WO2020097985A1 - Graphene and ultra-high molecular weight polyethylene composite fiber and preparation method therefor - Google Patents

Abstract

The present invention provides a graphene and ultra-high molecular weight polyethylene composite fiber and a preparation method therefor. The composite fiber comprises the following components: polyethylene, a reinforcement, a dispersant, and an antioxidant. The weight ratio of the polyethylene to the reinforcement is: 20-25 to 1.5-4.5. The reinforcement is hard fibers and graphene. The hard fibers and graphene of the present invention are mixed into ultra-high molecular weight polyethylene, so as to obtain an ultra-high molecular weight polyethylene composite fiber with high strength, cut resistance, improved puncture resistance, and high temperature resistance. Particularly, the composite fiber has a cut resistance level reaching level 5 of the U.S. Standard, and is mainly used in various cut-resistant and wear-resistant textiles, such as woven fabrics for hoses, cables, and woven fabrics for outer protective layers of optical cables; safety gear, including cut-resistant gloves, cut-resistant oversleeves, protective clothing, protective shoes, headgear, and aprons in the personal protection field; as well as sports apparel, civilian functional textiles, etc.

Description

Graphene ultra-high molecular weight polyethylene composite fiber and preparation method thereof Technical field

The invention relates to the technical field of polyethylene fibers, in particular, to a graphene ultra-high molecular weight polyethylene composite fiber and a preparation method thereof.

Background technique

UHMWPE fiber is one of the three high-tech fibers. It is the fiber with the highest specific strength that has been commercially produced. It is mainly used in safety protection, aviation, weapons, sports and other fields. Ultra-high molecular weight polyethylene (UHMWPE) refers to linear polyethylene with a weight average molecular weight greater than 1.5 million. Its chain structure is a typical linear structure, with very few branches, far lower than ordinary polyethylene, branching point is less than 1/1000, macromolecular chain is super long, reaching tens of thousands of nanometers, so it is a flexible chain high strength fiber Ideal material. In order to prevent the infringement of sharp objects, especially in the environment of speeding and emergencies, the development of a high-cut-resistant fiber and its woven products (such as various military and civilian facilities, coats, covers, etc.) has been received The attention of the industry at home and abroad.

Patent CN106149085A discloses a cutting-resistant ultra-high molecular weight polyethylene composite fiber, which is composed of ultra-high molecular weight polyethylene and expandable organosilicate clay, modified graphene, and antioxidant. The expandable organosilicate and graphene are introduced into the ultra-high molecular weight polyethylene fiber, so that the ultra-high molecular weight polyethylene fiber can achieve good cutting resistance without compounding other hard fibers, and its cutting resistance reaches the European standard Level 5 (equivalent to US Standard Level 3).

Patent CN106555244A discloses a cutting-resistant ultra-high molecular weight polyethylene fiber, including ultra-high molecular weight polyethylene fiber; hard fiber dispersed in the ultra-high molecular weight polyethylene fiber; the ultra-high molecular weight polyethylene fiber and hard The mass ratio of the quality fiber is 100: (2-8). This patent improves the tensile viscosity of the spinning dope during the preparation process by controlling the content of hard fibers, thereby further improving the mechanical properties of the finished fiber, and the resulting finished fiber has higher strength, high elongation at break and broken ends The number is low, and its cutting resistance reaches European standard level 5 (equivalent to American standard level 3).

Patent CN106555245A discloses a cutting-resistant ultra-high molecular weight polyethylene fiber, including ultra-high molecular weight polyethylene fiber; hard fiber and solvent oil dispersed in the ultra-high molecular weight polyethylene fiber; the ultra-high molecular weight polyethylene The mass ratio of fiber, hard fiber and solvent oil is 100: (3-6): (0.3-2). This patent makes the hard fiber more compatible with UHMWPE through the infiltration effect of solvent oil on the hard fiber. At the same time, the addition of solvent oil is conducive to the uniform distribution of hard fiber in the UHMWPE. , So that the finished fiber has a higher elongation at break, and its cutting resistance reaches the European standard level 5 (equivalent to the American standard level 3).

Patent CN106555247A discloses a cutting-resistant ultra-high molecular weight polyethylene fiber, including ultra-high molecular weight polyethylene fiber; hard fiber and iron powder dispersed in the ultra-high molecular weight polyethylene fiber; the ultra-high molecular weight polyethylene The mass ratio of fiber, hard fiber and iron powder is 100: (3 to 6): (0.01 to 0.05). This patent can improve the strength of the finished fiber through the interaction of iron powder and hard fiber; at the same time, the addition of iron powder is conducive to the uniform distribution of hard fiber in the ultra-high molecular weight polyethylene, so that the finished fiber has a lower strength change Rate, improve the quality stability of the finished fiber, and its cutting resistance reaches the European standard level 5 (equivalent to the American standard level 3).

Patent CN106555243A discloses a cutting-resistant ultra-high molecular weight polyethylene fiber, including ultra-high molecular weight polyethylene fiber; hard fiber and hard fiber slag dispersed in the ultra-high molecular weight polyethylene fiber; the ultra-high molecular weight The mass ratio of polyethylene fiber, hard fiber and hard fiber slag is 100: (3 to 6): (0.001 to 0.18). This patent adds hard fiber slag to make the hard fiber more evenly distributed in the ultra-high molecular weight polyethylene, so that the finished fiber has higher strength uniformity, and at the same time improves the friction resistance of the finished fiber, and its cutting resistance reaches European Standard 5 (equivalent to American Standard 3).

However, the ultra-high molecular weight polyethylene fibers obtained by the above patents are not very hot-melt, do not have good high temperature resistance, and the main physical characteristics-the highest cutting resistance can only reach the European standard 5 (equivalent to the United States Standard 3 level).

Summary of the invention

In view of the defects of the prior art, the object of the present invention is to provide a graphene ultra-high molecular weight polyethylene composite fiber and a preparation method thereof. The anti-cutting performance of the composite fiber prepared by the invention reaches the level of American standard level 5, and the high temperature resistance and puncture resistance are enhanced.

The purpose of the present invention is achieved by the following technical solutions:

The present invention provides a graphene ultra-high molecular weight polyethylene composite fiber, which includes the following components: polyethylene, reinforcement, dispersant, and antioxidant; the weight ratio of the polyethylene and reinforcement is: 20-25: 1.5 ～ 4.5;

The reinforcement is hard fiber and graphene.

Preferably, the weight percentage of the graphene in the composite fiber is 1 ‰ to 1%. More preferably, the ratio is 6 ‰ to 8 ‰.

Preferably, the graphene is at least one of single-layer or small-layer graphene, modified graphene, and graphene oxide.

Preferably, the modified graphene is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, polydienyl A modifier of propylene dimethyl ammonium chloride, dodecyl dimethyl ammonium oxide, dodecyl amine acetate, triacetamide bis-stearate methyl sulfate amine and n-ten Dialkyltriethoxysilane, n-dodecyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ- (methacryloyloxy) propyltrimethoxysilane, aminopropyl Graphene modified by a modifier of triethoxyvinylsilane and 3-aminopropyltrimethoxysilane.

Preferably, the hard fibers have a diameter of 2-10 microns and a length of 20-100 microns.

Preferably, the hard fiber includes: carbon fiber, and further includes at least one of basalt fiber, glass fiber, ceramic fiber, silicon carbide; more preferably, the hard fiber includes: carbon fiber, or carbon fiber and basalt fiber and / or Glass fiber composite.

More preferably, among the hard fibers, the mass of carbon fiber: basalt fiber and / or glass fiber is 1: 0.5 to 1.

Most preferably, among the hard fibers, the mass ratio of basalt fiber to glass fiber is 2 to 3: 1.

Preferably, the polyethylene is ultra-high molecular weight polyethylene, and its molecular weight is 1 × 10 ⁶ to 8 × 10 ⁶ ;

Preferably, the dispersant is stearate, zinc stearate, hexenyl bisstearic amide, oleoyl, polyethylene wax, polyethylene glycol; the amount of dispersant added is the total weight of the composite fiber 0.01 ～ 1%.

Preferably, the antioxidant is one of BASF B-215, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol or triphenyl phosphite; the antioxidant The added amount is 0.01 to 1% of the total weight of the composite fiber.

The invention also provides a method for preparing graphene ultra-high molecular weight polyethylene composite fiber, which includes the following steps:

A. Add polyethylene to white oil solvent, dissolve and disperse evenly at 50 ～ 100 ℃, and get the first mixed liquid;

B. According to the ratio, mix and mix the modified graphene, hard fiber, dispersant, and antioxidant, and then mix with the first mixture to obtain the polyethylene spinning stock solution;

C. Add the polyethylene spinning dope to the twin-screw blender, get the raw yarn through extrusion, cool it to a gel state, stand still to remove the internal stress of the raw yarn, and pre-draw, extract, heat draw and The winding molding process is to obtain the composite fiber;

In step A, the solvent is white oil; the weight ratio of the polyethylene to the solvent is: 20-25: 250-350.

The solvent added in step A of the present invention will be substantially removed during subsequent processing, so the resulting composite fiber is almost free of solvent.

Compared with the prior art, the present invention has the following beneficial effects:

The present invention adds hard fiber and graphene to ultra-high molecular weight polyethylene. The addition of hard fiber can enhance the cutting resistance and puncture resistance of the fiber, but will reduce the mechanical strength of the fiber (ie, tensile strength) The addition of graphene material can enhance the tensile strength and heat resistance of the fiber. Through the combination of hard fiber and graphene material and added to the PE resin, the effect of synergistically strengthening the ultra-high molecular weight polyethylene composite fiber can be achieved. Obtained ultra-high molecular weight polyethylene composite fiber with high strength, cut resistance, improved puncture resistance and temperature resistance, especially the cut resistance level reached US standard 5 level, mainly used in various cut-resistant wear-resistant textiles, such as hose woven Weaving cloth for outer protective layer of cloth, cable and optical cable, anti-cutting gloves, anti-cutting protective sleeves, protective clothing, protective shoes, caps, apron and other safety protective equipment in the field of personal protection, sports equipment, civilian functional textiles, etc.

detailed description

The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

In the following examples, the modified graphene used is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, polydi A modifier of alkenyl propylene dimethyl ammonium chloride, dodecyl dimethyl ammonium oxide, dodecyl amine acetate, triacetate bis-stearate methyl methyl sulfate And n-dodecyltriethoxysilane, n-dodecyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ- (methacryloyloxy) propyltrimethoxysilane, Graphene modified by a modifier in the amino triethoxyvinylsilane and 3-aminopropyltrimethoxysilane.

The hard fibers used have a diameter of 2 to 10 microns and a length of 20 to 100 microns.

The hard fibers used include carbon fiber, or a composite of carbon fiber and basalt fiber and / or glass fiber.

The polyethylene used is ultra-high molecular weight polyethylene with a molecular weight of 1 × 10 ⁶ ～ 8 × 10 ⁶ ;

The solvent used is white oil.

The dispersant used is stearate, zinc stearate, hexenyl bisstearic amide, oleoyl, polyethylene wax, polyethylene glycol; the amount of dispersant added is 0.01 to 1 of the total weight of the composite fiber %.

The antioxidant used is one of BASF B-215, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol or triphenyl phosphite; the amount of antioxidant added is 0.01 to 1% of the total weight of the composite fiber.

Example 1

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method includes the following steps:

A. Use ultra-high molecular weight polyethylene resin and add it to white oil, and stir until the dispersion is uniform at 50 ～ 100 ℃ to obtain the first mixed liquid;

B. According to the ratio, the graphene, hard fiber, dispersant, and antioxidant modified by cetyltrimethylammonium bromide and n-dodecyltrimethoxysilane will be added to the high mixer Stir at high speed until the dispersion is uniform, and mix with the first mixed liquid to obtain the ultra-high molecular weight polyethylene spinning stock solution;

C. Add the ultra-high molecular weight polyethylene spinning stock solution to the twin-screw mixer, extruded through the spinneret at a certain temperature to obtain the raw yarn, and quickly cooled into a gel in the cooling liquid (cooling liquid below 10 ℃) In this state, the internal stress of the raw silk is removed by standing (at least 20 hours), and after pre-drawing, extraction, heating, drawing and winding molding steps, the composite fiber is obtained.

Example 2

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method includes the following steps:

A. Add ultra-high molecular weight polyethylene resin to white oil, dissolve and disperse evenly at 50 ～ 100 ℃, and get the first mixed liquid;

B. According to the ratio, graphene, hard fiber, dispersant, antioxidant combined with dodecyl dimethyl benzyl ammonium chloride and aminopropyl triethoxyvinyl silane will be added High-speed mixing in the high-mixer and mixing with the first mixed liquid to obtain the ultra-high molecular weight polyethylene spinning stock solution;

C. Add the ultra-high molecular weight polyethylene spinning stock solution to the twin-screw mixer, extruded through the spinneret at a certain temperature to obtain the raw yarn, and quickly cooled into a gel in the cooling liquid (cooling liquid below 10 ℃) In the state, the internal stress of the raw silk is removed by standing (at least 24 hours), and after pre-drawing, extraction, and heating drawing, the composite fiber is obtained.

Example 3

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method includes the following steps:

A. Add ultra-high molecular weight polyethylene resin to white oil, dissolve and disperse evenly at 50 ～ 100 ℃, and get the first mixed liquid;

B. According to the ratio, the graphene, hard fiber, dispersant, and antioxidant modified by cetyltrimethylammonium bromide and n-dodecyltriethoxysilane will be added to the high mixer Stir at medium and high speed, and mix with the first mixed liquid to obtain the ultra-high molecular weight polyethylene spinning stock solution;

C. Add the ultra-high molecular weight polyethylene spinning stock solution to the twin-screw mixer, extruded through the spinneret at a certain temperature to obtain the raw yarn, and quickly cooled into a gel in the cooling liquid (cooling liquid below 10 ℃) In the state, the internal stress of the raw silk is removed by standing (at least 24 hours), and after pre-drawing, extraction, and heating drawing, the composite fiber is obtained.

Example 4

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method includes the following steps:

A. Use ultra-high molecular weight polyethylene resin and add it to white oil, dissolve and disperse evenly through 50-100 ℃ to obtain the first mixed liquid;

B. According to the ratio, the graphene, hard fiber, dispersant, and antioxidant modified by cetyltrimethylammonium bromide and n-dodecyltrimethoxysilane will be added to the high mixer High-speed stirring and mixing with the first mixed liquid to obtain ultra-high molecular weight polyethylene spinning stock solution;

C. Add the ultra-high molecular weight polyethylene spinning stock solution to the twin-screw mixer, extruded through the spinneret at a certain temperature to obtain the raw yarn, and quickly cooled into a gel in the cooling liquid (cooling liquid below 10 ℃) In the state, the internal stress of the raw silk is removed by standing (at least 24 hours), and after pre-drawing, extraction, and heating drawing, the composite fiber is obtained.

Example 5

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 4.

Example 6

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 4.

Example 7

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 4.

Example 8

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 4.

Example 9

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 4.

Example 10

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 4.

Example 11

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 4.

Example 12

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 4.

Example 13

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 1.

Example 14

This example provides the components and contents of a polyethylene composite fiber as shown in Table 2. The preparation method is the same as that in Example 1.

Table 1

Table 2

Example 15

This example provides a polyethylene composite fiber. The components and contents are basically the same as those in Example 1. The only difference is that the graphene used in this example is a single-layer graphene. The preparation method and implementation Example 1 is the same.

Example 16

This example provides a polyethylene composite fiber. The components and contents are basically the same as those in Example 1. The only difference is that the graphene used in this example is graphene oxide. The preparation method and example 1 Same.

Comparative Example 1

This comparative example provides a method for preparing polyethylene composite fibers, which is basically the same as the method in Example 1, except that in this comparative example, graphene is not added.

Comparative Example 2

This comparative example provides a method for preparing polyethylene composite fibers, which is basically the same as the method in Example 1, except that the hard fiber used in this comparative example is organic bentonite.

Effect verification:

The composite fibers prepared in the examples and comparative examples were made into cloth or gloves, and their cutting resistance was tested according to the ANSI-ISEA105: 2016 American Standard (as shown in Table 2), and the strength was tested using an Instron type tensile machine. Differential scanning calorimetry was used to test its high temperature resistance (melting point), and EN388 was used to test its puncture resistance. The test results are shown in Table 3.

Table 2

Index (g) Cut resistance grade ≥200 1 ≥500 2 ≥1000 3 ≥1500 4 ≥2200 5 ≥3000 6

table 3

From the test results in Table 3, it can be seen that the comprehensive effect of Examples 7 and 8 is the best, followed by 4, 5, and 11, followed by Examples 10 and 12. Moreover, the effects of Examples 6, 9 and Comparative Examples 1 and 2 are significantly inferior to all other examples, indicating that the effect of using reinforcing fibers of the present invention as carbon fibers or carbon fibers and basalt fibers and / or glass fibers is superior to other reinforcing fibers. The effects of Examples 15 and 16 are inferior to those of Example 1, indicating that the graphene modified with two modifiers is preferred for the carbon fiber.

There are many specific application paths of the present invention, and the above is only a preferred embodiment of the present invention. It should be noted that the above embodiments are only used to illustrate the present invention, but not to limit the protection scope of the present invention. For those of ordinary skill in the art, without departing from the principles of the present invention, several improvements can be made, and these improvements should also be regarded as the scope of protection of the present invention.

Claims (10)

A graphene ultra-high molecular weight polyethylene composite fiber, characterized by comprising the following components: polyethylene, reinforcement, dispersant, antioxidant; the weight ratio of the polyethylene and reinforcement is: 20-25: 1.5 ～ 4.5; The reinforcement is hard fiber and graphene. The graphene ultra-high molecular weight polyethylene composite fiber according to claim 1, wherein the weight percentage of the graphene in the composite fiber is 1 ‰ to 1%. The graphene ultra-high molecular weight polyethylene composite fiber according to claim 1 or 2, wherein the graphene is at least one of single-layer or small-layer graphene, modified graphene, and graphene oxide. The graphene ultra-high molecular weight polyethylene composite fiber according to claim 3, wherein the modified graphene is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride , Dodecyl dimethyl benzyl ammonium chloride, polydienyl propylene dimethyl ammonium chloride, dodecyl dimethyl ammonium oxide, dodecyl amine acetate, triacetate amine double hard A modifier in fatty acid ester methyl methyl sulfate amine and n-dodecyl triethoxysilane, n-dodecyl trimethoxysilane, γ-glycidyl ether oxypropyl trimethoxysilane, Graphene modified by one modifier of γ- (methacryloyloxy) propyltrimethoxysilane, aminopropyltriethoxyvinylsilane, and 3-aminopropyltrimethoxysilane. The graphene ultra-high molecular weight polyethylene composite fiber according to claim 1, wherein the hard fiber has a diameter of 2-10 microns and a length of 20-100 microns. The graphene ultra-high molecular weight polyethylene composite fiber according to claim 1, wherein the hard fiber comprises: carbon fiber, and further comprises at least one of basalt fiber, glass fiber, ceramic fiber, silicon carbide. The graphene ultrahigh molecular weight polyethylene composite fiber according to claim 1, wherein the polyethylene is ultrahigh molecular weight polyethylene, and its weight average molecular weight is 1 × 10 ⁶ to 8 × 10 ⁶ . The graphene ultra-high molecular weight polyethylene composite fiber according to claim 1, wherein the dispersant is stearate, zinc stearate, hexenyl bisstearic amide, oleoyl, polyethylene Wax, polyethylene glycol; the amount of dispersant added is 0.01 to 1% of the total weight of the composite fiber. The graphene ultra-high molecular weight polyethylene composite fiber according to claim 1, wherein the antioxidant is BASF B-215, 2,6-di-tert-butylphenol, 2,4,6-tri-tert One of butylphenol or triphenyl phosphite; the amount of antioxidant added is 0.01 to 1% of the total weight of the composite fiber. A method for preparing polyethylene composite fibers according to claim 1, characterized in that it includes the following steps: A. Add polyethylene to the solvent and dissolve and disperse it evenly at 50 ～ 100 ℃ to obtain the first mixed liquid; B. According to the ratio, mix and mix the modified graphene, hard fiber, dispersant, and antioxidant, and then mix with the first mixture to obtain the polyethylene spinning stock solution; C. Add the polyethylene spinning dope to the twin-screw blender, get the raw yarn through extrusion, cool it to a gel state, stand still to remove the internal stress of the raw yarn, and pre-draw, extract, heat draw and The winding molding process is to obtain the composite fiber; In step A, the solvent is white oil; the weight ratio of the polyethylene to the solvent is: 20-25: 250-350.