to obtain B; a, B, adding tetracyanoquinodimethane and deionized water, stirring and converting into ultrasonic waves for ultrasonic treatment, wherein the ultrasonic frequency is 45-50KHz, the ultrasonic power is 1500-2000W, and the ultrasonic time is 8-18 min.
Preparation of the functional modifier containing tea polyphenol and porous nano TiO2-SiO2The mass ratio of the microspheres to the tea polyphenol to the tetracyanoquinodimethane to the deionized water is 8-12:1:1-10: 10-50.
The preparation method of the functional master batch containing tea polyphenol comprises the step of preparing a functional modifier containing tea polyphenol, polyvinylpyrrolidone and PET slices in a mass ratio of 2:0.1: 4-15.
The mixing and melting are carried out, the mixing and melting temperature is 256-308 ℃, and the high-speed mixing rotating speed is 2.7-2.9 Kr/min.
The functional master batch containing tea polyphenol accounts for 1-8wt% of the total weight of the mixed melt.
The amino trimethylene phosphonic acid has an effective substance content of more than 95 percent, a chloride ion content of less than 0.1 percent and a CAS number of 6419-19-8;
the antioxidant is antioxidant T-9228, the pH value is 5-7, the content of active substances is 99.9%, and the CAS number is 154862-43-8.
The dispersing agent consists of 1 part by weight of hydroxyethyl cellulose, 0.1-5 parts by weight of sodium abietate, 1-10 parts by weight of BYK-358, 1-10 parts by weight of BYK-410 and 10-50 parts by weight of polyethylene oxide.
The falling film evaporation has melt feeding speed of 500-800Kg/h, temperature of 80-115 deg.c, vacuum pump pressure of 15-80Pa, degassing time of 5-24min and melt viscosity of 0.41-0.58 dL/g.
In the spinning process, the speed of the first drawing roller is 2950 and 3650m/min, the speed of the second drawing roller is 4680 and 6100m/min, and the temperature of the hot plate is 79-82 ℃.
The invention also provides a preparation method of the tea polyphenol modified polyester filament yarn, which comprises the following steps: selection of raw materials, porosityNano TiO22-SiO2Preparing microspheres, preparing a functional modifier containing tea polyphenol, preparing functional master batches containing tea polyphenol, mixing and melting, falling film evaporation and spinning.
1. Selection of raw materials
Selecting commercially available tea polyphenol powder, transferring the tea polyphenol powder into a vertical sand mill, controlling the rotating speed of the sand mill to be 0.8-2.5Kr/min, grinding for 20-50min, continuously and uniformly spraying a 5% polyvinyl alcohol aqueous solution on the surface of the tea polyphenol powder during the grinding process, controlling the particle size of the tea polyphenol powder to be more than 99%, and sieving by a 10000-mesh sieve to obtain the tea polyphenol.
In the polyvinyl alcohol aqueous solution, the spraying amount of polyvinyl alcohol is 2-3% of the mass of the tea polyphenol powder;
the tea polyphenol powder is white amorphous crystalline powder with the content of 99.80 percent, the heavy metal content of less than or equal to 38.0ug/g, the lead content of less than or equal to 9.1ug/g, the arsenic content of less than or equal to 3.0ug/g, the relative molecular weight of 362.23 and the melting point of 131.0-133.2 ℃.
The tea polyphenols mainly comprise flavanones, anthocyanidins, flavonols, anthocyanins, phenolic acids and depside 6 compounds.
2. Porous nano TiO2-SiO2Preparation of microspheres
Downward active TiO at 20 DEG C2Sequentially adding sorbitan, softened water and sodium methylsilicate into the hydrosol, stirring uniformly, adding dilute hydrochloric acid for acidification to obtain a light yellow transparent colloid, adding an n-hexane solvent, heating to 50-55 ℃ at the speed of 2 ℃/min, keeping the temperature, stirring until an emulsion appears, adding sodium hydroxide, heating to the solution at the speed of 5 ℃/min, starting layering, keeping the temperature for 10-15min, filtering to obtain a white precipitate, washing, and drying to obtain the porous nano TiO2-SiO2 microsphere.
The active TiO2The mass ratio of hydrosol, sorbitan, softened water, sodium methyl silicate, n-hexane solvent, hydrochloric acid and sodium hydroxide is 20-50: 0.05-0.2: 5-15: 1: 20-50: 0.1-2: 1-3.
The porous nano TiO2-SiO2Microspheres with the particle size of 0.1-10um, the aperture of 10-100nm and the sphericity rate of 98.9-99.4%; granuleThe diameter is 4-8um and the ratio is more than 90 percent;
3. preparation of functional modifier containing tea polyphenol
Pre-oriented porous nano TiO2-SiO2Adding 5-8% polyvinylpyrrolidone into the microsphere, and mixing uniformly to obtain A; adding 2-5% polyvinylpyrrolidone into tea polyphenols, and mixing to obtain B;
a, B, adding tetracyanoquinodimethane and deionized water, stirring and converting into ultrasonic waves for ultrasonic treatment, wherein the ultrasonic frequency is 45KHz, the ultrasonic power is 1500W, the ultrasonic time is 8-18min, and removing water to obtain the functional modifier containing tea polyphenol.
The porous nano TiO2-SiO2The mass ratio of the microspheres to the tea polyphenol to the tetracyanoquinodimethane to the deionized water is 8-12:1:1-10: 10-50.
4. Preparation of functional master batch containing tea polyphenol
Adding polyvinylpyrrolidone and PET slices into functional modifier containing tea polyphenol, and melting at high temperature to obtain functional master batch containing tea polyphenol, wherein the viscosity of the functional master batch containing tea polyphenol is 0.38-0.74 dl/g.
The weight ratio of the tea polyphenol-containing functional modifier to the polyvinylpyrrolidone to the PET slices is 2:0.1: 4-15.
5. Mixing and melting
Mixing and melting the functional master batch containing tea polyphenol, PET slices, amino trimethylene phosphonic acid, an antioxidant and a dispersing agent at high speed, wherein the mixing and melting temperature is 256-308 ℃, and the high-speed mixing rotating speed is 2.7-2.9 Kr/min.
The mass ratio of the PET slices, the amino trimethylene phosphonic acid, the antioxidant and the dispersant is 100: 0.1-20: 0.01-10:0.01-20.
The content of the functional master batch containing tea polyphenol is controlled by controlling the proportion of the tea polyphenol in the tea polyphenol modified polyester filament yarn of the invention to be 0.1-5%.
The PET slice has the density of 1.20-1.40g/cm3, the intrinsic viscosity of 0.77-0.82dL/g and the breaking elongation of 19.2-24.5%;
the amino trimethylene phosphonic acid has an effective substance content of more than 95 percent, a chloride ion content of less than 0.1 percent and a CAS number of 6419-19-8;
the antioxidant is antioxidant T-9228, the pH value is 5-7, the content of active substances is 99.9 percent, and the CAS number is 154862-43-8;
the dispersing agent consists of 1 part by weight of hydroxyethyl cellulose, 0.1-5 parts by weight of sodium abietate, 1-10 parts by weight of BYK-358, 1-10 parts by weight of BYK-410 and 10-50 parts by weight of polyethylene oxide.
6. Falling film evaporation
The melt after melting reaches a falling film evaporator through a melt pump for degassing, the melt feeding speed is 500-800Kg/h, the temperature value of the falling film evaporator is controlled within the range of 80-115 ℃, the pressure value of a vacuum pump is controlled within the range of 15-80Pa, the degassing time is 5-24min, and the viscosity of the final melt is 0.41-0.58 dL/g.
7. Spinning
And the melt reaches a spinning box through a melt pump, and is subjected to melt spinning, drafting and winding through a spinneret plate to obtain the tea polyphenol modified polyester filament.
In the spinning, the pressure of a spinning assembly is 40-42MPa, and circular blowing is adopted for drying;
the spinning has the oil-free silk production rate lower than 0.1 percent, and the floating silk production rate and the staggered silk production rate lower than 0.2 percent and 0.001 percent respectively.
The specification of the adopted spinneret plate is 100 holes, and the aperture is 0.3 mm;
the speed of the first drafting roller is 2950 and 3650m/min, the speed of the second drafting roller is 4680 and 6100m/min, and the temperature of the hot plate is 79-82 ℃;
the winding speed is 5800 and 6500 m/min.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the tea polyphenol modified polyester filament yarn has the antibacterial rate of 97.1-99.2% for staphylococcus aureus, escherichia coli, candida albicans and other bacteria and the antibacterial rate of 79.7-90.4% for tetanus bacillus;
(2) the tea polyphenol modified polyester filament yarn has lasting antibacterial effect, and the reduction range of the antibacterial effect is small when an exposure test is carried out according to the method of GB/T16422.3 part 3: the antibacterial rate to staphylococcus aureus, colibacillus, candida albicans and other bacteria is 96.7-99.2%, and the antibacterial rate to tetanus bacillus is 75.8-90.0%;
(3) the tea polyphenol modified polyester filament has the advantages that monofilament fiber is 0.1-0.5dpf, the breaking strength is 8.2-9.9cN/dtex, and the breaking elongation is 11.2-18.0%;
(4) the preparation method of the tea polyphenol modified polyester filament yarn has the advantages of high spinning speed and high spinning quality, the production rate of oil-free yarns is lower than 0.1%, and the production rates of floating yarns and staggered yarns are respectively lower than 0.2% and 0.001%.
Detailed Description
Example 1 tea polyphenol modified polyester filament yarn and preparation method thereof
The invention relates to a preparation method of tea polyphenol modified polyester filament yarns, which comprises the following steps: raw material selection, porous nano TiO2-SiO2Preparing microspheres, preparing a functional modifier containing tea polyphenol, preparing functional master batches containing tea polyphenol, mixing and melting, falling film evaporation and spinning.
1. Selection of raw materials
Selecting commercially available tea polyphenol powder, transferring the tea polyphenol powder into a vertical sand mill, controlling the rotating speed of the sand mill to be 0.8Kr/min, grinding for 50min, continuously and uniformly spraying a 5% polyvinyl alcohol aqueous solution on the surface of the tea polyphenol powder in the grinding process, controlling the particle size of the tea polyphenol powder to be more than 99%, and sieving by a 10000-mesh sieve to obtain the tea polyphenol.
In the polyvinyl alcohol aqueous solution, the spraying amount of polyvinyl alcohol is 2 percent of the mass of the tea polyphenol powder;
the tea polyphenol powder is white amorphous crystalline powder with the content of 99.80 percent, the heavy metal content of less than or equal to 38.0ug/g, the lead content of less than or equal to 9.1ug/g, the arsenic content of less than or equal to 3.0ug/g, the relative molecular weight of 362.23 and the melting point of 131.0 ℃.
The tea polyphenols mainly comprise flavanones, anthocyanidins, flavonols, anthocyanins, phenolic acids and depside 6 compounds.
2. Porous nano TiO2-SiO2Preparation of microspheres
Downward active TiO at 20 DEG C2Sequentially adding sorbitan, softened water and sodium methylsilicate into the hydrosol, stirring uniformly, adding dilute hydrochloric acid for acidification to obtain a light yellow transparent colloid, adding an n-hexane solvent, heating to 50 ℃ at the speed of 2 ℃/min, keeping the temperature, stirring until an emulsion appears, adding sodium hydroxide, heating to the solution at the speed of 5 ℃/min, layering, keeping the temperature for 15min, filtering to obtain a white precipitate, washing, and drying to obtain the porous nano TiO2-SiO2 microsphere.
The active TiO2The mass ratio of the hydrosol to the sorbitol anhydride to the softened water to the sodium methyl silicate to the n-hexane solvent to the hydrochloric acid to the sodium hydroxide is 20: 0.2: 5: 1: 50: 0.1: 3.
The porous nano TiO2-SiO2Microspheres with the particle size of 0.1-10um, the aperture of 10-100nm and the sphericity of 98.9%; the grain diameter is between 4 and 8um and accounts for 94.5 percent;
3. preparation of functional modifier containing tea polyphenol
Pre-oriented porous nano TiO2-SiO2Adding 5% of polyvinylpyrrolidone into the microspheres, and uniformly mixing to obtain A; adding 5% polyvinylpyrrolidone into tea polyphenols, and mixing to obtain B;
a, B, adding tetracyanoquinodimethane and deionized water, stirring and converting into ultrasonic waves for ultrasonic treatment, wherein the ultrasonic frequency is 45KHz, the ultrasonic power is 1500W, the ultrasonic time is 8min, and removing water to obtain the functional modifier containing tea polyphenol.
The porous nano TiO2-SiO2The mass ratio of the microspheres, the tea polyphenol, the tetracyanoquinodimethane and the deionized water is 8:1: 10: 10.
4. Preparation of functional master batch containing tea polyphenol
Adding polyvinylpyrrolidone and PET slices into functional modifier containing tea polyphenol, and melting at high temperature to obtain functional master batch containing tea polyphenol, wherein the viscosity of the functional master batch containing tea polyphenol is 0.38-0.74 dl/g.
The weight ratio of the tea polyphenol-containing functional modifier to the polyvinylpyrrolidone to the PET slices is 2:0.1: 4.4.
5. Mixing and melting
Mixing and melting the functional master batch containing tea polyphenol, PET slices, amino trimethylene phosphonic acid, an antioxidant and a dispersing agent at high speed, wherein the mixing and melting temperature is 256-308 ℃, and the high-speed mixing rotating speed is 2.7 Kr/min.
The mass ratio of the PET slices, the amino trimethylene phosphonic acid, the antioxidant and the dispersant is 100: 0.1: 10:0.01.
The content of the functional master batch containing tea polyphenol is controlled by controlling the proportion of the tea polyphenol in the tea polyphenol modified polyester filament yarn to be 3 percent.
The density of the PET slices is 1.29g/cm3, the intrinsic viscosity is 0.77-0.82dL/g, and the breaking elongation is 19.2-24.5%;
the amino trimethylene phosphonic acid has an effective substance content of 95.2 percent, a chloride ion content of less than 0.1 percent and a CAS number of 6419-19-8;
the antioxidant is antioxidant T-9228, the pH value is 5-7, the content of active substances is 99.9 percent, and the CAS number is 154862-43-8;
the dispersing agent consists of 1 part of hydroxyethyl cellulose, 0.1 part of sodium abietate, 10 parts of BYK-358, 1 part of BYK-410 and 50 parts of polyoxyethylene.
6. Falling film evaporation
The melt after melting reaches a falling film evaporator through a melt pump for degassing, the feeding speed of the melt is 500Kg/h, the temperature value of the falling film evaporator is controlled within the range of 80-115 ℃, the pressure value of a vacuum pump is controlled within the range of 80Pa, the degassing time is 15min, and the viscosity of the final melt is 0.41-0.58 dL/g.
7. Spinning
And the melt reaches a spinning box through a melt pump, and is subjected to melt spinning, drafting and winding through a spinneret plate to obtain the tea polyphenol modified polyester filament.
In the spinning, the pressure of a spinning assembly is 40MPa, and circular blowing is adopted for drying;
the spinning has the oil-free silk production rate of 0.001 percent, and the floating silk production rate and the staggered silk production rate of 0.2 percent and 0.000 percent respectively.
The specification of the adopted spinneret plate is 100 holes, and the aperture is 0.3 mm;
in the drafting, the speed of the first drafting roller is 2950m/min, the speed of the second drafting roller is 4680m/min, and the temperature of a hot plate is 82 ℃;
and the winding speed is 5800 m/min.
The tea polyphenol modified polyester filament prepared by the method in example 1 has a remarkable plant antibacterial effect, and has the antibacterial rate of 98.1-98.5% for staphylococcus aureus, escherichia coli and candida albicans and the antibacterial rate of 79.7% for tetanus bacillus; and the antibacterial time is long, after the tea polyphenol modified polyester filament is subjected to an exposure test according to the method of GB/T16422.3 part 3, the antibacterial rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is 96.7-99.2%, the antibacterial rate to tetanus bacillus is 75.8%, and the antibacterial action is reduced.
Example 2 tea polyphenol modified polyester filament yarn and preparation method thereof
The invention also provides a preparation method of the tea polyphenol modified polyester filament yarn, which comprises the following steps: raw material selection, porous nano TiO2-SiO2Preparing microspheres, preparing a functional modifier containing tea polyphenol, preparing functional master batches containing tea polyphenol, mixing and melting, falling film evaporation and spinning.
1. Selection of raw materials
Selecting commercially available tea polyphenol powder, transferring the tea polyphenol powder into a vertical sand mill, controlling the rotating speed of the sand mill to be 2.2Kr/min, grinding for 33min, continuously and uniformly spraying a 5% polyvinyl alcohol aqueous solution on the surface of the tea polyphenol powder in the grinding process, controlling the particle size of the tea polyphenol powder to be more than 99%, and sieving by a 10000-mesh sieve to obtain the tea polyphenol.
In the polyvinyl alcohol aqueous solution, the spraying amount of polyvinyl alcohol is 2-3% of the mass of the tea polyphenol powder;
the tea polyphenol powder is white amorphous crystalline powder with the content of 99.80 percent, the heavy metal content of 8.0ug/g, the lead content of 3.0ug/g, the arsenic content of 2.2ug/g, the relative molecular weight of 362.23 and the melting point of 132.4 ℃.
The tea polyphenols mainly comprise flavanones, anthocyanidins, flavonols, anthocyanins, phenolic acids and depside 6 compounds.
2. Porous nano TiO2-SiO2Preparation of microspheres
Downward active TiO at 20 DEG C2Sequentially adding sorbitan, softened water and sodium methylsilicate into the hydrosol, stirring uniformly, adding dilute hydrochloric acid for acidification to obtain a light yellow transparent colloid, adding an n-hexane solvent, heating to 54 ℃ at the speed of 2 ℃/min, keeping the temperature, stirring until an emulsion appears, adding sodium hydroxide, heating to the solution at the speed of 5 ℃/min, layering, keeping the temperature for 12min, filtering to obtain a white precipitate, washing, and drying to obtain the porous nano TiO2-SiO2 microsphere.
The active TiO2The mass ratio of hydrosol, sorbitan, softened water, sodium methyl silicate, n-hexane solvent, hydrochloric acid and sodium hydroxide is 35: 0.15: 12:1: 35: 1.2: 2.
the porous nano TiO2-SiO2Microspheres with the particle size of 0.1-10um, the aperture of 10-100nm and the sphericity of 99.4%; the grain diameter is 4-8um and accounts for 95.7 percent;
3. preparation of functional modifier containing tea polyphenol
Pre-oriented porous nano TiO2-SiO2Adding 6% of polyvinylpyrrolidone into the microspheres, and uniformly mixing to obtain A; adding 4% polyvinylpyrrolidone into tea polyphenols, and mixing to obtain B;
a, B, adding tetracyanoquinodimethane and deionized water, stirring and converting into ultrasonic waves for ultrasonic treatment, wherein the ultrasonic frequency is 45KHz, the ultrasonic power is 1500W, the ultrasonic time is 15min, and removing water to obtain the functional modifier containing tea polyphenol.
The porous nano TiO2-SiO2The mass ratio of the microspheres, the tea polyphenol, the tetracyanoquinodimethane and the deionized water is 10:1:8: 40.
4. Preparation of functional master batch containing tea polyphenol
Adding polyvinylpyrrolidone and PET slices into functional modifier containing tea polyphenol, and melting at high temperature to obtain functional master batch containing tea polyphenol, wherein the viscosity of the functional master batch containing tea polyphenol is 0.38-0.74 dl/g.
The weight ratio of the tea polyphenol-containing functional modifier to the polyvinylpyrrolidone to the PET slices is 2:0.1: 10.
5. Mixing and melting
Mixing and melting the functional master batch containing tea polyphenol, PET slices, amino trimethylene phosphonic acid, an antioxidant and a dispersing agent at high speed, wherein the mixing and melting temperature is 256-308 ℃, and the high-speed mixing rotating speed is 2.8 Kr/min.
The mass ratio of the PET slices to the amino trimethylene phosphonic acid to the antioxidant to the dispersant is 100: 15: 8:18.
The content of the functional master batch containing tea polyphenol is controlled by controlling the proportion of the tea polyphenol in the tea polyphenol modified polyester filament yarn to be 5 percent.
The PET slice has the density of 1.32-1.40g/cm3, the intrinsic viscosity of 0.77-0.82dL/g and the breaking elongation of 19.2-24.5%;
the amino trimethylene phosphonic acid has an effective substance content of 95.7 percent, a chloride ion content of 0.05 percent and a CAS number of 6419-19-8;
the antioxidant is antioxidant T-9228, the pH value is 5-7, the content of active substances is 99.9 percent, and the CAS number is 154862-43-8;
the dispersing agent consists of 1 part of hydroxyethyl cellulose, 4 parts of sodium abietate, 9 parts of BYK-358, 8 parts of BYK-410 and 45 parts of polyethylene oxide in parts by weight.
6. Falling film evaporation
The melt after melting reaches a falling film evaporator through a melt pump for degassing, the melt feeding speed is 700Kg/h, the temperature value of the falling film evaporator is controlled within 103 ℃, the pressure value of a vacuum pump is controlled within 70Pa, the degassing time is 12min, and the viscosity of the final melt is 0.41-0.58 dL/g.
7. Spinning
And the melt reaches a spinning box through a melt pump, and is subjected to melt spinning, drafting and winding through a spinneret plate to obtain the tea polyphenol modified polyester filament.
In the spinning, the pressure of a spinning assembly is 41MPa, and circular blowing is adopted for drying;
the spinning has the oil-free filament generation rate of 0.0002 percent, and the floating filament generation rate and the staggered filament generation rate are respectively 0.0001 percent and 0.0000 percent.
The specification of the adopted spinneret plate is 100 holes, and the aperture is 0.3 mm;
the speed of the first drawing roller is 3350m/min, the speed of the second drawing roller is 5540m/min, and the temperature of a hot plate is 79 ℃;
and the winding speed is 6000 m/min.
The tea polyphenol modified polyester filament prepared by the method in the embodiment 2 has a remarkable plant antibacterial effect, and has the antibacterial rate of 98.4-97.7% for staphylococcus aureus, escherichia coli and candida albicans and the antibacterial rate of 81.7% for tetanus bacillus; and the antibacterial time is long, after the tea polyphenol modified polyester filament is subjected to an exposure test according to the method of GB/T16422.3 part 3, the antibacterial rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is 97.9-98.0%, the antibacterial rate to tetanus bacillus is 79.1%, and the antibacterial action is reduced.
Example 3 tea polyphenol modified polyester filament yarn and preparation method thereof
The invention also provides a preparation method of the tea polyphenol modified polyester filament yarn, which comprises the following steps: raw material selection, porous nano TiO2-SiO2Preparing microspheres, preparing a functional modifier containing tea polyphenol, preparing functional master batches containing tea polyphenol, mixing and melting, falling film evaporation and spinning.
1. Selection of raw materials
Selecting commercially available tea polyphenol powder, transferring the tea polyphenol powder into a vertical sand mill, controlling the rotating speed of the sand mill to be 2.5Kr/min, grinding for 20min, continuously and uniformly spraying a 5% polyvinyl alcohol aqueous solution on the surface of the tea polyphenol powder in the grinding process, controlling the particle size of the tea polyphenol powder to be more than 99%, and sieving by a 10000-mesh sieve to obtain the tea polyphenol.
In the polyvinyl alcohol aqueous solution, the spraying amount of polyvinyl alcohol is 3 percent of the mass of the tea polyphenol powder;
the tea polyphenol powder is white amorphous crystalline powder with the content of 99.80 percent, the heavy metal content of less than or equal to 38.0ug/g, the lead content of less than or equal to 9.1ug/g, the arsenic content of less than or equal to 3.0ug/g, the relative molecular weight of 362.23 and the melting point of 133.2 ℃.
The tea polyphenols mainly comprise flavanones, anthocyanidins, flavonols, anthocyanins, phenolic acids and depside 6 compounds.
2. Porous nano TiO2-SiO2Preparation of microspheres
Downward active TiO at 20 DEG C2Sequentially adding sorbitan, softened water and sodium methylsilicate into the hydrosol, stirring uniformly, adding dilute hydrochloric acid for acidification to obtain a light yellow transparent colloid, adding a normal hexane solvent, heating to 55 ℃ at the speed of 2 ℃/min, keeping the temperature, stirring until an emulsion appears, adding sodium hydroxide, heating to the solution at the speed of 5 ℃/min, layering, keeping the temperature for 10min, filtering to obtain a white precipitate, washing, and drying to obtain the porous nano TiO2-SiO2 microsphere.
The active TiO2The mass ratio of hydrosol, sorbitan, softened water, sodium methyl silicate, n-hexane solvent, hydrochloric acid and sodium hydroxide is 50: 0.05: 15: 1: 20: 2: 1.
the porous nano TiO2-SiO2Microspheres with the particle size of 0.1-10um, the aperture of 10-100nm and the sphericity of 99.4%; the grain diameter is 4-8um, and the proportion is 92.3 percent;
3. preparation of functional modifier containing tea polyphenol
Pre-oriented porous nano TiO2-SiO2Adding 8% of polyvinylpyrrolidone into the microspheres, and uniformly mixing to obtain A; adding 2% polyvinylpyrrolidone into tea polyphenols, and mixing to obtain B;
a, B, adding tetracyanoquinodimethane and deionized water, stirring and converting into ultrasonic waves for ultrasonic treatment, wherein the ultrasonic frequency is 45KHz, the ultrasonic power is 1500W, the ultrasonic time is 18min, and removing water to obtain the functional modifier containing tea polyphenol.
The porous nano TiO2-SiO2The mass ratio of the microspheres to the tea polyphenol to the tetracyanoquinodimethane to the deionized water is 12:1:1: 50.
4. Preparation of functional master batch containing tea polyphenol
Adding polyvinylpyrrolidone and PET slices into functional modifier containing tea polyphenol, and melting at high temperature to obtain functional master batch containing tea polyphenol, wherein the viscosity of the functional master batch containing tea polyphenol is 0.38-0.74 dl/g.
The weight ratio of the tea polyphenol-containing functional modifier to the polyvinylpyrrolidone to the PET slices is 2:0.1: 15.
5. Mixing and melting
Mixing and melting the functional master batch containing tea polyphenol, PET slices, amino trimethylene phosphonic acid, an antioxidant and a dispersing agent at high speed, wherein the mixing and melting temperature is 256-308 ℃, and the high-speed mixing rotating speed is 2.9 Kr/min.
The mass ratio of the PET slices to the amino trimethylene phosphonic acid to the antioxidant to the dispersant is 100: 20: 0.01: 20.
The content of the functional master batch containing tea polyphenol is controlled by controlling the proportion of the tea polyphenol in the tea polyphenol modified polyester filament yarn to be 1.5 percent.
The PET slice has the density of 1.35-1.40g/cm3, the intrinsic viscosity of 0.77-0.82dL/g and the breaking elongation of 19.2-24.5%;
99.5 percent of active substance, 0.01 percent of chloride ion and 6419-19-8 percent of CAS number;
the antioxidant is antioxidant T-9228, the pH value is 5-7, the content of active substances is 99.9 percent, and the CAS number is 154862-43-8;
the dispersing agent consists of 1 part of hydroxyethyl cellulose, 5 parts of sodium abietate, 1 part of BYK-358, 10 parts of BYK-410 and 12 parts of polyethylene oxide in parts by weight.
6. Falling film evaporation
The melt after melting reaches a falling film evaporator through a melt pump for degassing, the melt feeding speed is 800Kg/h, the temperature value of the falling film evaporator is controlled within 95 ℃, the pressure value of a vacuum pump is controlled within 80Pa, the degassing time is 7min, and the viscosity of the final melt is 0.41-0.58 dL/g.
7. Spinning
And the melt reaches a spinning box through a melt pump, and is subjected to melt spinning, drafting and winding through a spinneret plate to obtain the tea polyphenol modified polyester filament.
In the spinning, the pressure of a spinning assembly is 42MPa, and circular blowing is adopted for drying;
the spinning has the oil-free silk production rate of 0.08 percent, and the floating silk production rate and the staggered silk production rate of 0.003 percent and 0.0001 percent respectively.
The specification of the adopted spinneret plate is 100 holes, and the aperture is 0.3 mm;
the speed of a first drawing roller is 3650m/min, the speed of a second drawing roller is 5600m/min, and the temperature of a hot plate is 82 ℃;
and the winding speed is 6000 m/min.
The tea polyphenol modified polyester filament prepared by the method in the embodiment 3 has a remarkable plant antibacterial effect, and has the antibacterial rate of 98.0-98.6% for staphylococcus aureus, escherichia coli and candida albicans and the antibacterial rate of 77.0% for tetanus bacillus; and the antibacterial time is long, after the tea polyphenol modified polyester filament is subjected to an exposure test according to the method of GB/T16422.3 part 3, the antibacterial rate to staphylococcus aureus, escherichia coli, candida albicans and other bacteria is 97.3-98.4%, the antibacterial rate to tetanus bacillus is 74.1%, and the antibacterial action is reduced.
Index detection of tea polyphenol modified polyester filament yarn
Index detection is carried out on the tea polyphenol modified polyester filament yarns prepared by the methods of examples 1-3, and the detection results are as follows (X pull):
Figure 501260DEST_PATH_IMAGE001
in conclusion, the tea polyphenol modified polyester filament prepared by the method of the embodiment 1-3 has the monofilament fiber of 0.1-0.5dpf, the breaking strength of 8.2-9.9cN/dtex and the elongation of 11.2-18.0%; the pilling rate of the fabric prepared by the tea polyphenol modified polyester filament yarn is obviously lower than that of the common polyester fabric.
The preparation method of the tea polyphenol modified polyester filament yarn has the advantages of high spinning speed and high spinning quality, the production rate of oil-free yarns is lower than 0.1%, and the production rates of floating yarns and staggered yarns are respectively lower than 0.2% and 0.001%.
All percentages used herein are weight percentages and all ratios described herein are mass ratios, unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The tea polyphenol modified polyester filament yarn is characterized in that the tea polyphenol mass content of the tea polyphenol modified polyester filament yarn is 0.1-5%.
2. The tea polyphenol modified polyester filament yarn as claimed in claim 1, wherein the tea polyphenol modified polyester filament yarn has a monofilament fiber of 0.1-0.5dpf, a breaking strength of 8.2-9.9cN/dtex, and a breaking elongation of 11.2-18.0%.
3. A preparation method of tea polyphenol modified polyester filament yarn is characterized in that,
the preparation method of the tea polyphenol modified polyester filament yarn comprises the following steps: preparing a functional modifier containing tea polyphenol, preparing a functional master batch containing tea polyphenol, mixing and melting, falling film evaporation and spinning.
4. The method for preparing tea polyphenol modified polyester filament yarn as claimed in claim 3,
the preparation of the functional modifier containing tea polyphenol is carried out to porous nano TiO2-SiO2Adding 5-8% polyvinylpyrrolidone into the microsphere, and mixing uniformly to obtain A; adding 2-5% polyvinylpyrrolidone into tea polyphenols, and mixing to obtain B; a, B, adding tetracyanoquinodimethane and deionized water, stirring and converting into ultrasonic waves for ultrasonic treatment, wherein the ultrasonic frequency is 45-50KHz, the ultrasonic power is 1500-2000W, and the ultrasonic time is 8-18 min.
5. The method for preparing tea polyphenol modified polyester filament yarn as claimed in claim 3,
preparation of the functional modifier containing tea polyphenol and porous nano TiO2-SiO2The mass ratio of the microspheres to the tea polyphenol to the tetracyanoquinodimethane to the deionized water is 8-12:1:1-10: 10-50.
6. The method for preparing tea polyphenol modified polyester filament yarn as claimed in claim 3,
the mixing and melting are carried out, the mixing and melting temperature is 256-308 ℃, and the high-speed mixing rotating speed is 2.7-2.9 Kr/min.
7. The method for preparing tea polyphenol modified polyester filament yarn as claimed in claim 3,
the amino trimethylene phosphonic acid has an effective substance content of more than 95 percent, a chloride ion content of less than 0.1 percent and a CAS number of 6419-19-8;
the antioxidant is antioxidant T-9228, the pH value is 5-7, the content of active substances is 99.9%, and the CAS number is 154862-43-8.
8. The method for preparing tea polyphenol modified polyester filament yarn as claimed in claim 3,
the dispersing agent consists of 1 part by weight of hydroxyethyl cellulose, 0.1-5 parts by weight of sodium abietate, 1-10 parts by weight of BYK-358, 1-10 parts by weight of BYK-410 and 10-50 parts by weight of polyethylene oxide.
9. The method for preparing tea polyphenol modified polyester filament yarn as claimed in claim 3,
the falling film evaporation has melt feeding speed of 500-800Kg/h, temperature of 80-115 deg.c, vacuum pump pressure of 15-80Pa, degassing time of 5-24min and melt viscosity of 0.41-0.58 dL/g.
10. The method for preparing tea polyphenol modified polyester filament yarn as claimed in claim 3,
in the spinning process, the speed of the first drawing roller is 2950 and 3650m/min, the speed of the second drawing roller is 4680 and 6100m/min, and the temperature of the hot plate is 79-82 ℃.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021088307A1 (en) * 2019-11-06 2021-05-14 百事基材料（青岛）股份有限公司 Plant functional polyester filament and preparation method therefor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021088307A1 (en) * 2019-11-06 2021-05-14 百事基材料（青岛）股份有限公司 Plant functional polyester filament and preparation method therefor

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