A coloring paste for ultra-high molecular weight polyethylene fibers and a preparation method thereof

Abstract

The present solution discloses a color paste for ultra-high molecular weight polyethylene fibers and a preparation method thereof. The color paste for ultra-high molecular weight polyethylene fibers is composed of components with the following mass percentages based on the total weight of the color paste for ultra-high molecular weight polyethylene fibers: white oil 72.38% - 93.84%, pigment 0.4% - 10.28%, dispersant 4.11% - 12.3%, emulsifier 0.4% - 2.05%, antioxidant 1.23% - 2.05%, and ultra-high molecular weight polyethylene 0.02% - 0.04%. This color paste is used in the preparation of colored ultra-high molecular weight polyethylene fibers by the spinning process of solution coloring. The prepared colored fibers have bright colors, mechanical properties of high strength and high modulus, and small batch color differences.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber coloring, and particularly relates to a coloring paste for ultra-high molecular weight polyethylene fibers and a preparation method thereof. Background Art

[0002] Ultra-high molecular weight polyethylene fibers have a high degree of orientation and crystallinity, and are one of the three high-performance fibers in this century. Their unique structure endows ultra-high molecular weight polyethylene fibers with excellent properties: such as good abrasion resistance and ultraviolet resistance; excellent tensile resistance, with strength superior to aramid and carbon fiber; resistant to strong acids, strong alkalis, and organic solvents; and long service life at low temperatures. Due to the excellent use performance of ultra-high molecular weight polyethylene fibers, they have been widely used in the fields of national defense military supplies, safety protection, ocean engineering, and fiber-reinforced composite materials.

[0003] However, while ultra-high molecular weight polyethylene fibers have excellent properties, their highly regular molecular structure and symmetry make them not react with other substances. For example, when dyeing ultra-high molecular weight polyethylene fibers, dye molecules cannot form hydrogen bonds or chemical bonds with them, and disperse dyes cannot be deposited inside the fiber molecules due to the plasticizing effect under high temperature and high pressure. Moreover, the strength of the fiber after being dyed with disperse dyes will be irreversibly damaged, and the strength and modulus will decrease with the increase of the treatment temperature.

[0004] When ultra-high molecular weight polyethylene fibers are used in the fields of fishing and ropes, etc., the method of coating with polymer glue is mostly adopted to improve the bonding and abrasion resistance of the fibers. Appropriate types of pigments can be added to the polymer glue to endow the ultra-high molecular weight polyethylene fibers with colorful colors during the sizing process. The conventional sizing colors are mainly red, yellow, and blue monochromes. After the fibers are woven into ropes, sizing treatment is carried out at a certain rate and temperature, and after baking, the polymer glue adheres to the surface of the ropes. This processing method has the defects of poor glue permeability, uneven rope color, and poor rubbing fastness during use, and the chromatogram is incomplete. Therefore, this processing method limits the in-depth development of ultra-high molecular weight polyethylene fibers.

[0005] CN106245136A discloses a colored ultra-high molecular weight polyethylene fiber and its preparation method. The coating dyes and pigments are added to the spinning dope, and the colored ultra-high molecular weight polyethylene fiber is prepared by the method of dope coloring. After dispersing dyes or pigments by ultrasonic crushing and air-flow crushing methods, the dyes or pigments are coated with coating materials under nitrogen protection and dispersed in an organic solvent to prepare a color paste with a certain concentration. Then the color paste is added to the spinning solution, and the colored ultra-high molecular weight polyethylene fiber is obtained through spinning, extraction, and multi-stage stretching. The colored ultra-high molecular weight polyethylene fiber prepared by using pigments as colorants by this method has bright colors and high color fastness, and also provides an industrially implementable method for coloring ultra-high molecular weight polyethylene fibers. However, this method requires dispersing dyes or pigments under nitrogen protection and then coating them, with a long process flow and many operation steps, which is difficult to control in actual production. Moreover, the crushing, coating, and adding equipment cannot be incorporated into the spinning system, making it difficult to achieve automated production. Summary of the Invention

[0006] One object of this solution is to provide a color paste for coloring ultra-high molecular weight polyethylene fibers, which is used in the preparation of colored ultra-high molecular weight polyethylene fibers by the dope coloring spinning process. The prepared colored fibers have bright colors and mechanical properties of high strength and high modulus. The second object of this solution is to provide a preparation method of the above color paste for coloring ultra-high molecular weight polyethylene fibers.

[0007] To achieve the above object, the solution is as follows:

[0008] A color paste for coloring ultra-high molecular weight polyethylene fibers, the color paste for coloring ultra-high molecular weight polyethylene fibers is composed of components with the following mass percentages based on the total weight of the color paste for coloring ultra-high molecular weight polyethylene fibers:

[0009] White oil 72.38% - 93.84%

[0010] Pigment 0.4% - 10.28%

[0011] Dispersant 4.11% - 12.3%

[0012] Emulsifier 0.4% - 2.05%

[0013] Antioxidant 1.23% - 2.05%

[0014] Ultra-high molecular weight polyethylene 0.02% - 0.04%.

[0015] Preferably, the kinematic viscosity of the white oil is 80 - 120 mPa·s.

[0016] Preferably, the pigment includes carbon black or organic pigments; the organic pigments include one or more of P.R.179, P.R.202, P.R.19, P.R.122, P.O.64, P.Y.181, P.Y.191, P.Y.183, P.Y.192, P.Y.110, P.B.15:1, P.B.15:4, and P.B.60.

[0017] Preferably, the dispersant is one of polycaprolactone polyol - polyethylenimine block copolymer type, acrylate polymer type, polyurethane, and polyester type.

[0018] Preferably, the emulsifier is one or more of lauryl alcohol polyoxyethylene ether, polyethylene oxide, and nonylphenol polyoxyethylene ether.

[0019] Preferably, the antioxidant is of type B225.

[0020] In a second aspect, a method for preparing the above - mentioned color paste for ultra - high molecular weight polyethylene fibers is provided, characterized in that the method comprises the following steps:

[0021] Add white oil, pigment, dispersant, and emulsifier into a sand mill, grind for 4 - 8 h to obtain a slurry suspension with a particle size ≤ 0.3 μm.

[0022] Place the slurry suspension and ultra - high molecular weight polyethylene powder in a heating kettle, heat to 60°C, add the antioxidant, continue to heat to 120 - 128°C, keep warm for 1.5 h, cool to 90°C, and transfer to a container for standby to obtain the color paste for ultra - high molecular weight polyethylene fibers.

[0023] Preferably, the raw materials and their mass percentages for preparing the color paste for ultra - high molecular weight polyethylene fibers are as follows:

[0024] White oil 76.86% - 88.87%

[0025] Pigment 0.4% - 7.25%

[0026] Dispersant 8.0% - 12.0%

[0027] Emulsifier 0.95% - 1.85%

[0028] Antioxidant 1.75% - 2.0%

[0029] Ultra - high molecular weight polyethylene 0.03% - 0.04%.

[0030] The beneficial effects of this solution are as follows:

[0031] The color paste is used in the preparation of colored ultra-high molecular weight polyethylene fibers by the spinning process of coloring the stock solution. The prepared colored fibers have bright colors, as well as high-strength and high-modulus mechanical properties, and small batch color differences. If a large number of different color pastes are prepared at one time, the cleaning steps caused by multiple color switches can be reduced, the solvent consumption can be reduced, and the efficiency of color paste preparation can be improved. Detailed implementation mode

[0032] The following further describes the implementation mode of this solution in detail. Obviously, the described embodiments are only a part of the embodiments of this solution, rather than an exhaustive list of all embodiments. It should be noted that, without conflict, the embodiments in this solution and the features in the embodiments can be combined with each other.

[0033] Due to the long process flow and many operation steps of the existing spinning process of coloring the stock solution, it is difficult to control in actual production, and the crushing, coating and adding equipment cannot be incorporated into the spinning system, making it difficult to achieve automated production. The inventor of this application provides a coloring paste for ultra-high molecular weight polyethylene fibers. When in use, the color paste, ultra-high molecular weight polyethylene powder, and white oil for spinning are uniformly mixed at 125°C, and then enter a twin-screw extruder, pass through a spinning component and a spinneret to obtain a gel precursor fiber with a certain color. Gel precursor fiber is a spinning method used for ultra-high molecular weight polyethylene fibers. The powdery raw material and the spinning solvent are mixed at a certain temperature and then formed after entering the screw extruder. The as-spun fiber obtained by this method is called gel precursor fiber or gel fiber.

[0034] A coloring paste for ultra-high molecular weight polyethylene fibers, which is composed of components with the following mass percentages based on the total weight of the coloring paste for ultra-high molecular weight polyethylene fibers:

[0035] White oil 72.38% - 93.84%

[0036] Pigment 0.4% - 10.28%

[0037] Dispersant 4.11% - 12.3%

[0038] Emulsifier 0.4% - 2.05%

[0039] Antioxidant 1.23% - 2.05%

[0040] Ultra-high molecular weight polyethylene 0.02% - 0.04%.

[0041] In one embodiment, the kinematic viscosity of the white oil is 80 - 120 mPa·s.

[0042] In one embodiment, the pigment includes carbon black or an organic pigment; the organic pigment includes one or more of P.R.179, P.R.202, P.R.19, P.R.122, P.O.64, P.Y.181, P.Y.191, P.Y.183, P.Y.192, P.Y.110, P.B.15:1, P.B.15:4, and P.B.60.

[0043] In one embodiment, the dispersant is one of polycaprolactone polyol - polyethylenimine block copolymer type, acrylate polymer type, polyurethane, and polyester type.

[0044] In one embodiment, the emulsifier is one or more of lauryl alcohol polyoxyethylene ether, polyethylene oxide, and nonylphenol polyoxyethylene ether.

[0045] In one embodiment, the antioxidant is of type B225.

[0046] Meanwhile, the present application also provides a preparation method of the above coloring paste, and the method includes the following steps:

[0047] Add white oil, pigment, dispersant, and emulsifier into a sand mill, grind for 4 - 8 h to obtain a slurry suspension with a particle size ≤ 0.3 μm;

[0048] Place the slurry suspension and ultra - high - molecular - weight polyethylene powder in a heating kettle, heat to 60 °C, add the antioxidant, continue to heat to 120 - 128 °C, keep warm for 1.5 h, cool to 90 °C, and transfer to a container for standby to obtain the coloring paste for ultra - high - molecular - weight polyethylene fibers.

[0049] The raw materials and their mass percentages for preparing the coloring paste are as follows:

[0050] White oil 76.86% - 88.87%

[0051] Pigment 0.4% - 7.25%

[0052] Dispersant 8.0% - 12.0%

[0053] Emulsifier 0.95% - 1.85%

[0054] Antioxidant 1.75% - 2.0%

[0055] Ultra - high - molecular - weight polyethylene 0.03% - 0.04%.

[0056] The following is an illustration of the present application through specific examples.

[0057] Example 1

[0058] Preparation of the coloring paste for black ultra - high - molecular - weight polyethylene fiber dope

[0059] a) Add 46508.4 g of white oil, 2664 g of carbon black, 2970 g of dispersant, and 918 g of emulsifier into a sand mill, and grind for 4.5 h to obtain a slurry suspension;

[0060] b) Use a pipette to suck 3 ml of the suspension and dilute it in 20 ml of white oil. Then suck 5 ml of the diluted color liquid and drop it on a qualitative filter paper to make it evenly diffuse on the filter paper. There are no carbon black particles on the filter paper, and the carbon black evenly diffuses with the white oil on the filter paper with clear boundaries, indicating that the carbon black is fully ground and evenly distributed in the white oil;

[0061] c) Mix 54 kg of the slurry suspension in b) with 21.6 g of ultra-high molecular weight polyethylene powder with a viscosity-average molecular weight of 5 million, place it in a shear kettle and stir for 1 h. Then pump the material in the stirring kettle into a heating kettle, heat it to 60 °C, add 918 g of antioxidant, continue to heat to 125 - 128 °C and keep it warm for 1.5 h, and then cool it to 90 °C and put it into a container for standby.

[0062] Example 2

[0063] Preparation of red ultra-high molecular weight polyethylene fiber

[0064] a) Add 46201.2 g of white oil, 1443 g of red, 135 g of yellow, 4212 g of dispersant, and 1026 g of emulsifier into a sand mill, and grind for 3 h to obtain a slurry suspension;

[0065] b) Use a pipette to suck 2 ml of the suspension and dilute it in 20 ml of white oil. Then suck 5 ml of the diluted color liquid and drop it on a qualitative filter paper to make it evenly diffuse on the filter paper. There are no red particles on the filter paper, and the color evenly diffuses with the white oil on the filter paper with clear boundaries, indicating that the pigment is fully ground and evenly distributed in the white oil;

[0066] c) Mix 54 kg of the slurry suspension in b) with 10.8 g of ultra-high molecular weight polyethylene powder with a viscosity-average molecular weight of 4 million, place it in a shear kettle and stir for 1 h. Then pump the material in the stirring kettle into a heating kettle, heat it to 60 °C, add 972 g of antioxidant, continue to heat to 120 - 125 °C and keep it warm for 1.5 h, and then cool it to 90 °C and put it into a container for standby;

[0067] d) Mix white oil, the color paste prepared in c), ultra-high molecular weight polyethylene powder, and antioxidant in a certain proportion, stir at room temperature for 30 - 45 min, then heat it to 115 - 118 °C at a heating rate of 1.5 °C / min, keep it warm for 120 min, enter a shear kettle and shear for 15 min to prepare a raw material mixture, and pump the mixture into a co-rotating twin-screw extruder;

[0068] e) After the raw materials enter the twin-screw extruder, control the rotation speed of the twin-screw extruder at 160 - 210 r / min, and gradually increase the screw temperature to 299 °C. After passing through the melt filter, filter screen, and spinneret plate, the red ultra-high molecular weight polyethylene frozen gel filaments are spun.

[0069] f) After the frozen gel filaments are balanced for 48 h and reach equilibrium with the white oil after phase separation and shrinkage, they are stretched and formed after passing through the beam rack, series extractor, series drying oven, and drawing hot box to obtain red ultra-high molecular weight polyethylene fibers of a certain specification.

[0070] g) The red fiber obtained by the colorant preparation method and the coloration process of the stock solution is compared with the commercially available red ultra-high molecular weight polyethylene fiber on the Datacolor colorimeter. Its color light intensity is 112.3%, indicating that the fiber obtained in this example has a more vivid color.

[0071] The structure of the colorant prepared by the present invention determines that when it is used on the color-developing substance, the substance can have a vivid color.

[0072] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly explaining the present invention, rather than limiting the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or variations can be made on the basis of the above description. It is impossible to list all the implementation manners here. Any obvious changes or variations derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A preparation method of a coloring paste for ultra-high molecular weight polyethylene fibers, characterized in that, The method comprises the following steps: Add white oil, pigment, dispersant, and emulsifier into a sand mill, grind for 4 - 8 h to obtain a slurry suspension with a particle size ≤ 0.3 μm; Place the slurry suspension and ultra-high molecular weight polyethylene powder in a heating kettle, heat to 60 °C, add an antioxidant, continue heating to 120 - 128 °C, keep warm for 1.5 h, cool to 90 °C, and transfer to a container for standby to obtain a colored paste for ultra-high molecular weight polyethylene fibers; The colored paste for ultra-high molecular weight polyethylene fibers is composed of components with the following mass percentages based on the total weight of the colored paste for ultra-high molecular weight polyethylene fibers: White oil 72.38% - 93.84% Pigment 0.4% - 10.28% Dispersant 4.11% - 12.3% Emulsifier 0.4% - 2.05% Antioxidant 1.23% - 2.05% Ultra-high molecular weight polyethylene 0.02% - 0.04%; Among them, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 4 million; The kinematic viscosity of the white oil is 80 - 120 mPa·s; The organic pigment includes one or more of P.R.179, P.R.202, P.R.19, P.R.122, P.O.64, P.Y.181, P.Y.191, P.Y.183, P.Y.192, P.Y.110, P.B.15:1, P.B.15:4, and P.B.60; The dispersant is one of polycaprolactone polyol - polyethyleneimine block copolymer type, acrylate polymer type, polyurethane, and polyester type; The emulsifier is one or more of lauryl alcohol polyoxyethylene ether, polyethylene oxide, and nonylphenol polyoxyethylene ether.

2. The color paste for coloring ultra-high molecular weight polyethylene fibers according to claim 1, wherein The antioxidant is of type B225.

3. A method for preparing colored ultra-high molecular weight polyethylene fibers, characterized in that, Using the colored paste according to any one of claims 1 - 2, it comprises the following steps: a) Mix white oil, the colored paste according to any one of claims 1 - 2, ultra-high molecular weight polyethylene powder, and antioxidant, stir at room temperature for 30 - 45 min, then heat up to 115 - 118 °C at a heating rate of 1.5 °C / min, keep warm for 120 min, enter a shear kettle for shearing for 15 min to prepare a raw material mixture, and pump the mixture into a co-rotating twin-screw extruder; b) After the raw materials enter the twin-screw extruder, control the rotation speed of the twin-screw extruder at 160 - 210 r / min, gradually increase the screw temperature to 299 °C, and spin through a melt filter, filter screen, and spinneret to obtain red ultra-high molecular weight polyethylene frozen raw filaments; c) The frozen raw filaments are balanced for 48 h, undergo phase separation and shrinkage with white oil to reach equilibrium, and then are stretched and formed after passing through a beam stand, a series of extraction machines, a series of drying ovens, and a drawing hot box to obtain red ultra-high molecular weight polyethylene fibers of a certain specification.