CN109385893A - A kind of polyester complex fiber and the preparation method and application thereof with intelligent surface - Google Patents

A kind of polyester complex fiber and the preparation method and application thereof with intelligent surface Download PDF

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Publication number
CN109385893A
CN109385893A CN201710671322.2A CN201710671322A CN109385893A CN 109385893 A CN109385893 A CN 109385893A CN 201710671322 A CN201710671322 A CN 201710671322A CN 109385893 A CN109385893 A CN 109385893A
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China
Prior art keywords
particles
polyester
fiber
group
bond
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Inventor
刘继广
石高丽
王锐
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Beijing Institute Fashion Technology
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Beijing Institute Fashion Technology
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Priority to CN201710671322.2A priority Critical patent/CN109385893A/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D06M10/10—Macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention discloses a kind of polyester complex fiber and the preparation method and application thereof with intelligent surface, the polyester complex fiber include the particle of polyester fiber matrix and covering thereon, wherein are chemical bonds between the particle and polyester fiber matrix；Preferably, the particle is polymer beads, more preferably with the polymer beads of environmental response, in this way, can not only improve the hydrophilic and hydrophobic of fiber in fibrous matrix surface covering particle, but also can assign fiber certain environment-responsive.The preparation is following to be carried out: first obtain surface have can reactive group polyester fiber matrix, then obtain have can reactive functionality particle, polyester fiber matrix is reacted with particle mixing finally, obtains the polyester complex fiber.Polyester complex fiber of the present invention can be used for intelligent textile, non-woven fabrics, perforated membrane, composite material and oil water separator, be preferred for intelligent textile and oil water separator.

Description

Polyester composite fiber with intelligent surface and preparation method and application thereof
Technical Field
The invention belongs to the field of fiber materials, particularly relates to polyester fibers, and particularly relates to a polyester composite fiber with an intelligent surface, and a preparation method and application thereof.
Background
Polyesters are a general term for high molecular compounds having ester bonds in the main chain, and are generally obtained by condensation polymerization of dibasic acids and dihydric alcohols. While polyester fiber materials are widely applied to various fields such as fabrics, filter materials, catalysis and the like, the conventional polyester fibers generally have smooth and uniform surface properties, so that the application of the polyester fiber materials is mainly determined by the properties of fiber bodies. The change of the hydrophilic and hydrophobic properties of the fiber surface seriously affects the use performance of the fiber, and the hydrophilic and hydrophobic properties of the material can be improved by changing the roughness or the surface energy of the material surface.
The prior art relates to improving the roughness through surface etching, thereby improving the hydrophilicity and hydrophobicity of the surface, however, the etching can reduce the mechanical property of the material to a certain extent, thereby reducing the practicability of the material.
The prior art also relates to the modification of the surface of a material by using silica particles so as to improve the hydrophilic and hydrophobic properties of the material, however, the modification mostly adopts physical modification, the properties are unstable, or even chemical modification, the efficiency is low.
Disclosure of Invention
In view of the problems in the prior art, the present inventors have made intensive studies to modify the surface of a fiber substrate with particles, preferably polymer particles, which are chemically bonded to the surface of the fiber to stabilize the properties of the obtained material and have a certain roughness on the surface, thereby effectively improving the hydrophilicity and hydrophobicity of the surface of the material, and more preferably particles having an environmental response, thereby providing the surface of the obtained material with a certain environmental response, such as a temperature response or a pH response, thereby completing the present invention.
The invention provides a polyester composite fiber with an intelligent surface, which comprises a polyester fiber matrix and particles covered on the polyester fiber matrix, wherein the particles and the polyester fiber matrix are chemically bonded.
The invention also provides a preparation method of the polyester composite fiber, which comprises the following steps:
step 1, obtaining a polyester fiber matrix with a reactive group on the surface;
step 2, obtaining particles with reactive groups;
and 3, adding the particles obtained in the step 2 into a solvent, adding the polyester fiber matrix obtained in the step 1 into the solvent, reacting, and performing post-treatment to obtain the polyester composite fiber with the intelligent surface.
In a third aspect, the present invention provides an application of the polyester composite fiber according to the first aspect of the present invention or the polyester composite fiber obtained by the method according to the second aspect of the present invention, wherein the polyester composite fiber can be used for intelligent textiles, non-woven fabrics, porous membranes, composite materials and oil-water separators, preferably for intelligent textiles and oil-water separators.
Drawings
FIG. 1 shows a transmission electron micrograph of the fiber obtained in example 1;
FIG. 2 shows a partial enlarged view of FIG. 1;
FIGS. 3 and 4 show the results of the water contact angle test at room temperature and 40 degrees for the fiber obtained in example 3, respectively;
FIG. 5 shows the results of the water contact angle test at room temperature for the fibers obtained in example 5;
FIG. 6 shows the results of the oil contact angle test at room temperature for the fibers obtained in example 5;
FIG. 7 is a schematic view showing an initial oil-water separation test using the fiber obtained in example 9;
FIG. 8 is a schematic view showing a post oil-water separation test using the fiber obtained in example 9.
Description of the reference numerals
1-polyester composite fiber.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The invention provides a polyester composite fiber with an intelligent surface, wherein the polyester composite fiber comprises a polyester fiber matrix and particles covering the polyester fiber matrix, and the particles and the polyester fiber matrix are chemically bonded.
According to a preferred embodiment of the present invention, the particles are bonded to the polyester fiber matrix via an ester bond, an amide bond, an ether bond, a C ═ N bond, an N — N bond, a C — C bond, a C ═ C bond, an S — S bond, a C — S bond, and/or an S — O bond.
In a further preferred embodiment, the particles are bonded to the polyester fiber matrix via an ester bond, an amide bond, an ether bond, a C ═ N bond, an S — S bond, and/or a C — S bond.
In a still further preferred embodiment, the particles are bonded to the polyester fiber matrix via ester, amide and/or ether linkages.
Wherein the particles are chemically bonded to the polyester fiber matrix, and thus the fiber has a very stable structure compared to simple blending or bonding by gluing.
In the invention, after the polyester composite fiber is washed under ultrasonic wave, the particles on the surface of the polyester composite fiber do not fall off, which shows that the particles and the polyester composite fiber matrix have strong bonding effect.
According to a preferred embodiment of the present invention, the polyester fiber matrix has a diameter of 5nm to 1 mm.
In a further preferred embodiment, the polyester fiber matrix has a diameter of 50nm to 50 μm.
In a further preferred embodiment, the polyester fiber matrix has a diameter of 5 to 50 μm, for example 20 to 40 μm.
Wherein, in order to ensure that the obtained fiber has certain use strength (namely practicability), the diameter of the fiber matrix is limited to be 5 nm-1 mm, preferably 50 nm-50 μm, more preferably 5-50 μm, such as 20-40 μm.
According to a preferred embodiment of the invention, the particles have a particle size of 1nm to 500 μm.
In a further preferred embodiment, the particles have a particle size of 20nm to 10 μm.
In a further preferred embodiment, the particles have a particle size of 100nm to 5 μm, for example 100 to 500 nm.
Wherein, the particles cover the surface of the fiber matrix to form a rough structure surface, so the particle size of the particles is not suitable to be too large or too small.
According to a preferred embodiment of the invention, the ratio of the particle size of the particles to the diameter of the fibrous matrix is 1 (2 to 10000).
In a further preferred embodiment, the ratio of the particle size of the particles to the diameter of the fiber matrix is 1 (4 to 1000).
In a further preferred embodiment, the ratio of the particle size of the particles to the diameter of the fibrous matrix is 1 (20 to 100), for example 1 (20 to 60).
Wherein the particles form a micro/nano structure on the fiber matrix, so that the surface of the fiber matrix has certain roughness, thereby improving the hydrophilicity and hydrophobicity of the fiber.
According to a preferred embodiment of the invention, the polyester composite fibre matrix is selected from the group consisting of a polyethylene terephthalate (PET) fibre matrix, a polybutylene terephthalate (PBT) fibre matrix, a polyarylate fibre matrix, a polybutylene succinate (PBS) fibre matrix, a Polyhydroxybutyrate (PHB) fibre matrix, a polybutylene fumarate (PBF) fibre matrix, a polyadipate fibre matrix, a polycaprolactone fibre matrix and/or a polycarbonate fibre matrix, such as a polyethylene terephthalate (PET) fibre matrix.
In a further preferred embodiment, optionally, other polymers or inorganic fillers are compounded in the polyester fiber matrix.
Wherein the other polymer is other than polyester.
In a still further preferred embodiment, the inorganic filler is selected from one or more of silica, titanium dioxide, iron trioxide, triiron tetroxide, barium sulfate, tungsten trioxide, carbon black and calcium carbonate, such as silica, titanium dioxide.
Wherein, other materials can be compounded in the polyester fiber matrix, so that different functions can be endowed to the polyester fiber matrix.
According to a preferred embodiment of the present invention, the surface of the polyester fiber substrate is modified with a reactive group.
In a further preferred embodiment, the surface of the polyester fiber substrate is modified with one or more reactive groups selected from hydroxyl, carboxyl, amino, double bond, mercapto, amide, epoxy, bromine and chlorine groups.
In a further preferred embodiment, the surface of the polyester fiber substrate is modified with one or more reactive groups selected from hydroxyl, amino and double bond.
The surface of the polyester fiber substrate is modified with a reactive group, so that the polyester fiber substrate can react with particles to form ester bonds, amido bonds and/or ether bonds and the like, and chemical bonding is realized.
According to a preferred embodiment of the invention, the particles are selected from polymer particles and/or inorganic particles.
In a further preferred embodiment, the particles are selected from polymer particles, optionally doped with an inorganic material.
In a still further preferred embodiment, the inorganic material is selected from one or more of silica, titanium dioxide, ferric oxide, ferroferric oxide, barium sulfate, tungsten trioxide, carbon black and calcium carbonate, such as silica and/or titanium dioxide.
Among them, the inorganic material is small in the bonding area with the polyester fiber matrix, and thus, it is difficult to bond, and even if it is bonded, the inorganic material is easily dropped, and therefore, in the present invention, it is preferable that the particles are polymer particles in which the contact area between the polymer particles and the polyester fiber matrix is large, that is, a plurality of chemical bonds can be bonded at the bonding site, and thus, the stability of bonding is secured.
In the present invention, the structure of the particles is not limited, such as a core-shell structure, a double-partition structure, a strawberry structure, a dumbbell structure; preferably from an asymmetric structure.
According to a preferred embodiment of the present invention, the polymer in the polymer particles is a polymer modified with a reactive group.
In a further preferred embodiment, the polymer in the polymer particles is a polymer modified with one or more of hydroxyl, carboxyl, amino, double bond, mercapto, amide, epoxy and chlorine groups.
In a further preferred embodiment, the polymer in the polymer particles is an environmentally responsive polymer modified with one or more of hydroxyl, carboxyl, mercapto and epoxy groups, such as carboxyl, amino and epoxy groups.
Wherein the polymer is a homopolymer or a copolymer, and the reactive group in the polymer particle reacts with the reactive group modified on the surface of the polyester fiber matrix, so that the polymer particle and the polyester fiber matrix are chemically bonded. The polymer may preferably be an environmentally responsive polymer, so that it is supported on a polyester fiber matrix, and can impart environmentally responsive characteristics to the fiber, with environmentally responsive properties.
According to a preferred embodiment of the invention, the environmentally responsive polymer is selected from the group consisting of temperature responsive polymers, pH responsive polymers, humidity responsive polymers, solvent responsive polymers, CO2One or more of the responsive polymer, the ion-responsive polymer and the photo-responsive polymer are selected from homopolymers shown in formulas (1) to (3) and/or copolymers containing polymer segments shown in formulas (1) to (3).
In a further preferred embodiment, in formula (1): r1、R2And R3Each independently selected from hydrogen or C1～C6Preferably selected from hydrogen or C1～C3Alkyl of (4); in the formula (2), R4Selected from hydrogen or C1～C6Preferably selected from hydrogen or C1～C3Alkyl groups of (a); in the formula (3), R5、R6And R7Each independently selected from hydrogen or C1～C6Preferably selected from hydrogen or C1～C3Alkyl groups of (a); in the formulae (1) to (3), 20>m≥0。
In a still further preferred embodiment, in formula (1): r1、R2And R3Each independently selected from hydrogen, methyl, ethyl or isopropyl; in thatIn the formula (2), R4Selected from hydrogen or methyl; in the formula (3), R5、R6And R7Each independently selected from hydrogen or methyl, for example methyl; in formulae (1) to (3), 10>m is 0 or more, for example, m is 0.
Wherein, the polymer or polymer chain segment shown in the formula (1) has temperature responsiveness, specifically, has LCST, in aqueous solution, when the temperature is lower than the LCST, the side chain can form hydrogen bond action with water molecule, and the molecular chain is stretched, but when the temperature is higher than the LCST, the intermolecular hydrogen bond is broken, and the molecular chain is curled, therefore, the polymer or polymer chain segment shown in the formula (1) has temperature responsiveness. The polymer or polymer segment shown in the formula (2) has pH responsiveness, and molecular chains respond differently at different pH values. The polymer or polymer segment represented by formula (3) has both temperature responsiveness and pH responsiveness.
According to a preferred embodiment of the present invention, the environmentally responsive polymer is selected from homopolymers and/or copolymers containing poly (N-isopropylacrylamide) (PNIPAM) segments, poly (N-isopropylmethacrylamide) (PNIPMAM) segments, poly (N, N-diethylacrylamide) (PDEA) segments, poly (N-ethylacrylamide) (PEMA) segments, poly (N, N-dimethylaminoethyl methacrylate) (PDMAEMA) segments, polyvinylpyridine, polyacrylic acid (PAA) segments and/or polymethacrylic acid (PMAA) segments.
The use of polymer particles having an environmental response can, among other things, impart environmental response properties to the fibers, for example, when particles containing poly (N-isopropylacrylamide) segments are used, temperature responsiveness to the fibers. Therefore, the fiber can be applied to intelligent textiles, the intelligent textiles can adjust the temperature to adapt to the requirements of human bodies, a comfortable microclimate environment is provided for human bodies, and the fiber has an active adjusting effect on the body temperature of the human bodies between the human bodies and the external environment. On the other hand, when the temperature of the external environment is too high, the molecular chains of the particles on the surface of the fiber shrink, and the air permeability of the textile is improved.
In a further preferred embodiment, the environmentally responsive polymer is selected from homopolymers and/or copolymers containing poly (N-isopropylacrylamide) (PNIPAM) segments, poly (N, N-dimethylaminoethyl methacrylate) (PDMAEMA) segments, and/or polyacrylic acid (PAA) segments.
More preferably, the environmentally responsive polymer is selected from homopolymers and/or copolymers containing poly (N-isopropylacrylamide) (PNIPAM) segments and/or poly (N, N-dimethylaminoethyl methacrylate) (PDMAEMA) segments.
The fiber can be used for the application of the intelligent environment responsiveness control, can also be used for oil-water separation, when the fiber has hydrophobicity, oil passes through the fiber, and water does not pass through the fiber, so that the oil-water separation is successfully realized, the separation effect is good, the speed is high, other chemical additives are not needed, toxic or side effect and secondary pollution are avoided, and the fiber can be repeatedly used.
Specifically, (1) when the particles compounded on the surface of the fiber are hydrophilic polymer particles, such as in example 1 and example 5, the fiber shows hydrophilicity, and normal water permeates the fiber but oil does not permeate the fiber, so that oil-water separation is realized; (2) when the particles compounded on the fiber surface are hydrophilic polymer-hydrophobic polymer copolymer particles, the hydrophilicity and hydrophobicity of the particles need to be analyzed according to the chain segment ratio of the hydrophilic block to the hydrophobic block, if the hydrophilic polymer occupies the main body, the hydrophilicity is shown, if the hydrophobic polymer occupies the main body, the hydrophobicity is shown, and oil-water separation can be realized as well; (3) when the particles compounded on the surface of the fiber are hydrophobic particles, the fiber is hydrophobic, general oil can permeate the fiber, and water cannot permeate the fiber, so that oil-water separation is realized.
In a second aspect, the present invention provides a method for preparing the polyester composite fiber according to the first aspect, the method comprising the steps of:
step 1, obtaining a polyester fiber matrix with a reactive group on the surface.
According to a preferred embodiment of the present invention, the polyester fiber substrate having the reactive group on the surface thereof can be purchased directly, or prepared directly by polymerization and spinning, or subjected to surface functionalization treatment to obtain the polyester fiber substrate having the reactive group on the surface thereof.
In a further preferred embodiment, the polyester fiber matrix is surface functionalized by plasma irradiation, chemical etching, uv graft polymerization or surface chemical modification.
Wherein, the polyester fiber matrix is subjected to surface functionalization treatment, so that the surface of the polyester fiber matrix is modified with reactive groups, such as one or more of hydroxyl, carboxyl, amino, double bonds, sulfydryl, amido, epoxy and chlorine groups.
And 2, obtaining particles with reactive groups.
Wherein the particles are preferably polymer particles, optionally doped with inorganic materials, such as one or more of titanium dioxide, silica, ferric oxide, ferroferric oxide, barium sulfate, tungsten trioxide, carbon black and calcium carbonate. The particles having reactive groups are purchased or prepared directly and are prepared according to the literature known from the prior art.
According to a preferred embodiment of the invention, the preparation of the polymer particles is carried out directly, with the polyester fiber matrix reacting with its own functional groups as reactable groups.
For example, polyacrylic acid particles can be reacted directly with the polyester fiber matrix after preparation without further functionalization.
According to another preferred embodiment of the invention, the polymer particles are functionalized after they have been obtained.
For example, poly (N, N-dimethylaminoethyl methacrylate-styrene) particles containing benzenesulfonic acid groups are prepared by first preparing poly (N, N-dimethylaminoethyl methacrylate-styrene) particles, which are then subjected to a sulfonation treatment to obtain polymer particles containing sulfonic acid groups.
According to a preferred embodiment of the present invention, when the polymer in the polymer particles is a polymer modified with hydroxyl groups, for example, particles containing polyvinyl alcohol or polyethylene oxide can be directly prepared, or a polymer without hydroxyl groups can be prepared and then functionalized to attach hydroxyl groups, thereby obtaining a polymer modified with hydroxyl groups.
In a further preferred embodiment, when the polymer in the polymer particles is a hydroxyl-modified polymer, such as polyvinyl alcohol or polyethylene oxide, the preparation is carried out directly.
According to a preferred embodiment of the present invention, when the polymer in the polymer particles is a polymer modified with carboxyl, for example, an acrylate polymer can be directly prepared, or a polymer without carboxyl can be prepared and then functionalized to obtain a polymer modified with carboxyl.
In a further preferred embodiment, when the polymer in the polymer particles is a polymer modified with a carboxyl group, an acrylic polymer may be prepared, and then the carboxyl group may be obtained by a functionalization treatment.
According to a preferred embodiment of the invention, when the polymer in the polymer particles is a thiol-modified polymer, reference is made to the literature (Olivia Z. Durham et al. colloid Polym Sci,2015,293, 2385-.
Among them, the method for producing the mercapto group-containing polymer is not limited to the method disclosed in the above-mentioned document as long as the mercapto group-containing polymer can be obtained.
According to a preferred embodiment of the present invention, when the polymer in the polymer particles is a polymer modified with an amide group, the acrylamide-based polymer may be directly prepared, or a polymer not containing an amide group may be prepared and then functionalized to obtain a polymer modified with an amide group.
In a further preferred embodiment, the acrylamide-based polymer is directly prepared.
According to a preferred embodiment of the present invention, when the polymer in the polymer particles is an epoxy-modified polymer, reference may be made to the literature (Jiaojun Tan et al, RSC adv.2014,4, 13334-13339).
Among them, the method for producing the epoxy group-containing polymer is not limited to the method disclosed in the above-mentioned document as long as the epoxy group-containing polymer can be obtained.
According to a preferred embodiment of the present invention, when the polymer in the polymer particles is a polymer modified with a chlorine group, the production of a polyvinyl chloride-based polymer can be directly performed to obtain a polymer modified with a chlorine group.
And 3, adding the particles obtained in the step 2 into a solvent, adding the polyester fiber matrix obtained in the step 1 into the solvent, reacting, and performing post-treatment to obtain the polyester fiber with the intelligent surface.
In a preferred embodiment of the process according to the invention, the order of addition can be changed in step 3.
According to a preferred embodiment of the present invention, in step 3, the solvent is a poor solvent for the polyester fiber matrix and the particles.
In a preferred embodiment according to the invention, in step 3, a catalyst is optionally added.
In a further preferred embodiment, the selection of the catalyst depends on the type of reaction between the polyester fiber matrix and the particles, for example, the catalyst is selected from one or more of acids (e.g. a compound of formula e) or acid salts, bases, lithium aluminum hydride, azobisisobutyronitrile or benzoin dimethyl ether, compounds of formula (a) to formula (d).
Wherein:
in formula (a), R'1Selected from hydroxyl, hydroxyl containing alkyl chain, phenyl, amido, bromine group, maleic succinimidyl butyric acid, acryloxy or group shown in formula (f); r'2Selected from H, carboxyl or sulfonic acid containing alkyl chain or sulfonate (such as sodium sulfonate);
in formulae (c) and (d), R'3And R'4Each independently selected from alkyl, alkoxy or aryl;
in formula (e), R'5And R'6Each independently selected from methyl, ethyl, isopropyl, N-cyclohexyl, 1, 3-di-p-tolyl, 1- (3-dimethylaminopropyl) -3-ethyl or a group of formula (g), wherein in formula (g), N is 2-8, preferably N is 2-5.
According to a preferred embodiment of the invention, the post-treatment is carried out as follows: the fibers are collected, washed and optionally dried.
In a third aspect of the present invention, there is provided a use of the polyester composite fiber according to the first aspect of the present invention or the polyester composite fiber obtained according to the second aspect of the present invention, wherein the polyester composite fiber can be used for intelligent textiles, non-woven fabrics, porous membranes, composite materials, and oil-water separators, preferably for intelligent textiles and oil-water separators.
The invention has the following beneficial effects:
(1) the polyester composite fiber has a special surface structure, and the roughness and the surface chemical property of the surface of the polyester fiber are improved by covering the polyester composite fiber with particles, so that the hydrophilicity and hydrophobicity of the polyester fiber are improved;
(2) the particles on the surface of the polyester composite fiber are bonded with the polyester fiber matrix through chemical bonds, so that the bonding degree can be improved, and the particles are not easy to fall off;
(3) the particles covered on the surface of the polyester composite fiber can have environmental responsiveness, so that the environmental responsiveness can be given to the fiber;
(4) the polyester composite fiber can be used for preparing intelligent textiles, specifically, the intelligent textiles can adjust the temperature to adapt to the requirements of human bodies, provide a comfortable microclimate environment for human bodies, and play a positive role in adjusting the body temperature of the human bodies between the human bodies and the external environment;
(5) the hydrophilicity of the polyester composite fiber can be adjusted according to the environment, so that the antistatic performance and the dyeability of polyester textiles are effectively improved;
(6) the polyester composite fiber can be used for an intelligent oil-water separator, and particularly, intelligent conversion is carried out between hydrophilic and hydrophobic according to different environmental responses, so that the external environment is equivalent to a switch, and the fiber is controlled to be converted between hydrophilic and hydrophobic.
Examples
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
In the examples:
preparation of epoxy group-containing poly (N-isopropylacrylamide) particles in example 1 is described in reference 1(Penghui Li et al, Colloid Surface B2013, 101, 251-255.);
the preparation of poly (acrylic acid-styrene) particles in example 2 is described in literature 2 (Xinlong Fan, equivalent. Polymer. chem.,2015,6, 703-713);
preparation of silica-containing N, N-dimethylaminoethyl methacrylate hybrid particles in example 3 is described in reference 3(Wanzhu Zhou et al, Powder tech. 2013,249, 1-6.);
preparation of epoxy group-containing poly (N, N-dimethylaminoethyl methacrylate-styrene) particles in example 4 is described in reference 4(s.fujii et al, Langmuir 2004,20(26), 11329-11335.);
in example 5, poly (N-isopropylacrylamide-methacrylic acid) particles were prepared as described in reference 5 (zhufuquan et al, synthesis and use, 2009, 24(4) 14-19.);
preparation of poly (N-isopropylacrylamide-acrylic acid) particles in example 6 is described in reference 6 (AnnaBurmeistorva et al.J.Mater. chem.2010,20, 3502-3507.);
see document 7(Qiang Ye et al, j. colloid inter f. sci.2002,253,279-284.) for the preparation of polyacrylamide particles in example 7;
the preparation of polystyrene/poly (N-isopropylacrylamide-methacrylic acid) composite particles in example 8 is described in document 8(m.ashraful Alam, et al.j.appl.sci. 2008,8(2), 352-;
for the preparation of the silica/poly (N-isopropylacrylamide-styrene) hybrid particles in example 9, see literature 9(jin Hu, et al, polymer. chem.2013,4, 3293-;
preparation of styrene-methyl methacrylate-butadiene copolymer particles of epoxy groups of example 10 is described in the literature (A.M. Aerdts, et al. Polymer 1997,38 (16), 4247-4252.).
Example 1
1g of poly (N-isopropylacrylamide) particles containing epoxy groups is dispersed in 500mL of toluene, 2g of PET polyester fibers containing hydroxyl groups are added, the mixture is reacted at 80 ℃ for 4 hours, and then the mixture is taken out and washed by ethanol and water to obtain the intelligent polyester composite fiber.
Wherein the particle diameter of the poly (N-isopropylacrylamide) particles containing epoxy groups is 250nm, and the diameter of the PET polyester fibers containing hydroxyl groups is 6 μm.
In example 1, a hydroxyl group-containing PET polyester fiber fabric was obtained as follows: and adding the PET polyester fiber into a sodium hydroxide solution, and reacting for 1 hour to obtain the hydroxyl-containing PET polyester fiber.
Example 2
1g of poly (acrylic acid-styrene) particles are dispersed in 200mL of decane, 2g of hydroxyl-containing PET polyester fiber is added, the reaction is carried out at 90 ℃ for 4 hours, and then the mixture is separated and washed, so as to obtain the polyester composite fiber.
Wherein the poly (acrylic acid-styrene) particles have a particle size of 300nm and the polyester fibers containing hydroxyl groups have a diameter of 6 μm.
In example 2, a hydroxyl group-containing PET polyester fiber fabric was obtained as follows: and adding the PET polyester fiber fabric into a sodium hydroxide solution, and reacting for 1 hour to obtain the hydroxyl-containing PET polyester fiber.
Example 3
Dispersing 1g of silicon dioxide-containing poly (N, N-dimethylaminoethyl methacrylate) hybrid particles into water, carrying out ultrasonic treatment for 80min, washing, drying, dispersing into anhydrous toluene, adding 0.05g of 3-mercaptopropyltrimethoxysilane, reacting at room temperature for 12 hours, washing with toluene, dispersing the silicon dioxide/poly (N, N-dimethylaminoethyl methacrylate) composite particles containing sulfydryl into 200mL of heptane, adding 2g of double bond-containing PET polyester fibers and 4 mg of benzoin dimethyl ether, irradiating with ultraviolet light for 4 hours, and washing with ethanol and water to obtain the polyester composite fibers.
Wherein the particle diameter of the N, N-dimethylaminoethyl methacrylate hybrid particles containing silicon dioxide is 5 μm, and the diameter of the polyester fiber fabric containing double bonds is 20 μm.
In example 3, the preparation of the double bond-containing PET polyester fiber is described in "the graft-compounding of polysiloxane/coupling modified titanium sol and the thin loading on the surface of the polyester fiber, doctrine, cong jun, zhejiang university".
Example 4
Dispersing 2g of poly (N, N-dimethylaminoethyl methacrylate-styrene) particles containing epoxy groups in concentrated sulfuric acid, reacting for 24 hours, then dispersing poly (N, N-dimethylaminoethyl methacrylate-styrene) particles containing carboxyl in 200ml of water, adding 0.1g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, after 30 minutes, adding 2g of aminated polyester fiber, reacting for 4 hours at room temperature, and then washing with water to obtain the intelligent polyester composite fiber.
Wherein the particle diameter of the poly (N, N-dimethylaminoethyl methacrylate-styrene) particles containing epoxy groups is 200nm, and the diameter of the aminated polyester fiber is 10 μm.
In examples 4 to 6, the preparation of the polyester fibers containing amino groups is described in the literature: research on cotton-like hydrophilic finishing process of novel modified polyester fiber, ShishuWen, Shanghai engineering technology university, 2014-02-01, Master thesis.
Example 5
Dispersing 2g of poly (N-isopropylacrylamide-methacrylic acid) particles into 500mL of heptane, adding 2g of polyester fiber containing amino groups, reacting at 80 ℃ for 4 hours, taking out, and washing with acetone and water to obtain the intelligent polyester composite fiber.
Wherein the particle diameter of the poly (N-isopropylacrylamide-methacrylic acid) particles is 200nm, and the diameter of the polyester fibers containing amino groups is 400 nm.
Example 6
0.1g of poly (N-isopropylacrylamide-acrylic acid) composite particles are dispersed in 500mL of water containing 1mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 2g of polyester fiber fabric containing amino groups and 0.1mg of N-hydroxythiosuccinimide are added after 1 hour, the mixture is reacted for 12 hours at 60 ℃, and then the mixture is taken out and washed with ethanol, acetone and water to obtain the intelligent polyester composite fiber.
Wherein the particle diameter of the poly (N-isopropylacrylamide-acrylic acid) particles is 200nm, and the diameter of the polyester fiber containing amino groups is 400 nm.
Example 7
20mg of polyacrylamide particles are dispersed in water, the pH value is adjusted to 3.5 by HCl solution, the reaction is carried out for 2 days at room temperature, then the particles are washed and separated, then the particles are dispersed in 50ml of water, 0.005g of N, N' -diisopropylcarbodiimide is added, then 0.5 g of functionalized polyester fiber containing amino groups is added, the reaction is carried out for 4 hours at room temperature, and then the reaction is washed by water, thus obtaining the intelligent polyester composite fiber.
Wherein the particle diameter of the polyacrylamide particles is 500nm, and the diameter of the polyester fiber containing amino groups is 10 μm.
Example 8
1g of polystyrene/poly (N-isopropylacrylamide-methacrylic acid) composite particles are dispersed in 500mL of heptane, 2g of polyester fiber fabric containing epoxy groups is added, the reaction is carried out at 60 ℃ for 1 hour, and then the mixture is taken out and washed with heptane, ethanol and water, so as to obtain the intelligent polyester composite fiber.
Wherein the particle diameter of the polystyrene/poly (N-isopropylacrylamide-methacrylic acid) composite particles is 1.8 mu m, and the diameter of the polyester fiber containing epoxy groups is 100 mu m.
In example 8, polyester fibers containing epoxy groups were prepared as described in the literature: the study on modified terylene with epoxy compound is disclosed in Jianming et al, journal of textile 1990, 11 (5), 210-.
Example 9
Dispersing 0.1g of silicon dioxide/poly (N-isopropylacrylamide-styrene) hybrid particles into 20mL of toluene, adding chloropropyltrimethoxysilane, reacting for 6 hours at room temperature, separating, drying, adding into 200mL of heptane solution containing 20 g of hydroxyl-functionalized polyester fiber, reacting for 6 hours at 40 ℃, taking out, and washing with toluene, ethanol and water to obtain the intelligent polyester composite fiber.
Wherein the particle diameter of the silicon dioxide/poly (N-isopropylacrylamide-styrene) hybrid particles is 300nm, and the diameter of the hydroxyl-functionalized polyester fiber is 20 μm.
In examples 9-10, the hydroxyl functionalized polyester fiber fabric was prepared as follows: research progress in the synthesis of hydroxyl-functionalized polyesters, Oldham's, et al, Chinese plastics, 2012, 26(11), 1-7.
Example 10
0.1g of epoxy group-containing poly (styrene-methyl methacrylate-butadiene) copolymer particles were dispersed in 100mL of octane, 20 g of hydroxyl group-containing polyester fiber was added, reacted at 80 ℃ for 6 hours, and then taken out and washed with ethanol and water to obtain a particle-bonded polyester composite fiber.
Wherein the particle diameter of the poly (styrene-methyl methacrylate-butadiene) copolymer particles containing epoxy groups is 90nm, and the diameter of the polyester fiber fabric containing hydroxyl groups is 100 μm.
Comparative example
Comparative example 1
The procedure of example 1 was repeated except that: only the PET polyester fiber containing hydroxyl groups is prepared, and the later compounding of the poly (N-isopropylacrylamide) particles containing epoxy groups is not carried out.
Comparative example 2
The procedure of example 5 was repeated except that: only the polyester fiber containing amino groups was prepared without post-compounding of poly (N-isopropylacrylamide-methacrylic acid) particles.
Comparative example 3
The procedure of example 9 was repeated except that: only hydroxyl-functionalized polyester fibers were prepared without compounding of the particles.
Examples of the experiments
Experimental example 1 Transmission Electron microscopy test
The transmission electron microscope test of the sample obtained in example 1 shows the results in fig. 1-2, wherein fig. 2 is a partial enlarged view of fig. 1, and as is apparent from fig. 1-2, the surface of the polyester fiber matrix is covered with the particle protrusions.
EXAMPLE 2 contact Angle test
(1) The polyester composite fiber obtained in example 3 was subjected to water contact angle tests at room temperature (about 25 ℃) and 40 degrees, respectively, and the results are shown in fig. 3 and 4, respectively.
As can be seen from FIG. 3, the water contact angle of the fiber at room temperature is close to 0 degrees, and the fiber has super-hydrophilic property;
as can be seen from fig. 4, the fiber has a water contact angle of 100 ° at 40 ℃, showing hydrophobicity;
thus, at different temperatures, the fibers have a "hydrophilic-hydrophobic" transition;
(2) the water contact angle and the oil contact angle of example 5 were measured at 40 ℃ and the results are shown in fig. 5 and 6, respectively.
As can be seen from fig. 5, the fiber has a water contact angle of approximately 100 degrees at 40 ℃, and exhibits hydrophobic properties;
as can be seen from fig. 6, the fiber has an oil contact angle of 0 degree at 40 ℃, showing oleophilic properties;
thus, at 40 ℃, the fibers have "hydrophobic-lipophilic".
In combination with (1) and (2), it is found that the obtained polyester composite fiber has temperature responsiveness, and the temperature can be switched between "hydrophilic-oleophobic property" and "hydrophobic-lipophilic property" as its hydrophilic-hydrophobic switch.
Experimental example 3 oil-water separation test
The fiber obtained in example 9 was subjected to an oil-water separation test at room temperature (about 30 ℃ C.), wherein decane was used as the oil. The test is schematically shown in fig. 7 to 8, and in fig. 7 to 8, the composite fiber obtained in example 9 was provided at the fork of the flow dividing head.
(1) As shown in fig. 7, the water at the initial stage of separation is on the lower side, and therefore, the water first flows down from the separatory funnel and drops onto the polyester composite fiber 1, but the water drops do not fall through the polyester fiber 1 but fall along the right side of the flow dividing head to the right beaker (in fig. 7, the arrow indicates the flow direction of the oil);
the reason for the analysis is that the polyester fiber 1 exhibits "hydrophobic" characteristics, and therefore, water droplets do not permeate the polyester fiber 1, but fall only from the right side of the flow dividing head.
(2) As shown in fig. 8, when the water drops on the lower side, the oil drops fall, and it can be seen that the oil drops wet the polyester fiber 1 and fall vertically into the left beaker (in fig. 8, the arrow indicates the flow direction of the oil);
the reason for the analysis is that at room temperature, the polyester fiber 1 exhibits "oleophilic" properties, so that water droplets can infiltrate the polyester fiber 1 and fall down into the left beaker at the orifice in the vertical direction of the dividing head.
Therefore, in this experimental example, it can be seen that the polyester composite fiber described herein has oil-water separation performance, and can separate oil from water.
This experimental example demonstrates the functionality of the fibers according to the invention, wherein the particles used are hybrid silica/poly (N-isopropylacrylamide-styrene) particles, wherein, although N-isopropylacrylamide has a hydrophilic character below its LCST, the styrene blocks influence its hydrophilic character and impart hydrophobic and lipophilic properties to the bulk material.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made in the technical solution of the present invention and the embodiments thereof without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is to be determined by the appended claims.

Claims (10)

1. A polyester composite fiber having a smart surface, comprising a polyester fiber matrix and particles bonded thereto.
2. The polyester composite fiber according to claim 1, wherein the particles are bonded to the polyester fiber matrix by a chemical bond, preferably by an ester bond, an amide bond, an ether bond, a C ═ N bond, an N — N bond, a C — C bond, a C ═ C bond, an S-S bond, a C — S bond, and/or an S — O bond, preferably by an ester bond, an amide bond, an ether bond, a C ═ N bond, an S — S bond, and/or a C — S bond, more preferably by an ester bond, an amide bond, and/or an ether bond.
3. The polyester composite fiber according to claim 1 or 2,
the polyester fiber matrix is selected from a polyethylene terephthalate (PET) fiber matrix, a polybutylene terephthalate (PBT) fiber matrix, a polyarylate fiber matrix, a polybutylene succinate (PBS) fiber matrix, Polyhydroxybutyrate (PHB), a polybutylene fumarate (PBF) fiber matrix, a polyadipate fiber matrix, a polycaprolactone fiber matrix and/or a polycarbonate fiber matrix, and optionally other polymers or inorganic fillers are compounded in the polyester fiber matrix, preferably, the inorganic fillers are selected from one or more of silicon dioxide, titanium dioxide, ferric oxide, ferroferric oxide, barium sulfate, tungsten trioxide, carbon black and calcium carbonate, such as silicon dioxide and titanium dioxide; and/or
The surface of the polyester fiber substrate is modified with a reactive group, preferably, the surface of the polyester fiber substrate is modified with one or more of hydroxyl, carboxyl, amino, double bond, sulfydryl, amido, epoxy, chlorine group and bromine group, and more preferably, the surface of the polyester fiber substrate is modified with one or more of hydroxyl, amino, carboxyl and double bond.
4. The polyester composite fiber according to any one of claims 1 to 3,
the particles are selected from polymer particles and/or inorganic particles, preferably the particles are selected from polymer particles, optionally doped with inorganic materials, more preferably the inorganic materials are selected from one or more of silica, titanium dioxide, ferric oxide, ferroferric oxide, barium sulfate, tungsten trioxide, carbon black and calcium carbonate, such as silica and/or titanium dioxide; and/or
The polymer in the polymer particles is a polymer modified with a reactive group, preferably a polymer modified with one or more of a hydroxyl group, a carboxyl group, an amino group, a double bond, a sulfhydryl group, an amido group, an epoxy group and a chlorine group, and more preferably an environment-responsive polymer modified with one or more of a hydroxyl group, a carboxyl group, a sulfhydryl group and an epoxy group, such as a carboxyl group, an amino group and an epoxy group.
5. The polyester composite fiber according to one of claims 1 to 4, wherein the environment-responsive polymer is selected from the group consisting of a temperature-responsive polymer, a pH-responsive polymer, a humidity-responsive polymer, a solvent-responsive polymer, CO2One or more of responsive polymer, ion responsive polymer and light responsive polymer, preferably, the environment responsive polymer is selected from homopolymer shown in formulas (1) to (3) and/or copolymer containing polymer chain segment shown in formulas (1) to (3);
wherein,
in formula (1): r1、R2And R3Each independently selected from hydrogen or C1～C6Preferably selected from hydrogen or C1～C3More preferably selected from hydrogen, methyl, ethyl or isopropyl;
in the formula (2), R4Selected from hydrogen or C1～C6Preferably selected from hydrogen or C1～C3More preferably selected from hydrogen or methyl;
in the formula (3), R5、R6And R7Each independently selected from hydrogen or C1～C6Preferably selected from hydrogen or C1～C3More preferably selected from hydrogen or methyl, for example methyl;
in formulae (1) to (3), 20> m.gtoreq.0, preferably 10> m.gtoreq.0, and more preferably m is 0.
6. The polyester composite fiber according to one of claims 1 to 5, wherein the environmentally responsive polymer is selected from homopolymers and/or copolymers containing poly (N-isopropylacrylamide) (PNIPAM) segments, poly (N-isopropylacrylamide) (PNIPMAM) segments, poly (N, N-diethylacrylamide) (PDEA), poly (N-ethylacrylamide) (PEMA) segments, poly (N, N-dimethylaminoethyl methacrylate) (PDMAEMA) segments, polyvinylpyridine, polyacrylic acid (PAA) segments and/or polymethacrylic acid (PMAA) segments;
preferably, the environmentally responsive polymer is selected from homopolymers and/or copolymers containing poly (N-isopropylacrylamide) (PNIPAM) segments, poly (N, N-dimethylaminoethyl methacrylate) (PDMAEMA) segments and/or polyacrylic acid (PAA) segments;
more preferably, the environmentally responsive polymer is selected from homopolymers and/or copolymers containing poly (N-isopropylacrylamide) (PNIPAM) segments and/or poly (N, N-dimethylaminoethyl methacrylate) (PDMAEMA) segments.
7. The polyester composite fiber according to any one of claims 1 to 6,
the diameter of the polyester fiber matrix is 5 nm-1 mm, preferably 100 nm-200 μm, more preferably 400 nm-100 μm, such as 5-100 μm; and/or
The particle size of the particles is 1 nm-500 μm, preferably 20 nm-10 μm, more preferably 100 nm-5 μm; and/or
The ratio of the particle size of the particles to the diameter of the fiber matrix is 1 (2-10000), preferably 1 (4-1000), and more preferably 1 (20-100).
8. A method for preparing the polyester composite fiber with the intelligent surface according to claims 1 to 7, wherein the method comprises the following steps:
step 1, obtaining a polyester fiber matrix with a reactive group on the surface;
step 2, obtaining particles with reactive groups;
and 3, adding the particles obtained in the step 2 into a solvent, adding the polyester fiber matrix obtained in the step 1 into the solvent, reacting, and performing post-treatment to obtain the polyester composite fiber with the intelligent surface.
9. The method according to claim 8,
in step 1, the polyester fiber substrate with the surface having the reactive group can be purchased directly or through surface functionalization treatment; preferably, performing surface functionalization treatment on the polyester fiber substrate by adopting plasma irradiation, chemical corrosion, ultraviolet graft polymerization or surface chemical modification to obtain the polyester fiber substrate with reactive groups on the surface; and/or
In step 2, the particles are preferably polymeric particles, optionally doped with an inorganic material, such as titanium dioxide or silicon dioxide; and/or
In step 3:
the solvent is a poor solvent of a polyester fiber matrix and particles; and/or
Optionally adding a catalyst in the reaction, preferably, the catalyst is selected from one or more of compounds shown in formulas (a) to (d), acid (for example, a compound shown in formula e), acid salt, alkali, lithium aluminum hydride, azodiisobutyronitrile and benzoin dimethyl ether;AlR′4、LiR′3、R'6-N＝C＝N-R′5
the formula (a), the formula (b), the formula (c), the formula (d) and the formula (e)
Wherein R'1Selected from hydroxyl, hydroxyl containing alkyl chain, phenyl, amido, bromine radical, maleic succinimidylAminobutyric acid, acryloxy group, or a group represented by the formula (f),
R'2selected from H, carboxyl containing alkyl chain, sulfonic acid group or sulfonate (such as sodium sulfonate); r'3And R'4Each independently selected from alkyl, alkoxy or aryl;
R'5and R'6Each independently selected from methyl, ethyl, isopropyl, N-cyclohexyl, 1, 3-di-p-tolyl, 1- (3-dimethylaminopropyl) -3-ethyl or a group of formula (g),
in formula (g), n is 2 to 8, preferably 2 to 5.
10. Use of the polyester composite fiber with intelligent surface of claims 1 to 7 or the polyester composite fiber with intelligent surface obtained by the preparation method of claims 8 to 9, wherein the polyester composite fiber is preferably functional or intelligent; can be used for intelligent textiles, non-woven fabrics, porous membranes, composite materials and oil-water separators, and is preferably used for the intelligent textiles and the oil-water separators.
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CN110004710B (en) * 2019-03-26 2020-04-28 华南理工大学 Super-hydrophilic underwater super-oleophobic and super-oleophilic oil super-hydrophobic fabric and preparation method and application thereof
CN109999570A (en) * 2019-04-13 2019-07-12 瑞德纳米科技（广州）有限公司 A kind of preparation method of air filting material
CN109999570B (en) * 2019-04-13 2021-11-26 山东奥博环保科技有限公司 Preparation method of air filtering material
CN110237727A (en) * 2019-06-19 2019-09-17 中国科学技术大学 A kind of preparation method of super-hydrophobic seperation film
CN112195530B (en) * 2019-07-08 2023-01-31 财团法人纺织产业综合研究所 Temperature response material, temperature response fiber and preparation method thereof
CN112195530A (en) * 2019-07-08 2021-01-08 财团法人纺织产业综合研究所 Temperature response material, temperature response fiber and preparation method thereof
US11739445B2 (en) 2019-07-08 2023-08-29 Taiwan Textile Research Institute Temperature-responsive material, temperature-responsive fiber and preparation method thereof
TWI753274B (en) * 2019-07-08 2022-01-21 財團法人紡織產業綜合研究所 Temperature-responsive material, temperature-responsive fiber and preparation method thereof
CN112831158A (en) * 2019-11-25 2021-05-25 北京服装学院 Conductive hybrid particle/polyester composite material, fiber and fabric thereof
CN112831178A (en) * 2019-11-25 2021-05-25 北京服装学院 Conductive hybrid particle/polyamide composite material, fiber and fabric thereof
CN114668893A (en) * 2022-03-11 2022-06-28 华南理工大学 Method for preparing nerve repair material in high flux based on surface patterning experimental platform
CN117626534A (en) * 2024-01-26 2024-03-01 东华大学 Solvent response color-changing piezoelectric material and preparation method and application thereof
CN117626534B (en) * 2024-01-26 2024-05-14 东华大学 Solvent response color-changing piezoelectric material and preparation method and application thereof

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Application publication date: 20190226