阅读说明：本技术 一种抗静电低温远红外聚酯纤维的制备方法 (Preparation method of antistatic low-temperature far infrared polyester fiber ) 是由 孙妍妍 池玉玲 徐伟成 于 2020-06-10 设计创作，主要内容包括：本发明提供了一种抗静电低温远红外聚酯纤维的制备方法,涉及功能性纺织材料技术领域,包括以下制备步骤：(1)将石墨烯置于乙二醇中,随后经剪切搅拌、超声分散交替联用处理后,制备得到分散均匀的石墨烯浆料；(2)将石墨烯浆料与对苯二甲酸和聚合催化剂投入反应釜中进行打浆,随后进行酯化、缩聚反应,出料后在水下切片,制备得到石墨烯改性聚酯切片；(3)采用熔融纺丝工艺,将石墨烯改性聚酯切片经挤出纺丝、拉伸,制备得到抗静电低温远红外聚酯纤维；本发明将石墨烯与聚酯进行复合后,可以赋予聚酯抗静电、低温远红外性能,将石墨烯改性聚酯进行切片,熔融纺丝之后,制备得到具有抗静电性、低温远红外性能,且力学性能高的聚酯纤维。(The invention provides a preparation method of antistatic low-temperature far infrared polyester fiber, relating to the technical field of functional textile materials and comprising the following preparation steps: (1) placing graphene in ethylene glycol, and then carrying out shearing stirring and ultrasonic dispersion alternating combination treatment to prepare uniformly dispersed graphene slurry; (2) putting the graphene slurry, terephthalic acid and a polymerization catalyst into a reaction kettle for pulping, then carrying out esterification and polycondensation reactions, discharging, and slicing under water to obtain graphene modified polyester slices; (3) the preparation method comprises the following steps of (1) preparing the antistatic low-temperature far infrared polyester fiber by adopting a melt spinning process and carrying out extrusion spinning and stretching on the graphene modified polyester chip; according to the invention, after graphene and polyester are compounded, antistatic and low-temperature far infrared properties can be endowed to the polyester, and after the graphene modified polyester is sliced and melt-spun, the polyester fiber with antistatic properties, low-temperature far infrared properties and high mechanical properties is prepared.)

1. The preparation method of the antistatic low-temperature far infrared polyester fiber is characterized by comprising the following preparation steps of:

(1) placing graphene in ethylene glycol, and then carrying out shearing stirring and ultrasonic dispersion alternating combination treatment to prepare uniformly dispersed graphene slurry;

(2) putting the graphene slurry, terephthalic acid and a polymerization catalyst into a reaction kettle for pulping, then carrying out esterification and polycondensation reactions, discharging, and slicing under water to obtain graphene modified polyester slices;

(3) the antistatic low-temperature far infrared polyester fiber is prepared by adopting a melt spinning process and carrying out extrusion spinning and stretching on the graphene modified polyester chip.

2. The method for preparing antistatic low-temperature far-infrared polyester fiber as claimed in claim 1, wherein the stirring speed of the shearing stirring in step (1) is 1000-3000rpm for 1-1.5 h; the ultrasonic dispersion power is 1000-3000W, and the time is 1-1.5 h; the number of the alternate combined treatment is 1-3; the concentration of the graphene slurry is 0.4-0.6 wt%.

3. The method for preparing antistatic low-temperature far-infrared polyester fiber according to claim 1, wherein the feeding molar ratio of the ethylene glycol to the terephthalic acid in the step (2) is 1.2-1.6: 1; the polymerization catalyst is a titanium-silicon composite catalyst, and the dosage of the polymerization catalyst is 2-6ppm of the theoretical discharge amount of the polyester.

4. The method for preparing antistatic low-temperature far-infrared polyester fiber as claimed in claim 1, wherein the esterification reaction condition in the step (2) is that the reaction is continued for 2-3h at 240-260 ℃ and 0.2-0.4 Mpa; the polycondensation reaction condition is that the reaction is continued for 1.5 to 3.5 hours at the temperature of 260 ℃ and 280 ℃ and under the pressure of 30 to 1000 Pa.

5. The preparation method of the antistatic low-temperature far-infrared polyester fiber according to claim 1, wherein the graphene is functionalized modified graphene, and comprises the following preparation steps:

s1: placing graphene oxide in an ethanol aqueous solution, adding a diamine functional reagent after shearing stirring and ultrasonic dispersion alternative combination treatment, and uniformly stirring to prepare a dispersion liquid;

s2: placing a condensation coupling agent in a solvent to prepare a coupling agent solution;

s3: mixing the dispersion liquid and the coupling agent solution, stirring and refluxing for 2-8h at 25-80 ℃, and cooling to room temperature to prepare suspension;

s4: and (3) carrying out suction filtration and washing on the suspension, and carrying out vacuum drying for 12-24h at the temperature of 50-60 ℃ to prepare the functionalized graphene.

6. The method of claim 5, wherein the diamine-based functionalizing agent in step S1 includes one or more of ethylenediamine, butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, and p-phenylenediamine; in step S2, the condensation coupling agent includes one or two of O- (7-azabenzotriazole-1-yl) -N, N '-tetramethyluronium hexafluorophosphate or benzotriazol-N, N' -tetramethyluronium hexafluorophosphate, the solvent is one or two of acetone or acetonitrile, and the concentration of the coupling agent solution is: 0.05-0.3 g/mL.

7. The preparation method of the antistatic low-temperature far infrared polyester fiber as claimed in claim 5, wherein the preparation process comprises the following components in parts by weight: 20-25 parts of graphene oxide, 0.5-10 parts of diamine functional reagent and 0.5-3 parts of condensation coupling agent.

8. The preparation method of the antistatic low-temperature far-infrared polyester fiber according to claim 5, wherein the functionalized graphene is further subjected to intercalation modification treatment:

a: putting the functionalized graphene into deionized water, and performing ultrasonic treatment to obtain a functionalized graphene suspension;

b: adding polymethacrylic acid into the functionalized graphene suspension, and stirring and dissolving to obtain a mixed solution;

c: gradually heating the mixed solution to 75-80 ℃, then stirring at a high speed for 1-2h by using an emulsification homogenizer under a heat preservation state, and then reducing the speed to a low speed for continuously stirring for 0.5-1h to prepare a suspension A;

d: gradually cooling the suspension A to room temperature, standing for 1-2h, and then carrying out ultrasonic stripping for 2-2.5h at 40-45 ℃ under 3000-;

e: and carrying out suction filtration and washing on the dispersion liquid B, and carrying out freeze drying at-45 to-50 ℃ for 12-24h to prepare the functionalized graphene for further intercalation.

9. The preparation method of the antistatic low-temperature far infrared polyester fiber according to claim 8, wherein the preparation process comprises the following components in parts by weight: 20-25 parts of functionalized graphene, 1000 parts of deionized water and 1200 parts of polymethacrylic acid; the molecular weight of the polymethacrylic acid is 3000-6000.

10. The method for preparing antistatic low-temperature far-infrared polyester fiber as claimed in claim 8, wherein the stirring speed during the high-speed stirring treatment in step C is 2000-2500 rpm; the stirring rate was 300-.

Technical Field

The invention relates to the technical field of functional textile materials, in particular to a preparation method of antistatic low-temperature far infrared polyester fibers.

Background

Polyethylene terephthalate (PET) is a thermoplastic polyester material with the largest global productivity and the widest application. Because of good mechanical property, thermal property, chemical property and economy, PET has the highest neutral-price ratio in all polymer materials, and therefore, PET is widely applied to the fields of fibers, packaging bottles, films, engineering plastics and the like. PET has excellent fiberizability and is the dominant product in chemical fibers. The PET is modified, so that differentiation and functionalization of fiber products can be realized, and the additional value of the fiber products is increased.

The antistatic far infrared functional polyester fiber has good antistatic performance, and is widely applied to the fields of electrostatic shielding protective clothing, conductive clothing, dustproof clothing, conductive ropes and the like. In addition, the far infrared functional fiber also has excellent heat preservation, health care, antibacterial and other effects, and the far infrared has good thermal effect due to the resonance with water molecules and organic matters, so that the far infrared textile has good heat retention; the far infrared ray can also promote the temperature rise of subcutaneous deep skin, promote blood circulation, improve the microcirculation system of human body and promote the metabolism of human body.

At present, the antistatic far infrared polyester fiber is mainly prepared by a method of adding an inorganic antistatic agent and nano ceramic powder into a conventional polyester chip. However, both the inorganic antistatic agent and the ceramic powder are essentially nano-scale inorganic particles with very high surface energy, so that agglomeration is easy to occur in a polyester melt to form large-sized agglomerated particles, thereby affecting the spinning filterability and spinnability of the chips. In addition, the compatibility of the inorganic powder and a polyester system is poor, so that the dispersibility of the antistatic agent and the ceramic powder in the polyester is poor, broken filaments and broken filaments can occur during spinning, and even spinning equipment can be damaged.

For example, patent CN1763276A discloses a method for manufacturing far infrared-antistatic polyester fiber, which comprises adding inorganic antistatic agent during polymerization process, blending, and then blending and spinning antistatic slice and nanometer far infrared ceramic powder master batch to obtain fiber with far infrared-antistatic composite function, but in order to ensure good composite function, the content of far infrared ceramic powder added is up to 4%, and the specific gravity of antistatic agent is up to 3%. Although this method can achieve the multifunctionality of the fiber, the addition amount of the inorganic powder is too high, which results in deterioration of melt flowability, reduction of spinnability, reduction of strength of the fiber and deterioration of hand.

Disclosure of Invention

The invention provides a preparation method of antistatic low-temperature far infrared polyester fiber, aiming at overcoming the problems of excessively high addition amount of functional powder, poor spinnability, poor fiber comfort and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of antistatic low-temperature far infrared polyester fiber comprises the following preparation steps:

(1) placing graphene in ethylene glycol, and then carrying out shearing stirring and ultrasonic dispersion alternating combination treatment to prepare uniformly dispersed graphene slurry;

(2) putting the graphene slurry, terephthalic acid and a polymerization catalyst into a reaction kettle for pulping, then carrying out esterification and polycondensation reaction, discharging, and slicing under water to prepare a graphene modified polyester slice;

(3) the antistatic low-temperature far infrared polyester fiber is prepared by adopting a melt spinning process and carrying out extrusion spinning and stretching on the graphene modified polyester chip.

When the antistatic low-temperature far infrared polyester fiber is prepared, graphene is efficiently dispersed in ethylene glycol by adopting a homogeneous shearing and ultrasonic dispersion mode to prepare graphene slurry, then reaction monomer terephthalic acid and a catalyst are added into the graphene slurry, and the graphene modified polyester is prepared after esterification and polycondensation, wherein the graphene is sp modified polyester²The hybridized carbon atoms are arranged into a planar two-dimensional carbon material with a hexagonal honeycomb structure, and the planar two-dimensional carbon material has ultrahigh specific surface area and excellent mechanical, electrical, thermal and optical properties. After compounding the graphene and the polyester, the polyester can be endowed with antistatic and low-temperature far infrared performances, and the polyester fiber with antistatic and low-temperature far infrared performances is prepared after slicing and melt spinning the graphene modified polyester.

Preferably, the stirring speed of the shearing stirring in the step (1) is 1000-3000rpm, and the time is 1-1.5 h; the ultrasonic dispersion power is 1000-3000W, and the time is 1-1.5 h; the number of the alternate combined treatment is 1-3; the concentration of the graphene slurry is 0.4-0.6 wt%.

The mode of shearing, stirring and ultrasonic alternative combined treatment can enable graphene to be dispersed more uniformly, and the prepared fiber has better antistatic property, low-temperature far infrared property and mechanical property.

Preferably, the feeding molar ratio of the ethylene glycol to the terephthalic acid in the step (2) is 1.2-1.6: 1; the polymerization catalyst is a titanium-silicon composite catalyst, and the dosage of the polymerization catalyst is 2-6ppm of the theoretical discharge amount of the polyester.

Preferably, the esterification reaction condition in the step (2) is that the reaction is continuously carried out for 2 to 3 hours at the temperature of 240 ℃ and 260 ℃ and at the pressure of 0.2 to 0.4 Mpa; the polycondensation reaction condition is that the reaction is continued for 1.5 to 3.5 hours at the temperature of 260 ℃ and 280 ℃ and under the pressure of 30 to 1000 Pa.

Preferably, the graphene is functionalized modified graphene, and the preparation method comprises the following steps:

s1: placing graphene oxide in an ethanol aqueous solution, adding a diamine functional reagent after shearing stirring and ultrasonic dispersion alternative combination treatment, and uniformly stirring to prepare a dispersion liquid;

s2: placing a condensation coupling agent in a solvent to prepare a coupling agent solution;

s3: mixing the dispersion liquid and the coupling agent solution, stirring and refluxing for 2-8h at 25-80 ℃, and cooling to room temperature to prepare suspension;

s4: and (3) carrying out suction filtration and washing on the suspension, and carrying out vacuum drying for 12-24h at the temperature of 50-60 ℃ to prepare the functionalized graphene.

Due to the strong van der waals acting force between the graphene sheets, the sheets are very easy to stack and difficult to peel; in addition, the graphene is an inorganic material, and has weak interfacial bonding force with a polymer and poor interfacial compatibility, so that the graphene is difficult to uniformly disperse in a polyester matrix. Therefore, in order to achieve a certain filling effect in the prior art, the actual addition amount of graphene needs to be doubled or even more, which not only increases the production cost, but also greatly affects the fibrigenicity of graphene polyester and the mechanical properties of composite fibers. In contrast, the amino functionalized graphene is prepared by functionally grafting the surface of the graphene. Firstly, adding a diamine functional reagent into an ethanol dispersion liquid of graphene oxide, then adding a coupling agent solution containing a condensation coupling agent, wherein the condensation coupling agent can activate carboxyl on the graphene oxide during a reflux reaction, so that the diamine functional reagent is promoted to be grafted on the surface of the graphene oxide, the interlayer spacing can be increased, the stripping and dispersion of the graphene can be promoted, and the grafted amino group can be stably connected with a polyester molecular chain through covalent bonds, so that the interface compatibility of two phases is improved, and the binding force between the graphene and polyester is enhanced. And the invention adopts the condensation coupling agent to promote the grafting of the diamine functionalized reagent, the preparation process is simple, the reaction condition is mild, compared with the method that the acylation organic solvent is adopted in the functionalized graphene process of preparing the grafted amino by adopting the acyl halogenation-amidation method in the prior art, the method is easy to decompose to generate toxic and irritant gases such as sulfur dioxide, hydrogen chloride and the like under the condition of meeting water or being heated, and is easy to generate bad influence on human health and environment, the invention does not adopt the toxic acylation organic solvent in the amino functionalization process, can not generate toxic gas when being applied to the high-temperature polyester polymerization reaction and the melt spinning process, is safe and environment-friendly, and is very suitable for the preparation of the polyester composite fiber.

Preferably, the diamine-based functionalizing agent in step S1 includes one or more of ethylenediamine, butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, and p-phenylenediamine; in step S2, the condensation coupling agent includes one or two of O- (7-azabenzotriazole-1-yl) -N, N '-tetramethyluronium hexafluorophosphate or benzotriazol-N, N' -tetramethyluronium hexafluorophosphate, the solvent is one or two of acetone or acetonitrile, and the concentration of the coupling agent solution is: 0.05-0.3 g/mL.

According to the invention, O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate or benzotriazole-N, N, N ', N' -tetramethylurea hexafluorophosphate is used as a condensation coupling agent, so that the amination reaction rate can be remarkably increased, and the amino grafting rate of the graphene surface can be increased; compared with the traditional acyl halide-amide amination method, the method only needs the assistance of a little coupling agent, and the modification reaction is completed in one step, so the method is more economical and efficient.

Preferably, the preparation process comprises the following components in parts by weight: 20-25 parts of graphene oxide, 0.5-10 parts of diamine functional reagent and 0.5-3 parts of condensation coupling agent.

Preferably, the functionalized graphene is further subjected to intercalation modification treatment:

a: putting the functionalized graphene into deionized water, and performing ultrasonic treatment to obtain a functionalized graphene suspension;

b: adding polymethacrylic acid into the functionalized graphene suspension, and stirring and dissolving to obtain a mixed solution;

c: gradually heating the mixed solution to 75-80 ℃, then stirring at a high speed for 1-2h by using an emulsification homogenizer under a heat preservation state, and then reducing the speed to a low speed for continuously stirring for 0.5-1h to prepare a suspension A;

d: gradually cooling the suspension A to room temperature, standing for 1-2h, and then carrying out ultrasonic stripping for 2-2.5h at 40-45 ℃ under 3000-;

e: and carrying out suction filtration and washing on the dispersion liquid B, and carrying out freeze drying at-45 to-50 ℃ for 12-24h to prepare the functionalized graphene for further intercalation.

After amino functional modification, although the functionalized graphene has better interlayer spacing and compatibility with a matrix, in order to further increase the antistatic property and the low-temperature far infrared performance of the polyester fiber, the functional graphene is further subjected to intercalation modification treatment by the invention group. Firstly, after a functionalized graphene suspension is prepared, adding polymethacrylic acid to dissolve at room temperature to prepare a mixed solution, then gradually heating the mixed solution, when the temperature is raised to 75 ℃ and above 75 ℃, the polymethacrylic acid can generate high-temperature stimulation response, and the molecular chain generates high-temperature hydrophobic shrinkage, at the moment, because the functionalized graphene is subjected to amino primary intercalation modification treatment, the interlamination is preliminarily enlarged, and is matched with an emulsification homogenizer to be stirred at high speed in a heat preservation state, polymethacrylic acid molecules in a volume shrinkage state can be inserted into the interlamination of the functionalized graphene (if the amino functional primary intercalation modification treatment is not carried out, the polymethacrylic acid molecules cannot enter the interlamination of the graphene), and then continuously stirring at low speed, so that the polymethacrylic acid can be fully intercalated and adsorbed in the interlamination of the functionalized graphene, obtaining an intercalation modified suspension A, and then gradually reducing the suspension A to room temperature, wherein polymethacrylic acid molecules generate low-temperature stimulation response, the hydrophilicity is recovered, and molecular chains are stretched and expanded in volume, so that the interlayer spacing of the functionalized graphene is further enlarged. Then controlling the temperature at 40-45 ℃, carrying out ultrasonic stripping to prepare a monodisperse few-layer functionalized graphene dispersion liquid B, removing excessive free polymethacrylic acid molecules through suction filtration and washing, and freeze-drying to prepare a few-layer functionalized graphene with further enlarged interlayer spacing and better dispersibility; according to the invention, the interlayer spacing is initially enlarged through amino functionalization of diamine micromolecules, and the graphene prepared by using a double modification method of further intercalation modification of water-soluble macromolecular polymethacrylic acid has higher stripping degree, in the in-situ polymerization process of the graphene and polyester, a polyester molecular chain can be covalently bonded to the surface of the graphene through amino and carboxyl, so that the interfacial force of the graphene-polyester two phases is further enhanced, the compatibility and the dispersibility of the graphene in a polyester matrix are improved, the prepared polyester has good filterability and spinnability, and the polyester fiber has excellent antistatic property and low-temperature far infrared performance under the condition of a low addition amount.

Preferably, the preparation process comprises the following components in parts by weight: 20-25 parts of functionalized graphene, 1000 parts of deionized water and 1200 parts of polymethacrylic acid; the molecular weight of the polymethacrylic acid is 3000-6000.

When the molecular weight of the polymethacrylic acid is controlled within the range of 3000-6000, the interlayer spacing of the functionalized graphene can be further enlarged when low-temperature stimulation response occurs and a molecular chain is stretched and the volume is expanded between the layers of the functionalized graphene better during high-temperature hydrophobic shrinkage.

Preferably, the stirring speed in the high-speed stirring treatment in the step C is 2000-2500 rpm; the stirring rate was 300-.

The high-speed stirring and the low-speed stirring are matched for enabling the polymethacrylic acid molecules in a volume shrinkage state to be fully inserted and adsorbed between the layers of the functionalized graphene.

Therefore, the invention has the following beneficial effects:

(1) compounding graphene and polyester to endow the polyester with antistatic and low-temperature far infrared properties, slicing the graphene modified polyester, and performing melt spinning to prepare the polyester fiber with antistatic, low-temperature far infrared properties and high mechanical properties;

(2) the method does not adopt toxic acylated organic solvent in the amino functionalization process, does not generate toxic gas when being applied to high-temperature polyester polymerization reaction and melt spinning process, is safe and environment-friendly, and is very suitable for preparing the polyester composite fiber;

(3) according to the invention, firstly, the interlayer spacing is preliminarily enlarged through amino functionalization of diamine micromolecules, and then, the monodisperse few-layer graphene with higher graphene stripping degree is prepared by utilizing a double modification method of further intercalation modification of water-soluble macromolecular polymethacrylic acid.

Detailed Description

The invention is further described with reference to specific embodiments.

General example: a preparation method of antistatic low-temperature far infrared polyester fiber comprises the following preparation steps:

(1) placing graphene in ethylene glycol, shearing and stirring at 3000rpm of 1000-;

(2) putting the graphene slurry, terephthalic acid and a titanium-silicon composite catalyst into a reaction kettle for pulping, wherein the feeding molar ratio of ethylene glycol to terephthalic acid is 1.2-1.6:1, the dosage of the titanium-silicon composite catalyst is 2-6ppm of the theoretical discharge amount of polyester, and then carrying out esterification reaction for 2-3h at the temperature of 240 ℃ and 260 ℃ under the pressure of 0.2-0.4 MPa; carrying out polycondensation reaction at 260-280 ℃ and 30-1000Pa for 1.5-3.5h, discharging and then slicing under water to obtain graphene modified polyester slices;

(3) the preparation method comprises the following steps of (1) preparing the antistatic low-temperature far infrared polyester fiber by adopting a melt spinning process and carrying out extrusion spinning and stretching on the graphene modified polyester chip;

the graphene is functionalized modified graphene and comprises the following preparation steps:

s1: placing graphene oxide in an ethanol aqueous solution, adding a diamine functional reagent after shearing stirring and ultrasonic dispersion alternative combination treatment, and uniformly stirring to prepare a dispersion liquid; the diamine functionalization reagent comprises one or more of ethylenediamine, butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine and p-phenylenediamine;

s2: putting the condensation coupling agent into a solvent to prepare a coupling agent solution with the concentration of 0.05-0.3 g/mL; the condensation coupling agent comprises one or two of O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate or benzotriazole-N, N, N ', N' -tetramethylurea hexafluorophosphate, and the solvent is one or two of acetone or acetonitrile;

s3: mixing the dispersion liquid and the coupling agent solution, stirring and refluxing for 2-8h at 25-80 ℃, and cooling to room temperature to prepare suspension;

s4: carrying out suction filtration and washing on the suspension, and carrying out vacuum drying for 12-24h at 50-60 ℃ to prepare functionalized graphene; the preparation process comprises the following components in parts by weight: 20-25 parts of graphene oxide, 0.5-10 parts of diamine functional reagent and 0.5-3 parts of condensation coupling agent;

the functionalized graphene is subjected to further intercalation modification treatment:

a: putting the functionalized graphene into deionized water, and performing ultrasonic treatment to obtain a functionalized graphene suspension;

b: adding polymethacrylic acid with the molecular weight of 3000-6000 into the functionalized graphene suspension, and stirring and dissolving to obtain a mixed solution; the preparation process comprises the following components in parts by weight: 20-25 parts of functionalized graphene, 1000 parts of deionized water and 1200 parts of polymethacrylic acid;

c: gradually heating the mixed solution to 75-80 ℃, then adopting an emulsification homogenizer to stir at a high speed of 2500rpm for 1-2h under the heat preservation state, and then reducing the speed to 500rpm at 300-;

d: gradually cooling the suspension A to room temperature, standing for 1-2h, and then carrying out ultrasonic stripping for 2-2.5h at 40-45 ℃ under 3000-;

e: and carrying out suction filtration and washing on the dispersion liquid B, and carrying out freeze drying at-45 to-50 ℃ for 12-24h to prepare the functionalized graphene for further intercalation.