A graphene-modified multifunctional polyester fiber and preparation method thereof and application in down filling

Abstract

The present invention relates to a graphene-modified multifunctional polyester fiber and a preparation method and an application in down filling, belonging to the technical field of down filling. The preparation method of the present invention comprises the following steps: S1, under the action of an acid binding agent, trimethylolethane and phosphorus oxychloride are reacted in a solvent in the first stage, and then graphene oxide is added for the second stage reaction to obtain modified graphene oxide; S2, the modified graphene oxide and polyester powder are granulated to obtain a multifunctional polyester masterbatch; S3, the multifunctional polyester masterbatch and polyester slices are spun to obtain a graphene-modified multifunctional polyester fiber. The far-infrared normal emissivity of the graphene-modified multifunctional polyester fiber is 0.89-0.92, the far-infrared radiation temperature rise is 2.3℃-3.1℃, the limiting oxygen index reaches 28.3%-29.0%, the antibacterial performance is higher than 99.9%, and the breaking strength is 3.2cN / detx-3.4cN / detx.

Description

Technical Field

[0001] The invention belongs to the technical field of down fillings, and in particular relates to a graphene-modified multifunctional polyester fiber, a preparation method thereof, and an application thereof in down fillings. Background Art

[0002] Down jackets are usually filled with duck or goose down. These fillings can effectively lock air due to their three-dimensional flower-like structure and hollow fine down fibers, thus providing good warmth retention. However, down is expensive, and down jackets may encounter some problems during wearing and washing, such as down drilling and decreased warmth retention due to improper washing. In addition, down is a protein fiber with poor antibacterial properties, which can easily cause down jackets to mold. Polyester fillers have high strength and elastic recovery ability, are not easy to deform, and are relatively cheap, so they are cost-effective and have excellent impedance. Therefore, they are widely used in various plush toys and warm clothing, but their assembly properties are poor. Therefore, the development of composite filling materials that combine far-infrared warmth retention, antibacterial, flame retardant and other properties has attracted the attention of R&D personnel.

[0003] Graphene is a single layer of carbon atoms in sp 2 The two-dimensional material composed of hybrid orbitals has excellent thermal, mechanical, electrical and optical properties. The far-infrared polyester fiber prepared with graphene has excellent far-infrared warmth retention, antistatic and antibacterial properties. However, graphene has high surface energy and poor compatibility with polyester. It is easy to agglomerate in polyester fibers, resulting in spinning difficulties and even damage to spinning equipment.

[0004] Chinese invention patent CN 106222789 A discloses a method for manufacturing biomass graphene flame-retardant polyester fiber, firstly, a dispersant is mixed with biomass graphene to obtain a biomass graphene dispersion, and then the biomass graphene dispersion, diethyl aluminum hypophosphite, diethyl magnesium hypophosphite, aluminum hydrogen phosphite and other flame retardants are added to polyester through polymerization reaction to prepare biomass graphene flame-retardant polyester chips and polyester fibers. However, the polymerization process is complicated and difficult to control, and has high requirements for equipment, etc., and the amount of flame retardant added is small, and the flame retardant performance is difficult to meet high requirements.

[0005] Chinese invention patent CN 104630928 A discloses a method for preparing graphene-reinforced flame-retardant recycled polyester staple fibers. First, graphene is sulfonated to prepare graphene masterbatch, and then a reactive phosphorus-based flame retardant is mixed with polyester to prepare a phosphorus-based halogen-free flame-retardant masterbatch. Then, the graphene masterbatch and the phosphorus-based halogen-free flame-retardant masterbatch are used to prepare the reinforced flame-retardant recycled polyester fiber by melt blending technology. However, the introduction of anionic sulfonic acid groups cannot improve the dispersion and compatibility of graphene in polyester fibers, and the flame retardants used are N-hydroxymethylpropionamide methyl phosphonate, dimethyl methyl phosphate and other flame retardants, which have poor thermal stability and are easily decomposed during the melt blending process, thereby affecting the dispersion and compatibility of the flame retardant in the polyester fiber.

[0006] Based on the above background, it is still necessary to develop composite down filling materials based on graphene. Summary of the invention

[0007] In order to solve the above technical problems, the present invention provides a graphene-modified multifunctional polyester fiber, a preparation method and an application of the fiber in down filling. Firstly, phosphorus oxychloride and trimethylolethane are used to synthesize a six-membered ring phosphate modifier containing active chlorine, and the six-membered ring phosphate modifier containing active chlorine is used to modify graphene oxide to obtain modified graphene. Then, the modified graphene oxide is used to prepare graphene-modified multifunctional polyester fiber by melt blending. Finally, the graphene-modified multifunctional polyester fiber is mixed with down in a certain proportion to prepare the graphene-modified multifunctional polyester fiber.

[0008] The first object of the present invention is to provide a method for preparing a graphene-modified multifunctional polyester fiber, comprising the following steps:

[0009] S1. Under the action of an acid binding agent, trimethylolethane and phosphorus oxychloride are reacted in a solvent in a first stage, and then graphene oxide is added to carry out a second stage reaction to obtain modified graphene oxide;

[0010] S2, granulating the modified graphene oxide and polyester powder described in S1 to obtain a multifunctional polyester masterbatch;

[0011] S3, spinning the multifunctional polyester masterbatch and polyester chips described in S2 to obtain the graphene-modified multifunctional polyester fiber.

[0012] In one embodiment of the present invention, in S1, the acid binding agent is triethylamine, trimethylolethane reacts with phosphorus oxychloride to generate hydrochloric acid, and the addition of the acid binding agent helps to promote the reaction.

[0013] In one embodiment of the present invention, in S1, the molar ratio of the acid binding agent to trimethylolethane is 1:(1-1.2); the molar ratio of trimethylolethane to phosphorus oxychloride is 1:(1.3-1.5); the mass ratio of trimethylolethane to solvent is 1:(30-40); the mass ratio of phosphorus oxychloride to graphene oxide is 1:(3-5); three active chlorine groups per mole of phosphorus oxychloride can undergo nucleophilic substitution reaction with three active hydroxyl groups of trimethylolethane to generate a long chain structure of a six-membered ring phosphate containing active chlorine, and maintaining an excess of phosphorus oxychloride helps to promote the reaction and maintain the active chlorine structure at the end of the molecular chain of the six-membered ring phosphate containing active chlorine.

[0014] In one embodiment of the present invention, in S1, the temperature of the first stage reaction is 30°C-40°C, and the time is 2h-3h; the temperature of the second stage reaction is 40°C-50°C, and the time is 6h-8h.

[0015] In one embodiment of the present invention, before S2, it also includes a step of drying the modified graphene oxide and the polyester powder, the drying temperature of the modified graphene oxide is 60°C-70°C, and the time is 6h-8h; the drying temperature of the polyester powder is 115°C-125°C, and the time is 10h-12h.

[0016] In one embodiment of the present invention, in S2, the granulation is performed by melt blending, extrusion molding, cooling and pelletizing through a twin-screw extruder; the granulation temperature is 260° C.-270° C. If the processing temperature is too low, the modified graphene oxide and the polyester powder cannot be mixed evenly, which is not conducive to granulation, and if the temperature is too high, it will cause energy waste.

[0017] In one embodiment of the present invention, in S2, the mass fraction of modified graphene oxide in the multifunctional polyester masterbatch is 20%-25%.

[0018] In one embodiment of the present invention, before S3, the multifunctional polyester masterbatch and the polyester chips are further included in the step of drying, wherein the drying is performed by pre-crystallization at 95°C-105°C for 3h-4h, and then drying at 125°C-135°C for 10h-15h, to ensure that the final moisture content of the multifunctional polyester masterbatch and the polyester chips is less than 200ppm.

[0019] In one embodiment of the present invention, in S3, the spinning is carried out by a melt spinning machine, followed by oiling, pre-stretching, winding, and stretching; the spinning process parameters are: speed of 2800m / min-3000m / min, temperature of 270℃-285℃, and traction ratio of 2-2.5.

[0020] In one embodiment of the present invention, in S3, the mass fraction of the multifunctional polyester masterbatch in the graphene-modified multifunctional polyester fiber is 10%-15%.

[0021] The second object of the present invention is to provide a graphene-modified multifunctional polyester fiber prepared by the method described.

[0022] In one embodiment of the present invention, the far-infrared normal emissivity of the graphene-modified multifunctional polyester fiber is 0.89-0.92, the far-infrared radiation temperature rise is 2.3°C-3.1°C, the limiting oxygen index reaches 28.3%-29.0%, the antibacterial property is higher than 99.9%, and the breaking strength is 3.2cN / detx-3.4cN / detx.

[0023] The third object of the present invention is to provide a down filling material, comprising the graphene-modified multifunctional polyester fiber and down; the mass fraction of the graphene-modified multifunctional polyester fiber in the down filling material is 30%-60%; and the down is selected from goose down and / or duck down.

[0024] The technical solution of the present invention has the following advantages over the prior art:

[0025] (1) The preparation method of the present invention allows the active hydroxyl group of trimethylolethane to undergo a nucleophilic substitution reaction with the active chlorine of phosphorus oxychloride to generate a long chain structure of a six-membered ring phosphate containing active chlorine, and the phosphorus oxychloride is kept in excess so that the end of the modifier molecular chain contains an active chlorine structure; the surface of graphene oxide contains a small amount of hydroxyl group, carboxyl group, epoxy group, etc., and the six-membered ring phosphate modifier containing active chlorine can produce covalent bond cross-linking with these groups, thereby grafting the six-membered ring phosphate modifier containing active chlorine on the surface of graphene oxide; in addition, graphene oxide is a sheet material and has a low content of active groups, so the molecular chain segment of the six-membered ring phosphate modifier containing active chlorine is longer, and the active chlorine is more active and easy to react. In addition, the six-membered ring phosphate modifier is rich in six-membered ring structure and can produce strong π-π stacking with graphene oxide, so that the long chain of the six-membered ring phosphate modifier can form a stable coating on the surface of the flaky graphene oxide.

[0026] (2) The long-chain structure of the six-membered cyclic phosphate in the modified graphene oxide described in the present invention is similar to the aromatic structure of polyester fibers and has good compatibility with polyester fibers. The modified graphene oxide is evenly dispersed in the polyester fibers and not only has high functionality but also has little damage to the strength properties of the polyester fibers.

[0027] (3) The modified graphene oxide described in the present invention is rich in phosphate groups and has strong flame retardant properties. In addition, graphene oxide has strong charring properties under the action of phosphate. There is a synergistic flame retardant effect between the phosphate groups and graphene oxide, and the flame retardant efficiency is high. Therefore, the graphene-modified multifunctional polyester fiber also has good flame retardant properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:

[0029] Figure 1 This is a schematic diagram of the structure of modified graphene oxide according to Example 1 of the present invention. DETAILED DESCRIPTION

[0030] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. It should be understood that the specific embodiments are only used to explain the present invention, but the embodiments are not intended to limit the present invention.

[0031] In the present invention, unless otherwise defined, technical and scientific terms used in the present invention have the same meanings as commonly understood by those skilled in the art to which the present invention belongs.

[0032] In the present invention, unless otherwise stated, the term "and / or" used in the present invention includes any and all combinations of one or more of the associated listed items.

[0033] In the present invention, unless otherwise stated, the experimental methods used in the embodiments of the present invention are conventional methods unless otherwise stated, and the materials, reagents, etc. used are all commercially available unless otherwise stated.

[0034] In the present invention, unless otherwise specified, the graphene oxide used in the examples of the present invention was purchased from Wuxi Origin Technology Co., Ltd.

[0035] Example 1

[0036] The graphene-modified multifunctional polyester fiber and its preparation method and application in down filling of this embodiment specifically include the following steps:

[0037] S1. Dissolve trimethylolethane and triethylamine in dichloromethane, add dichloromethane solution of phosphorus oxychloride dropwise at 35°C, and continue to react for 2.5 hours after the addition is complete; then add graphene oxide at 45°C and continue to react for 7 hours, distill under reduced pressure, and wash with ethanol to obtain modified graphene oxide powder ( Figure 1); wherein the molar ratio of triethylamine to trimethylolethane is 1:1.1; the molar ratio of trimethylolethane to phosphorus oxychloride is 1:1.4; the mass ratio of trimethylolethane to dichloromethane is 1:35; the mass ratio of phosphorus oxychloride to graphene oxide is 1:4;

[0038] S2, the modified graphene oxide powder was vacuum dried at 65°C for 7h; the polyester powder was vacuum dried at 120°C for 11h, and after mixing, melt blending, extrusion molding, cooling and pelletizing were carried out through a twin-screw extruder, and the temperature of the twin-screw extruder was 265°C to obtain a multifunctional polyester masterbatch with a mass fraction of 23% of the modified graphene oxide powder;

[0039] S3, the multifunctional polyester masterbatch and the polyester chips were pre-crystallized in a 100°C blast oven for 3.5 hours, and then dried at 130°C for 13 hours, so that the final moisture content of the multifunctional polyester masterbatch and the polyester chips was less than 200 ppm. After mixing, they were spun through a melt spinning machine, cooled and oiled, pre-stretched, wound and stretched. The speed of the melt spinning machine was 2900 m / min, the temperature was 278°C, and the traction ratio was 2.3, to obtain a graphene-modified multifunctional polyester fiber with a mass fraction of 13% of the multifunctional polyester masterbatch.

[0040] Example 2

[0041] The graphene-modified multifunctional polyester fiber and its preparation method and application in down filling of this embodiment specifically include the following steps:

[0042] S1. Dissolve trimethylolethane and triethylamine in dichloromethane, add a dichloromethane solution of phosphorus oxychloride dropwise at 30°C, and continue to react for 3 hours after the addition is completed; then add graphene oxide at 40°C and continue to react for 8 hours, distill under reduced pressure, and wash with ethanol to obtain modified graphene oxide powder; wherein the molar ratio of triethylamine to trimethylolethane is 1:1; the molar ratio of trimethylolethane to phosphorus oxychloride is 1:1.3; the mass ratio of trimethylolethane to dichloromethane is 1:30; and the mass ratio of phosphorus oxychloride to graphene oxide is 1:3;

[0043] S2, the modified graphene oxide powder was vacuum dried at 60°C for 8h; the polyester powder was vacuum dried at 115°C for 12h, and after mixing, melt blending, extrusion molding, cooling and pelletizing were carried out through a twin-screw extruder, and the temperature of the twin-screw extruder was 260°C to obtain a multifunctional polyester masterbatch with a mass fraction of 20% of the modified graphene oxide powder;

[0044] S3, the multifunctional polyester masterbatch and polyester chips are pre-crystallized in a 95°C blast oven for 4 hours, and then dried at 125°C for 15 hours to make the final moisture content of the multifunctional polyester masterbatch and polyester chips less than 200 ppm. After mixing, they are spun through a melt spinning machine, cooled and oiled, pre-stretched, wound and stretched. The speed of the melt spinning machine is 2800 m / min, the temperature is 270°C, and the pulling ratio is 2, so as to obtain multifunctional polyester fibers modified with graphene having a mass fraction of 10%-15% of the multifunctional polyester masterbatch.

[0045] Example 3

[0046] The graphene-modified multifunctional polyester fiber and its preparation method and application in down filling of this embodiment specifically include the following steps:

[0047] S1. Dissolve trimethylolethane and triethylamine in dichloromethane, add a dichloromethane solution of phosphorus oxychloride dropwise at 40°C, and continue to react for 2 hours after the addition is completed; then add graphene oxide at 50°C and continue to react for 6 hours, distill under reduced pressure, and wash with ethanol to obtain modified graphene oxide powder; wherein the molar ratio of triethylamine to trimethylolethane is 1:1.2; the molar ratio of trimethylolethane to phosphorus oxychloride is 1:1.5; the mass ratio of trimethylolethane to dichloromethane is 1:40; and the mass ratio of phosphorus oxychloride to graphene oxide is 1:5;

[0048] S2, the modified graphene oxide powder was vacuum dried at 70°C for 6 hours; the polyester powder was vacuum dried at 125°C for 10 hours, and after mixing, it was melt blended, extruded, cooled and pelletized by a twin-screw extruder. The temperature of the twin-screw extruder was 270°C to obtain a multifunctional polyester masterbatch with a mass fraction of 25% of the modified graphene oxide powder;

[0049] S3, the multifunctional polyester masterbatch and polyester chips are pre-crystallized in a 105°C blast oven for 3 hours, and then dried at 135°C for 10 hours to make the final moisture content of the multifunctional polyester masterbatch and polyester chips less than 200 ppm. After mixing, they are spun through a melt spinning machine, cooled and oiled, pre-stretched, wound and stretched. The speed of the melt spinning machine is 3000 m / min, the temperature is 285°C, and the traction ratio is 2.5 to obtain multifunctional polyester fibers modified with graphene having a mass fraction of 10%-15% of the multifunctional polyester masterbatch.

[0050] Comparative Example 1

[0051] The method is basically the same as Example 1, except that trimethylolethane is replaced by ethylene glycol when modifying graphene oxide.

[0052] Comparative Example 2

[0053] The method is basically the same as Example 1, except that trimethylolethane is not used to modify graphene oxide.

[0054] Comparative Example 3

[0055] The method is basically the same as Example 1, except that phosphorus oxychloride is replaced by phosphoric acid when modifying graphene oxide.

[0056] Comparative Example 4

[0057] The method is basically the same as Example 1, except that phosphorus oxychloride is not used to modify graphene oxide.

[0058] Comparative Example 5

[0059] The method is basically the same as Example 1, except that graphene oxide and polyester powder are directly used for granulation and spinning.

[0060] Comparative Example 6

[0061] The process is basically the same as Example 1, except that polyester powder is directly used for granulation and spinning (unmodified polyester fiber).

[0062] Test Case

[0063] The far infrared properties of the graphene-modified multifunctional polyester fibers (modified polyester fibers) and unmodified polyester fibers prepared in Examples 1-3 and Comparative Examples 1-6 were tested:

[0064] Far infrared performance: Refer to GB / T30127-2013 "Testing and evaluation of far infrared performance of textiles" to test the far infrared emissivity and heating performance of unmodified polyester fiber and modified polyester fiber;

[0065] Flame retardant properties: Refer to the standard FZ / T50017-2011 "Polyester fiber flame retardant properties test method oxygen index method" to test the limiting oxygen index of unmodified polyester fiber and modified polyester fiber;

[0066] Antibacterial performance: Refer to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method" to test the antibacterial rate of unmodified polyester fiber and modified polyester fiber;

[0067] Physical properties: Refer to GB / T14344-2022 "Test method for tensile properties of chemical fiber filaments" to test the breaking strength of unmodified polyester fiber and modified polyester fiber;

[0068] Table 1 shows the relevant properties of the unmodified polyester fiber and the modified polyester fiber finally measured:

[0069] Table 1

[0070]

[0071]

[0072] As can be seen from Table 1, the modified polyester fiber has excellent far-infrared emission performance and far-infrared heating performance, flame retardant performance and antibacterial performance, and the mechanical properties of the modified polyester fiber are less damaged. This is because the modified graphene oxide has high compatibility with polyester fibers and is easy to be evenly dispersed in the polyester fibers.

[0073] By comparing Example 1 and Comparative Example 1, it can be seen that when graphene oxide is modified by ethylene glycol and phosphorus oxychloride, a six-membered ring structure cannot be generated, resulting in poor compatibility of the modified graphene oxide with polyester fibers, making it difficult to disperse evenly in the polyester fibers, and the mechanical properties of the modified polyester fibers are greatly damaged and have poor functionality.

[0074] By comparing Example 1 and Comparative Example 2, it can be seen that when phosphorus oxychloride is directly used to modify graphene oxide, a six-membered ring structure cannot be generated, resulting in poor compatibility of the modified graphene oxide with polyester fibers, making it difficult to disperse evenly in the polyester fibers, and the mechanical properties of the modified polyester fibers are greatly damaged and have poor functionality.

[0075] By comparing Example 1 and Comparative Example 3, it can be seen that when trimethylolethane and phosphoric acid are used to modify graphene oxide, the functionality of the modified polyester fiber is poor and the mechanical properties are poor. This is because trimethylolethane and phosphoric acid cannot be grafted to modify graphene oxide, resulting in poor compatibility between the modified graphene oxide and the polyester fiber.

[0076] By comparing Example 1 and Comparative Example 4, it can be seen that when trimethylolethane is directly used to modify graphene oxide, the functionality of the modified polyester fiber is poor and the mechanical properties are poor. This is because trimethylolethane cannot be grafted to modify graphene oxide, resulting in poor compatibility between the modified graphene oxide and the polyester fiber.

[0077] By comparing Example 1 and Comparative Example 5, it can be seen that when trimethylolethane and phosphorus oxychloride are not used to modify graphene oxide, the mechanical properties of the modified polyester fiber are poor. This is because graphene oxide is difficult to disperse evenly in the polyester fiber, resulting in uneven modification of graphene oxide and significant damage to the mechanical properties of the polyester fiber.

[0078] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. A method for preparing a graphene-modified multifunctional polyester fiber, characterized in that: The following steps are involved: S1. Under the action of an acid binding agent, trimethylolethane and phosphorus oxychloride are reacted in a solvent in a first stage, and then graphene oxide is added to carry out a second stage reaction to obtain modified graphene oxide; S2, granulating the modified graphene oxide and polyester powder described in S1 to obtain a multifunctional polyester masterbatch; S3, spinning the multifunctional polyester masterbatch and polyester chips described in S2 to obtain the graphene-modified multifunctional polyester fiber.

2. The method for preparing the graphene-modified multifunctional polyester fiber according to claim 1, characterized in that: In S1, the acid binding agent is triethylamine.

3. The method for preparing the graphene-modified multifunctional polyester fiber according to claim 1, characterized in that: In S1, the molar ratio of the acid binding agent to trimethylolethane is 1:(1-1.2); the molar ratio of trimethylolethane to phosphorus oxychloride is 1:(1.3-1.5); the mass ratio of trimethylolethane to solvent is 1:(30-40); and the mass ratio of phosphorus oxychloride to graphene oxide is 1:(3-5).

4. The method for preparing the graphene-modified multifunctional polyester fiber according to claim 1, characterized in that: In S1, the temperature of the first stage reaction is 30°C-40°C, and the time is 2h-3h; the temperature of the second stage reaction is 40°C-50°C, and the time is 6h-8h.

5. The method for preparing the graphene-modified multifunctional polyester fiber according to claim 1, characterized in that: In S2, the granulation is performed by melt blending, extrusion molding, cooling and pelletizing through a twin-screw extruder; the granulation temperature is 260°C-270°C.

6. The method for preparing the graphene-modified multifunctional polyester fiber according to claim 1, characterized in that: In S2, the mass fraction of modified graphene oxide in the multifunctional polyester masterbatch is 20%-25%.

7. The method for preparing the graphene-modified multifunctional polyester fiber according to claim 1, characterized in that: In S3, the spinning is carried out by a melt spinning machine, followed by oiling, pre-stretching, winding, and stretching. The spinning process parameters are: a speed of 2800m / min-3000m / min, a temperature of 270℃-285℃, and a drawing ratio of 2-2.

5.

8. The method for preparing graphene-modified multifunctional polyester fiber according to claim 1, characterized in that: In S3, the mass fraction of the multifunctional polyester masterbatch in the graphene-modified multifunctional polyester fiber is 10%-15%.

9. A graphene-modified multifunctional polyester fiber prepared by the method according to any one of claims 1 to 8.

10. A down filling material, characterized in that: It comprises the graphene-modified multifunctional polyester fiber and down as described in claim 9; the mass fraction of the graphene-modified multifunctional polyester fiber in the down filling is 30%-60%; and the down is selected from goose down and / or duck down.

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