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

Abstract

The invention discloses a polyester composite fiber with an intelligent surface and a preparation method and application thereof. The polyester composite fiber comprises a polyester fiber matrix and particles covering it, wherein the particles and the polyester fiber matrix are formed between the particles and the polyester fiber matrix. chemical bonds; preferably, the particles are polymer particles, more preferably polymer particles with environmental response, so that covering the particles on the surface of the fiber matrix can not only improve the hydrophilicity and hydrophobicity of the fibers, but also impart a certain environment to the fibers Responsiveness. The preparation is carried out as follows: firstly obtaining a polyester fiber matrix with reactive groups on the surface, then obtaining particles with reactive functional groups, and finally mixing the polyester fiber matrix and the particles for reaction to obtain the polyester composite fiber. The polyester composite fibers of the present invention can be used in smart textiles, non-woven fabrics, porous membranes, composite materials and oil-water separators, and are preferably used in smart textiles and oil-water separators.

Description

A kind of polyester composite fiber with smart surface and its preparation method and application

technical field

The invention belongs to the field of fiber materials, in particular to polyester fibers, and in particular to a polyester composite fiber with an intelligent surface and a preparation method and application thereof.

Background technique

Polyester is a general term for polymer compounds containing ester bonds on the main chain, and is generally formed by condensation polymerization of dibasic acid and dihydric alcohol. Polyester fiber materials are widely used in various fields such as fabrics, filter materials, and catalysis. However, traditional polyester fibers generally have smooth and uniform surface properties, so so far their applications are mainly determined by the properties of the fiber body. The change of the hydrophilic and hydrophobic properties of the fiber surface seriously affects its performance, and the hydrophilicity and hydrophobicity of the material can be improved by changing the roughness or surface energy of the material surface.

The prior art involves increasing the roughness through surface etching, thereby improving the hydrophilicity and hydrophobicity of the surface. However, the etching will reduce the mechanical properties of the material to a certain extent, thereby reducing its practicality.

In the prior art, silica particles are also used to modify the surface of the material, thereby improving the hydrophilic and hydrophobic properties of the material. However, the modification is mostly physical modification, and its performance is unstable, or even chemical modification is used. modification, its efficiency is low.

SUMMARY OF THE INVENTION

In view of the problems existing in the prior art, the present inventors have carried out keen research, using particles to modify the surface of the fiber matrix, preferably the particles are polymer particles, and are chemically bonded to the surface of the fiber, so that the obtained material performance is stable, and , the surface has a certain roughness, which effectively improves the hydrophilicity and hydrophobicity of the surface of the material. At the same time, the particles that are more preferably used are particles with environmental response, so that the obtained material surface has a certain environmental responsiveness, such as temperature response or pH response, Thus, the present invention has been completed.

One aspect of the present invention provides a polyester composite fiber with an intelligent surface, the polyester composite fiber includes a polyester fiber matrix and particles covering the polyester fiber matrix, wherein the particles and the polyester fiber matrix are chemically bonded .

Another aspect of the present invention provides the preparation method of above-mentioned polyester composite fiber, and described method comprises the following steps:

Step 1, obtaining a polyester fiber matrix with reactive groups on the surface;

Step 2, obtaining particles with reactive groups;

Step 3, adding the particles obtained in step 2 into a solvent, and then adding the polyester fiber matrix obtained in step 1 to the solvent, reacting, and then post-processing to obtain the polyester composite fiber with smart surface.

The third aspect of the present invention provides the application of the polyester composite fiber of the first aspect of the present invention or the polyester composite fiber obtained by the method of the second aspect of the present invention, wherein the polyester composite fiber can be used for smart textiles , non-woven fabrics, porous membranes, composite materials, and oil-water separators, preferably for smart textiles and oil-water separators.

Description of drawings

Fig. 1 shows the transmission electron microscope image of the fiber obtained in Example 1;

Fig. 2 shows a partial enlarged view of Fig. 1;

Figure 3 and Figure 4 show the test results of the water contact angle of the fibers obtained in Example 3 at room temperature and 40 degrees, respectively;

Fig. 5 shows the test result of the water contact angle of the fiber obtained in Example 5 at room temperature;

Fig. 6 shows the test result of the oil contact angle of the fiber obtained in Example 5 at room temperature;

Fig. 7 shows the schematic diagram of the initial test of oil-water separation using the fibers obtained in Example 9;

Figure 8 shows a schematic diagram of the later stage test of oil-water separation using the fibers obtained in Example 9.

Explanation of reference numerals

1- Polyester composite fiber.

Detailed ways

The features and advantages of the present invention will become clearer and clearer through the detailed description of the present invention below.

One aspect of the present invention provides a polyester composite fiber with an intelligent surface, wherein the polyester composite fiber includes 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, ester bonds, amide bonds, ether bonds, C=N bonds, N-N bonds, C-C bonds, C=C bonds, S-S bonds, C-S bonds are formed between the particles and the polyester fiber matrix. bond and/or S-O bond.

In a further preferred embodiment, the particles are bound to the polyester fiber matrix by ester bonds, amide bonds, ether bonds, C=N bonds, S-S bonds and/or C-S bonds.

In a further preferred embodiment, the particles are bound to the polyester fiber matrix by ester bonds, amide bonds and/or ether bonds.

Wherein, the particles and the polyester fiber matrix are bonded by chemical bonds, so that the fibers of the present invention have a very stable structure compared to simple blending or bonding by gluing.

In the present invention, the particles on the surface of the polyester composite fiber did not fall off after the polyester composite fiber was washed under ultrasonic, indicating that the particles had a strong binding effect with the polyester composite fiber matrix.

According to a preferred embodiment of the present invention, the diameter of the polyester fiber matrix is 5 nm˜1 mm.

In a further preferred embodiment, the diameter of the polyester fiber matrix is 50 nm to 50 μm.

In a further preferred embodiment, the diameter of the polyester fiber matrix is 5-50 µm, for example 20-40 µm.

The diameter of the fiber matrix is limited to 5 nm-1 mm, preferably 50 nm-50 μm, more preferably 5-50 μm, such as 20-40 μm, in order to ensure that the obtained fibers have certain strength (ie practicality).

According to a preferred embodiment of the present invention, the particle size of the particles ranges from 1 nm to 500 μm.

In a further preferred embodiment, the particle size of the particles ranges from 20 nm to 10 μm.

In a further preferred embodiment, the particle size of the particles is 100 nm to 5 μm, such as 100 to 500 nm.

Among them, the particles cover the surface of the fiber matrix to form a rough structure surface, therefore, the particle size of the particles should not be too large or too small.

According to a preferred embodiment of the present invention, the ratio of the particle size of the particles to the diameter of the fiber matrix is 1:(2-10000).

In a further preferred embodiment, the ratio of the particle size of the particles to the diameter of the fiber matrix is 1:(4-1000).

In a still further preferred embodiment, the ratio of the particle size of the particles to the diameter of the fiber matrix is 1:(20-100), for example 1:(20-60).

Wherein, the particles form a micro/nano structure on the fiber matrix, so that the surface of the fiber matrix has a certain roughness, thereby improving the hydrophilicity and hydrophobicity of the fiber.

According to a preferred embodiment of the present invention, the polyester composite fiber matrix is selected from the group consisting of polyethylene terephthalate (PET) fiber matrix, polybutylene terephthalate (PBT) fiber matrix, poly Arylate fiber matrix, polybutylene succinate (PBS) fiber matrix, polyhydroxybutyrate (PHB) fiber matrix, polybutylene fumarate (PBF) fiber matrix, polyadipic acid Ester fiber matrix, polycaprolactone fiber matrix and/or polycarbonate fiber matrix, eg polyethylene terephthalate (PET) fiber matrix.

In a further preferred embodiment, optionally, other polymers or inorganic fillers are compounded in the polyester fiber matrix.

Wherein, the other polymers are other polymers other than polyester.

In a further preferred embodiment, the inorganic filler is selected from one or more of silicon dioxide, titanium dioxide, ferric oxide, ferric oxide, barium sulfate, tungsten trioxide, carbon black and calcium carbonate , such as silicon dioxide, titanium dioxide.

Wherein, other materials can be compounded in the polyester fiber matrix, so that different functions can be imparted to the polyester fiber matrix.

According to a preferred embodiment of the present invention, reactive groups are modified on the surface of the polyester fiber matrix.

In a further preferred embodiment, one or more of hydroxyl groups, carboxyl groups, amino groups, double bonds, mercapto groups, amide groups, epoxy groups, bromine groups and chlorine groups are modified on the surface of the polyester fiber matrix. a reactive group.

In a further preferred embodiment, the surface of the polyester fiber matrix is modified with one or more reactive groups selected from hydroxyl, amino and double bonds.

Wherein, the surface of the polyester fiber matrix is modified with reactive groups, so that it can react with the particles to form ester bonds, amide bonds and/or ether bonds, etc., to realize chemical bonding.

According to a preferred embodiment of the present invention, the particles are selected from polymer particles and/or inorganic particles.

In a further preferred embodiment, the particles are selected from polymeric particles, optionally doped with inorganic materials.

In a further preferred embodiment, the inorganic material is selected from one or more of silicon dioxide, titanium dioxide, ferric oxide, ferric oxide, barium sulfate, tungsten trioxide, carbon black and calcium carbonate , such as silicon dioxide and/or titanium dioxide.

Among them, the bonding area between the inorganic material and the polyester fiber matrix is small, so it is difficult to bond, and even if the inorganic material is bonded, the inorganic material is easy to fall off. Therefore, in the present invention, the particles are preferably polymer particles, wherein The contact area between the polymer particles and the polyester fiber matrix is large, that is, a plurality of chemical bonds can be combined at the joint, thus ensuring the stability of the joint.

In the present invention, the structure of the particles is not limited, such as core-shell structure, double-partition structure, strawberry structure, dumbbell structure; self-asymmetric structure is preferred.

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 modified with one or more of hydroxyl, carboxyl, amino, double bond, mercapto, amide, epoxy and chlorine groups of polymers.

In a further preferred embodiment, the polymer in the polymer particles is an environment-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 groups in the polymer particles react with the reactive groups modified on the surface of the polyester fiber matrix, so that the two are chemically bonded. The polymer may preferably be an environmentally responsive polymer, so that, when supported on a polyester fiber matrix, it can impart environmentally responsive properties to the fiber and have environmentally responsive properties.

According to a preferred embodiment of the present invention, the environment-responsive polymer is selected from the group consisting of temperature-responsive polymers, pH-responsive polymers, humidity-responsive polymers, solvent-responsive polymers, CO ₂ -responsive polymers, One or more of ion-responsive polymers and photo-responsive polymers, for example, selected from homopolymers represented by formulas (1) to (3) and/or polymers containing formulas (1) to (3) segmented copolymers.

In a further preferred embodiment, in formula (1): R ₁ , R ₂ and R ₃ are each independently selected from hydrogen or C ₁ -C ₆ alkyl, preferably from hydrogen or C ₁ -C ₃ Alkyl; in formula (2), R ₄ is selected from hydrogen or C ₁ -C ₆ alkyl, preferably hydrogen or C ₁ -C ₃ alkyl; in formula (3), R ₅ , R ₆ and R ₇ are each independently selected from hydrogen or C ₁ -C ₆ alkyl groups, preferably hydrogen or C ₁ -C ₃ alkyl groups; in formulas (1) to (3), 20>m≥0 .

In a further preferred embodiment, in formula (1): R ₁ , R ₂ and R ₃ are each independently selected from hydrogen, methyl, ethyl or isopropyl; in formula (2), R ₄ is selected from hydrogen or methyl; in formula (3), R ₅ , R ₆ and R ₇ are each independently selected from hydrogen or methyl, such as methyl; in formula (1) to (3), 10> m≧0, eg m=0.

Among them, the polymer or polymer segment represented by formula (1) has temperature responsiveness, specifically, has LCST, in aqueous solution, when the temperature is lower than its LCST, its side chain can form hydrogen bonds with water molecules, However, when the temperature is higher than its LCST, the intermolecular hydrogen bonds are broken, and the molecular chain is twisted. Therefore, the polymer or polymer segment represented by formula (1) has temperature responsiveness. The polymer or polymer segment represented by formula (2) is pH-responsive, and the molecular chain responds 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 environment-responsive polymer is selected from the group consisting of poly(N-isopropylacrylamide) (PNIPAM) chain segments, poly(N-isopropylmethacrylamide) (PNIPAMAM) ) segment, poly(N,N-diethylacrylamide) (PDEA) segment, poly(N-ethylacrylamide) (PEMA) segment, poly(N,N-dimethylamino methacrylate) ethyl ester) (PDMAEMA) segments, polyvinylpyridine, polyacrylic acid (PAA) segments and/or polymethacrylic acid (PMAA) segments homopolymers and/or copolymers.

Among them, the use of environmentally responsive polymer particles can impart environmental responsive properties to the fibers, for example, when particles containing poly(N-isopropylacrylamide) segments are used, temperature responsiveness can be imparted to the fibers. Therefore, the fibers can be applied to smart textiles, which can adjust the temperature to meet the needs of the human body, provide a comfortable microclimate environment for the human body, and play a positive role in regulating the body temperature between the human body and the external environment. On the other hand, when the external ambient temperature is too high, the particle molecular chains on the surface of the fibers shrink to improve the breathability of the textile.

In a further preferred embodiment, the environment-responsive polymer is selected from the group consisting of poly(N-isopropylacrylamide) (PNIPAM) segments, poly(N,N-dimethylaminoethyl methacrylate) Homopolymers and/or copolymers of (PDMAEMA) segments and/or polyacrylic acid (PAA) segments.

More preferably, the environmentally responsive polymer is selected from poly(N-isopropylacrylamide) (PNIPAM) segments and/or poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) ) segments of homopolymers and/or copolymers.

In the present invention, the fibers can not only be used for the above-mentioned intelligent environmental responsive control applications, but also can be used for oil-water separation. When the fibers are hydrophobic, oil passes through the fibers and water does not pass, and oil-water separation is successfully achieved. , and the separation effect is good, the speed is fast, no other chemical additives are needed, there is no toxic side effect and secondary pollution, and it can be reused.

Specifically, (1) when the particles composited on the surface of the fibers are hydrophilic polymer particles, such as Example 1 and Example 5, the fibers are hydrophilic, and generally water will permeate the fibers and oil (2) When the particles composited on the surface of the fibers are hydrophilic polymer-hydrophobic polymer copolymer particles, it is necessary to analyze the ratio of the segments of the hydrophilic block to the hydrophobic block. Hydrophilic and hydrophobic, if the hydrophilic polymer is the main body, it will be hydrophilic, and if the hydrophobic polymer is the main body, it will be hydrophobic, and oil-water separation can also be achieved; (3) When the particles composited on the fiber surface are hydrophobic particles When , the fibers exhibit hydrophobicity, and generally oil will permeate the fibers but water will not permeate, thus realizing oil-water separation.

A second aspect of the present invention provides a method for preparing the polyester composite fiber described in the first aspect of the present invention, the method comprising the following steps:

Step 1. Obtain a polyester fiber matrix with reactive groups on the surface.

According to a preferred embodiment of the present invention, the polyester fiber matrix with reactive groups on the surface can be directly purchased, or directly prepared by polymerization or spinning, or the polyester fiber matrix can be subjected to surface functionalization treatment. , to obtain a polyester fiber matrix with reactive groups on the surface.

In a further preferred embodiment, the polyester fiber matrix is subjected to surface functionalization treatment 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 its surface is modified with reactive groups, such as one of hydroxyl, carboxyl, amino, double bond, mercapto, amide, epoxy and chlorine groups. species or several.

Step 2, obtaining particles with reactive groups.

Among them, the particles are preferably polymer particles, optionally doped with inorganic materials such as titanium dioxide, silicon dioxide, ferric oxide, ferric tetroxide, barium sulfate, tungsten trioxide, carbon black and One or more of calcium carbonate. The particles with reactive groups are directly purchased or prepared, and the preparation is carried out with reference to the documents disclosed in the prior art.

According to a preferred embodiment of the present invention, the preparation of polymer particles is carried out directly, and its own functional groups are used as reactive groups to react with the polyester fiber matrix.

For example, polyacrylic acid particles can be directly reacted with a polyester fiber matrix after preparation without further functionalization.

According to another preferred embodiment of the present invention, the polymer particles are functionalized after they are obtained.

For example, poly(N,N-dimethylaminoethyl methacrylate-styrene) particles containing benzenesulfonic acid groups, first prepare poly(N,N-dimethylaminoethyl methacrylate- styrene) particles, which are then subjected to 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, the particles containing polyvinyl alcohol or polyethylene oxide can be directly prepared, or, the particles can be prepared first A hydroxyl group-free polymer is obtained, and then functionalized to connect it with hydroxyl groups to obtain a hydroxyl-modified polymer.

In a further preferred embodiment, when the polymer in the polymer particles is a polymer modified with hydroxyl groups, for example, polyvinyl alcohol or polyethylene oxide is directly prepared.

According to a preferred embodiment of the present invention, when the polymer in the polymer particles is a polymer modified with carboxyl groups, for example, acrylate polymers can be directly prepared, or a carboxyl group-free polymer can be prepared first. The polymer is then functionalized to obtain a polymer modified with carboxyl groups.

In a further preferred embodiment, when the polymer in the polymer particles is a polymer modified with carboxyl groups, acrylate polymers can be prepared, and then functionalized to obtain carboxyl groups.

According to a preferred embodiment of the present invention, when the polymer in the polymer particles is a polymer modified with thiol groups, reference can be made to the literature (Olivia Z. Durham et al. Colloid Polym Sci, 2015, 293, 2385- 2394.).

Among them, the preparation method of the mercapto group-containing polymer is not limited to the methods disclosed in the above-mentioned documents, 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, an acrylamide-based polymer can be directly prepared, or a polymer without an amide group can be prepared first , and then functionalized to obtain a polymer modified with an amide group.

In a further preferred embodiment, the acrylamide-based polymer is prepared directly.

According to a preferred embodiment of the present invention, when the polymer in the polymer particles is a polymer modified with epoxy groups, reference can be made to the literature (Jiaojun Tan et al., RSC Adv. 2014, 4, 13334- 13339.).

Among them, the preparation method of the epoxy group-containing polymer is not limited to the methods disclosed in the above-mentioned documents, 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 chlorine groups, the preparation of polyvinyl chloride polymers can be carried out directly to obtain a polymer modified with chlorine groups. polymer.

Step 3. Add the particles obtained in step 2 into a solvent, and then add the polyester fiber matrix obtained in step 1 to the solvent, carry out a reaction, and then post-process to obtain the polyester fiber with smart surface.

According to a preferred embodiment of the present invention, in step 3, the feeding sequence can be changed.

According to a preferred embodiment of the present invention, in step 3, the solvent is a poor solvent for the polyester fiber matrix and particles.

According to a preferred embodiment of the present invention, in step 3, a catalyst is optionally added.

In a further preferred embodiment, the choice of the catalyst depends on the type of reaction between the polyester fiber matrix and the particles, for example, the catalyst is selected from acids (such as compounds of formula e) or acid salts, bases, hydrogenation One or more of lithium aluminum, azobisisobutyronitrile, benzoin dimethyl ether, and compounds represented by formula (a) to formula (d).

in:

In formula (a), R' ₁ is selected from hydroxyl group, hydroxyl group containing alkyl chain, phenyl group, amide group, bromo group, malesuccinimidobutyric acid, acryloyloxy group or the group of formula (f) _R'2 is selected from H, carboxyl group, carboxyl group containing alkyl chain or sulfonic acid group or sulfonic acid salt (such as sodium sulfonate);

In formula (c) and formula (d), _R'3 and _R'4 are each independently selected from alkyl, alkoxy or aryl;

In formula (e), _R'5 and _R'6 are each independently selected from methyl, ethyl, isopropyl, N-cyclohexyl, 1,3-di-p-tolyl, 1-(3-dimethyl aminopropyl)-3-ethyl or a group represented by formula (g), wherein, in formula (g), n=2-8, preferably n=2-5.

According to a preferred embodiment of the present invention, the post-treatment is carried out as follows: collecting the fibers, washing and optionally drying.

The third aspect of the present invention provides the application of the polyester composite fiber according to the first aspect of the present invention or the polyester composite fiber obtained in the second aspect of the present invention, wherein the polyester composite fiber can be used for smart textiles, non-woven fabrics , porous membranes, composites, and oil-water separators, preferably for smart textiles and oil-water separators.

The beneficial effects that the present invention has:

(1) The polyester composite fiber of the present invention has a special surface structure, and the surface roughness and surface chemical properties of the polyester fiber are improved by covering the particles, thereby improving the hydrophilicity and hydrophobicity of the polyester fiber;

(2) The particles on the surface of the polyester composite fiber of the present invention and the polyester fiber matrix are chemically bonded, so that the degree of bonding can be improved, so that the particles are not suitable for falling;

(3) The particles covered on the surface of the polyester composite fiber of the present invention can have environmental responsiveness, so the fiber can be given environmental responsiveness;

(4) The polyester composite fibers of the present invention can be used to prepare smart textiles. Specifically, the smart textiles can adjust the temperature to meet the needs of the human body and provide a comfortable microclimate environment for the human body. Actively regulate body temperature;

(5) The polyester composite fiber of the present invention can adjust its hydrophilicity according to the environment, thus effectively improving the antistatic performance and dyeability of polyester textiles;

(6) The polyester composite fiber of the present invention can be used in an intelligent oil-water separator. Specifically, according to different environmental responses, intelligent conversion is performed between "hydrophilic-hydrophobic". Therefore, the external environment is equivalent to a "switch" , which controls the conversion of the fibers between hydrophilic and hydrophobic.

Example

The present invention is further described below through specific examples. However, these examples are only exemplary, and do not constitute any limitation to the protection scope of the present invention.

In an example:

For the preparation of poly(N-isopropylacrylamide) particles containing epoxy groups in Example 1, see document 1 (Penghui Li et al., Colloid Surface B 2013, 101, 251-255.);

For the preparation of poly(acrylic acid-styrene) particles in Example 2, see Document 2 (Xinlong Fan, et al. Polym. Chem., 2015, 6, 703-713);

For the preparation of N,N-dimethylaminoethyl methacrylate hybrid particles containing silicon dioxide in Example 3, see document 3 (Wanzhu Zhou et al., Powder Tech. 2013, 249, 1-6.);

For the preparation of epoxy group-containing poly(N,N-dimethylaminoethyl methacrylate-styrene) particles in Example 4, see document 4 (S.Fujii et al., Langmuir 2004, 20(26) , 11329-11335.);

For the preparation of poly(N-isopropylacrylamide-methacrylic acid) particles in Example 5, see document 5 (Zhang Fuquan et al., Synthesis Technology and Application, 2009, 24(4)14-19.);

For the preparation of poly(N-isopropylacrylamide-acrylic acid) particles in Example 6, see Document 6 (Anna Burmistrova et al. J. Mater. Chem. 2010, 20, 3502-3507.);

For the preparation of polyacrylamide particles in Example 7, see document 7 (Qiang Ye et al., J.ColloidInterf.Sci.2002,253,279-284.);

For the preparation of polystyrene/poly(N-isopropylacrylamide-methacrylic acid) composite particles in Example 8, see document 8 (M.Ashraful Alam, et al.J.Appl.Sci. 2008, 8(2) , 352-357.);

For the preparation of silica/poly(N-isopropylacrylamide-styrene) hybrid particles in Example 9, see document 9 (Jing Hu, et al., Polym. Chem. 2013, 4, 3293-3299.) ;

The preparation of epoxy-group styrene-methyl methacrylate-butadiene copolymer particles of Example 10 is described in the literature (A.M. Aerdts, et al. Polymer 1997, 38(16), 4247-4252.).

Example 1

Disperse 1 g of poly(N-isopropylacrylamide) particles containing epoxy groups in 500 mL of toluene, then add 2 g of PET polyester fibers containing hydroxyl groups, react at 80 degrees for 4 hours, then take out and wash with ethanol and water , to obtain intelligent polyester composite fibers.

The particle size of the epoxy group-containing poly(N-isopropylacrylamide) particles was 250 nm, and the diameter of the hydroxyl group-containing PET polyester fiber was 6 m.

In Example 1, the hydroxyl-containing PET polyester fiber fabric was obtained as follows: PET polyester fiber was added to a sodium hydroxide solution, and the hydroxyl-containing PET polyester fiber was obtained after 1 hour of reaction.

Example 2

Disperse 1 g of poly(acrylic acid-styrene) particles in 200 mL of decane, add 2 g of PET polyester fibers containing hydroxyl groups, react at 90 degrees for 4 hours, and then separate and wash to obtain polyester composite fibers.

The particle diameter of the poly(acrylic-styrene) particles was 300 nm, and the diameter of the hydroxyl group-containing polyester fiber was 6 m.

In Example 2, the hydroxyl group-containing PET polyester fiber fabric was obtained as follows: the PET polyester fiber fabric was added to a sodium hydroxide solution, and the hydroxyl group-containing PET polyester fiber was obtained after 1 hour of reaction.

Example 3

Disperse 1 g of poly(N,N-dimethylaminoethyl methacrylate) hybrid particles containing silica into water, ultrasonically treat for 80 min, then wash and dry, disperse into anhydrous toluene, add 3-mercapto 0.05 g of propyltrimethoxysilane, reacted at room temperature for 12 hours, then washed with toluene, and dispersed these mercapto-containing silica/poly(N,N-dimethylaminoethyl methacrylate) composite particles in 200 mL In heptane, 2 grams of PET polyester fibers containing double bonds and 4 mg of benzoin dimethyl ether are added, irradiated with ultraviolet light for 4 hours, and then washed with ethanol and water to obtain polyester composite fibers.

Among them, the particle size of the silica-containing N,N-dimethylaminoethyl methacrylate hybrid particles is 5 μm, and the diameter of the polyester fiber fabric containing double bonds is 20 μm.

In Example 3, for the preparation of PET polyester fibers containing double bonds, please refer to "The Grafting Composite of Polysiloxane/Coupling-Modified Titanium Sol and Its Thin Loading on the Surface of Polyester Fibers, Doctoral Dissertation, Cao Jun, Zhejiang Sci-Tech the University".

Example 4

2g of poly(N,N-dimethylaminoethyl methacrylate-styrene) particles containing epoxy groups were dispersed in concentrated sulfuric acid, reacted for 24 hours, and then the poly(N,N-methacrylic acid methacrylate) containing carboxyl group was reacted for 24 hours. N-dimethylaminoethyl ester-p-styrene) particles were dispersed in 200 ml of water, 0.1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added, and after 30 minutes, 2 grams of aminated polyester fibers were added, reacted at room temperature for 4 hours, and then washed with water to obtain smart polyester composite fibers.

The particle size of the epoxy group-containing poly(N,N-dimethylaminoethyl methacrylate-styrene) particles was 200 nm, and the diameter of the aminated polyester fiber was 10 μm.

In Examples 4-6, the preparation of polyester fibers containing amino groups is referred to in the literature: Research on the Hydrophilic Finishing Process of New Modified Polyester Fibers Like Cotton, Shi Shuwen, Shanghai University of Engineering Technology, 2014-02-01, Master's thesis.

Example 5

Disperse 2 g of poly(N-isopropylacrylamide-methacrylic acid) particles in 500 mL of heptane, add 2 g of polyester fibers containing amino groups, react at 80 degrees for 4 hours, then take out and wash with acetone and water , to obtain intelligent polyester composite fibers.

Among them, the particle size of the poly(N-isopropylacrylamide-methacrylic acid) particles was 200 nm, and the diameter of the polyester fiber containing amino groups was 400 nm.

Example 6

Disperse 0.1 g of poly(N-isopropylacrylamide-acrylic acid) composite particles in 500 mL of water containing 1 mg of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, and after 1 hour Add 2 grams of polyester fiber fabric containing amino groups and 0.1 mg of N-hydroxythiosuccinimide, react at 60 degrees for 12 hours, then take out and wash with ethanol, acetone and water to obtain smart polyester composite fibers.

Among them, the particle diameter of the poly(N-isopropylacrylamide-acrylic acid) particles is 200 nm, and the diameter of the polyester fiber containing amino groups is 400 nm.

Example 7

Disperse 20mg of polyacrylamide particles in water, adjust the pH value to 3.5 with HCl solution, react at room temperature for 2 days, then wash and separate, then disperse these particles in 50ml of water, add N,N'-diisopropylcarbodiimide 0.005 g of amine, and then 0.5 g of functionalized polyester fiber containing amino group was added, reacted at room temperature for 4 hours, and then washed with water to obtain intelligent polyester composite fiber.

Among them, the particle size of the polyacrylamide particles was 500 nm, and the diameter of the amino group-containing polyester fibers was 10 m.

Example 8

Disperse 1 g of polystyrene/poly(N-isopropylacrylamide-methacrylic acid) composite particles in 500 mL of heptane, add 2 g of polyester fiber fabric containing epoxy groups, react at 60 degrees for 1 hour, and then Take out and wash with heptane, ethanol and water to obtain intelligent polyester composite fibers.

The diameter of the polystyrene/poly(N-isopropylacrylamide-methacrylic acid) composite particles was 1.8 m, and the diameter of the polyester fibers containing epoxy groups was 100 m.

In Example 8, the preparation of epoxy group-containing polyester fibers can be found in the literature: Research on Epoxy Compound Modified Polyester, Yu Jianming et al., Textile Journal 1990, 11 (5), 210-214.

Example 9

Disperse 0.1 g of silica/poly(N-isopropylacrylamide-styrene) hybrid particles in 20 mL of toluene, add chloropropyltrimethoxysilane, and react at room temperature for 6 hours. 20 grams of hydroxyl-functionalized polyester fibers in 200 mL of heptane solution were reacted at 40 degrees for 6 hours, then taken out and washed with toluene, ethanol and water to obtain smart polyester composite fibers.

The particle size of the silica/poly(N-isopropylacrylamide-styrene) hybrid particles is 300 nm, and the diameter of the hydroxyl-functionalized polyester fiber is 20 m.

In Examples 9-10, for the preparation of the hydroxyl-functionalized polyester fiber fabric, please refer to: Research Progress in Synthesis of Hydroxyl-functionalized Polyester, Lu Baoping et al., China Plastics, 2012, 26(11), 1-7.

Example 10

Disperse 0.1 g of epoxy group-containing poly(styrene-methyl methacrylate-butadiene) copolymer particles in 100 mL of octane, add 20 g of hydroxyl-containing polyester fiber, and react at 80 degrees for 6 hours. Then, it is taken out and washed with ethanol and water to obtain a polyester composite fiber with bound particles.

Among them, the particle size of the epoxy group-containing poly(styrene-methyl methacrylate-butadiene) copolymer particles is 90 nm, and the diameter of the hydroxyl group-containing polyester fiber fabric is 100 μm.

Comparative ratio

Comparative Example 1

The procedure of Example 1 was repeated, with the difference that only hydroxyl-containing PET polyester fibers were prepared, and no later compounding of epoxy group-containing poly(N-isopropylacrylamide) particles was performed.

Comparative Example 2

The procedure of Example 5 was repeated, with the difference that only polyester fibers containing amino groups were prepared without post-compounding of the 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.

Experimental example

Experimental Example 1 Transmission electron microscope test

The samples obtained in Example 1 were tested by transmission electron microscopy, and the results are shown in Figures 1 to 2, wherein Figure 2 is a partial enlarged view of Figure 1. It can be clearly seen from Figures 1 to 2 that in the polymer The surface of the ester fiber matrix is covered with particle protrusions.

Experimental Example 2 Contact Angle Test

(1) The polyester composite fiber obtained in Example 3 was tested for water contact angle at room temperature (about 25°C) and 40 degrees, and the results are shown in Figure 3 and Figure 4, respectively.

It can be seen from Figure 3 that the water contact angle of the fiber at room temperature is close to 0°, which is super hydrophilic;

It can be seen from Figure 4 that the water contact angle of the fiber at 40°C is 100°, which is hydrophobic;

Therefore, at different temperatures, the fibers have a "hydrophilic-hydrophobic" transition;

(2) The water contact angle and the oil contact angle were tested for Example 5 at 40°C, and the results are shown in Figure 5 and Figure 6, respectively.

It can be seen from Fig. 5 that the water contact angle of the fibers at 40°C is close to 100 degrees, showing hydrophobic properties;

It can be seen from Figure 6 that the oil contact angle of the fiber at 40°C is 0 degrees, which shows lipophilic performance;

Therefore, at 40°C, the fibers are "hydrophobic-lipophilic".

Combining the above (1) and (2), it can be seen that the obtained polyester composite fiber has temperature responsiveness, and temperature can be used as its hydrophilic-hydrophobic switch to switch between "hydrophilic-oleophobic" and "hydrophobic-oleophilic" .

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 the oil was decane. Schematic diagrams of the tests are shown in FIGS. 7 to 8 . In FIGS. 7 to 8 , the conjugate fibers obtained in Example 9 were provided at the fork of the split head.

(1) As shown in FIG. 7 , the water is on the lower side at the initial stage of separation. Therefore, the water first flows down from the separatory funnel and drips onto the polyester composite fibers 1. However, the water droplets do not fall through the polyester fibers 1, but flow along the The right side of the split head drops to the right beaker (in Figure 7, the arrows indicate the direction of oil flow);

The reason for analysis is that the polyester fiber 1 exhibits "hydrophobic" properties, so that the water droplets do not penetrate the polyester fiber 1, but only fall from the right side of the diverter head.

(2) As shown in Fig. 8, after the water droplets on the lower side are finished, the oil droplets fall down, and it can be seen that the oil droplets infiltrate the polyester fiber 1 and fall vertically into the beaker on the left (in Fig. 8, the arrows indicate the flow of oil) direction);

The reason for the analysis is that the polyester fiber 1 exhibits "lipophilic" properties at room temperature, so water droplets can soak the polyester fiber 1 and fall into the beaker on the left from the vertical opening of the split head.

Therefore, in this experimental example, it can be seen that the polyester composite fiber described in the present application has oil-water separation performance, and can separate oil and water.

Among them, this experimental example shows that the fibers of the present invention have functionality, wherein the particles used are silica/poly(N-isopropylacrylamide-styrene) hybrid particles, wherein although N-isopropyl Acrylamide is hydrophilic below its LCST, however, the styrene block affects its hydrophilicity to impart hydrophobicity and lipophilicity to the bulk material.

The present invention has been described in detail above in conjunction with specific embodiments and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, various equivalent replacements, modifications or improvements can be made to the technical solutions of the present invention and the embodiments thereof, which all fall within the scope of the present invention. The protection scope of the present invention is subject to 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.