Polyurethane bristle material for cleaning brush and preparation method thereof

Abstract

The invention relates to a polyurethane bristle material for a cleaning brush and a preparation method thereof, belonging to the technical field of polymer composite materials; the bristle material comprises, by weight, 100 parts of a thermoplastic polyurethane elastomer, 4.6-5.5 parts of a surface modifier, 9-12 parts of a metal oxide filler, 0.6-0.7 parts of a lubricant and 0.1-0.13 parts of an antioxidant, wherein the surface modifier is obtained by adding diallylamine and alkyldithiol to form a chain compound, which is then terminated by highly active hydroxyethyl methacrylate to prepare an intermediate, and then p-fluorobenzoyl chloride reacts with an imine group in a molecular chain of the intermediate to introduce a fluoroamide structure modification, so as to obtain the surface modifier, which interacts with the metal oxide filler to give the bristle material excellent mechanical properties and surface properties.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer composite materials, and in particular relates to a polyurethane bristle material for a cleaning brush and a preparation method thereof. Background Art

[0002] Traditional brush bristle materials mainly include animal hair and natural plant fibers, but the performance of these materials is unstable and difficult to meet the needs of industrial production. With the development of science and technology, artificial fibers such as polyethylene, polyurethane, nylon, etc. are widely used in brush bristle materials. Among them, polyurethane, as a general polymer material with diverse structures, exhibits excellent properties in various application fields, such as high processability, flexibility and elasticity. The application of polyurethane materials in the field of brush bristle manufacturing has attracted more and more attention.

[0003] However, the high friction coefficient between polyurethane and most materials results in insufficient friction resistance of the bristle material. In addition, polyurethane bristles have insufficient corrosion resistance. The brushing conditions are mostly acidic or alkaline, resulting in insufficient stability of the bristles, which greatly limits the application of polyurethane bristles. Summary of the invention

[0004] In order to solve the technical problems mentioned in the background technology, the object of the present invention is to provide a polyurethane bristle material for a cleaning brush and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A polyurethane bristle material for a cleaning brush, comprising, by weight:

[0007] 100 parts of thermoplastic polyurethane elastomer, 4.6-5.5 parts of surface modifier, 9-12 parts of metal oxide filler, 0.6-0.7 parts of lubricant and 0.1-0.13 parts of antioxidant;

[0008] The surface modifier is prepared by the following method:

[0009] Step A1: Mix diallylamine, alkyl dithiol, benzoin dimethyl ether, azobisisobutyronitrile and dioxane, heat to 85-95°C, stir at 40-60 rpm and heat at 150-200 W / m 2 The mixture was subjected to ultraviolet irradiation for 3-4 hours, and then hydroxyethyl methacrylate was added to continue the reaction for 1.2-1.6 hours. After the reaction was completed, the dioxane was removed by vacuum rotary evaporation to obtain an intermediate;

[0010] Further, the amount ratio of diallylamine, alkyl dithiol, hydroxyethyl methacrylate, benzoin dimethyl ether, azobisisobutyronitrile and dioxane is 0.1 mol: 0.11-0.12 mol: 25-30 mmol: 0.15-0.22 g: 0.1-0.13 g: 60-75 mL, and under the action of initiation, diallylamine and alkyl dithiol are added to form a chain compound, which is then capped by highly active hydroxyethyl methacrylate;

[0011] Preferably, the alkyl dithiol is one or more of 1,3-propanedithiol, 1,8-octanedithiol and 1,10-decanedithiol.

[0012] Step A2: The intermediate, triethylamine and anhydrous toluene are mixed, the temperature is controlled to be no higher than 20°C in an ice-water bath, dry nitrogen is introduced for protection, p-fluorobenzoyl chloride is slowly added to react for 2-2.5h, and then the temperature is raised to 70-80°C and the reaction is continued for 1-1.5h. After the reaction is completed, the toluene is removed by rotary evaporation to obtain a surface modifier;

[0013] Furthermore, the usage ratio of the intermediate, p-fluorobenzoyl chloride, triethylamine and anhydrous toluene is 10 g: 8-14 mmol: 3-5 mL: 35-50 mL, and p-fluorobenzoyl chloride reacts with the imine group in the intermediate molecular chain to introduce fluoroamide structure modification.

[0014] Preferably, the thermoplastic polyurethane elastomer is selected from polyester polyurethane, which has good toughness and elasticity.

[0015] Preferably, the metal oxide filler is selected from alumina micropowder with a fineness of not less than 500 mesh, low cost and good wear resistance.

[0016] Preferably, the lubricant is selected from erucamide, which has good lubricity between the polyester polyurethane elastomer and the alumina powder, and is beneficial to improving the surface smoothness of the bristles.

[0017] Preferably, the antioxidant is selected from a compound of antioxidant 1010 and antioxidant 168, and has good resistance to light and heat aging.

[0018] A method for preparing a polyurethane bristle material for a cleaning brush comprises the following steps:

[0019] Step S1: Mix all the raw materials in a high-speed mixer, transfer them into a mixer and mix them at 170° C. until the torque is stable, and cut the materials into pellets to prepare composite masterbatch;

[0020] Step S2: melt-extrude the composite masterbatch at 200±5°C, spin the mixture, draw and cool it to form it, and cut it to obtain the polyurethane bristle material.

[0021] Beneficial effects of the present invention:

[0022] The brush bristle material of the present invention uses a traditional polyester-type polyurethane elastomer as a matrix, and adds a homemade surface modifier to interact with a metal oxide filler to give the brush bristle material excellent mechanical properties and surface properties; the surface modifier is formed by the addition of diallylamine and alkyl dithiol to form a chain compound, and then is capped with highly active hydroxyethyl methacrylate to prepare an intermediate, and then p-fluorobenzoyl chloride reacts with the imine group in the intermediate molecular chain to introduce a fluoroamide structure modification, thereby obtaining the surface modifier; the fluorine structure introduced on the molecular side chain of the surface modifier enables it to have a certain segregation effect in the polyurethane matrix, migrates to the near-surface layer for enrichment during the melt spinning process of the brush bristle material, and then gives the bristles good surface properties, and specific indicators include relatively The high water contact angle makes it difficult for the brush to be contaminated during the brushing process, making the bristles easy to clean. It also includes a lower acid, alkali, and solvent corrosion weight loss rate, as well as a lower friction coefficient, so that the bristles can maintain good stability when brushed in different media, which is beneficial to increasing the life of the bristles. In addition, the surface modifier of the present invention is different from the existing fluoride composite materials. It is a low molecular weight polymer with a moderate mobility during the melt molding process and can form a uniform enrichment layer on the surface. The sulfur-nitrogen structure in its main chain forms a complex with the compounded metal oxide filler, which effectively improves the bonding strength between the surface modifier and the matrix polyurethane, so that the bristle material has excellent mechanical properties and a higher bending recovery rate, further improving the stability of the bristles from the physical properties. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] Example 1, preparing a polyurethane bristle material for a cleaning brush, the specific implementation process is as follows:

[0025] (1) Preparation of surface modifier

[0026] Step A1: Mix diallylamine, alkyl dithiol, benzoin dimethyl ether, azobisisobutyronitrile and dioxane, heat to 95°C, stir at 60 rpm and apply 200 W / m 2The reaction was carried out under ultraviolet irradiation for 3 hours, and then hydroxyethyl methacrylate was added to continue the reaction for 1.2 hours, wherein the amount ratio of diallylamine, alkyl dithiol, hydroxyethyl methacrylate, benzoin dimethyl ether, azobisisobutyronitrile and dioxane was 0.1 mol: 0.12 mol: 30 mmol: 0.15 g: 0.13 g: 75 mL, the alkyl dithiol was 1,8-octanedithiol, and the reaction was completed by vacuum rotary evaporation to remove dioxane to obtain an intermediate.

[0027] Step A2: Take the intermediate, triethylamine and anhydrous toluene, mix them, control the temperature at 20°C in an ice-water bath, introduce dry nitrogen for protection, slowly add p-fluorobenzoyl chloride to react for 2 hours, then raise the temperature to 80°C and continue the reaction for 1 hour, wherein the amount ratio of the intermediate, p-fluorobenzoyl chloride, triethylamine and anhydrous toluene is 10g:14mmol:5mL:50mL. After the reaction is completed, remove toluene by rotary evaporation to obtain a surface modifier.

[0028] (2) Preparation of polyurethane bristle materials

[0029] Ingredients: The raw materials are taken by weight, 100 parts of thermoplastic polyurethane elastomer, 1180A polyester elastomer is used in the implementation process, provided by BASF Corporation; 4.6 parts of surface modifier, prepared by this embodiment; 9 parts of metal oxide filler, 500 mesh alumina powder is used in the implementation process, provided by Gongyi Xinyuan Friction Material Co., Ltd.; 0.6 parts of lubricant, industrial grade erucic acid amide is used in the implementation process, provided by Haimen Hualong Oil Additive Factory Co., Ltd.; 0.1 parts of antioxidant, antioxidant 1010 and antioxidant 168 are compounded in a weight ratio of 2:1 in the implementation process, both provided by BASF Corporation.

[0030] Step S1: Add the above raw materials into a high-speed mixer and mix at 600 rpm for 30 minutes, then transfer to a mixer and mix at 170° C. for 12 minutes. When the torque tends to be stable, cut the material into pellets to prepare composite masterbatch.

[0031] Step S2: melt-extrude the composite masterbatch at 200±5°C, spin the mixture, draw and cool it to form it, and cut it to obtain the polyurethane bristle material.

[0032] Example 2, preparing a polyurethane bristle material for a cleaning brush, the specific implementation process is as follows:

[0033] (1) Preparation of surface modifier

[0034] Step A1: Mix diallylamine, alkyl dithiol, benzoin dimethyl ether, azobisisobutyronitrile and dioxane, heat to 85°C, stir at 40 rpm and apply 150 W / m 2The reaction was carried out under ultraviolet irradiation for 4 hours, and then hydroxyethyl methacrylate was added to continue the reaction for 1.6 hours, wherein the dosage ratio of diallylamine, alkyl dithiol, hydroxyethyl methacrylate, benzoin dimethyl ether, azobisisobutyronitrile and dioxane was 0.1 mol: 0.11 mol: 25 mmol: 0.22 g: 0.1 g: 60 mL, and the alkyl dithiol was 1,3-propanedithiol and 1,8-octanedithiol in a molar ratio of 2:1. After the reaction was completed, the dioxane was removed by reduced pressure rotary evaporation to obtain an intermediate.

[0035] Step A2: Take the intermediate, triethylamine and anhydrous toluene, mix them, control the temperature at 10°C in an ice-water bath, introduce dry nitrogen for protection, slowly add p-fluorobenzoyl chloride to react for 2.5 hours, then raise the temperature to 70°C and continue the reaction for 1.5 hours, wherein the amount ratio of the intermediate, p-fluorobenzoyl chloride, triethylamine and anhydrous toluene is 10g:8mmol:3mL:35mL. After the reaction is completed, remove toluene by rotary evaporation to obtain a surface modifier.

[0036] (2) Preparation of polyurethane bristle materials

[0037] Ingredients: The raw materials are taken by weight, 100 parts of thermoplastic polyurethane elastomer, 1180A polyester elastomer is used in the implementation process, provided by BASF Corporation; 5.5 parts of surface modifier, prepared by this embodiment; 12 parts of metal oxide filler, 500 mesh alumina powder is used in the implementation process, provided by Gongyi Xinyuan Friction Material Co., Ltd.; 0.7 parts of lubricant, industrial grade erucamide is used in the implementation process, provided by Haimen Hualong Oil Additive Factory Co., Ltd.; 0.13 parts of antioxidant, antioxidant 1010 and antioxidant 168 are compounded in a weight ratio of 2:1 in the implementation process, both provided by BASF Corporation.

[0038] Step S1: Add the above raw materials into a high-speed mixer and mix at 600 rpm for 30 minutes, then transfer to a mixing kettle and mix at 170° C. for 14 minutes. When the torque tends to be stable, the material is discharged and pelletized to prepare a composite masterbatch.

[0039] Step S2: melt-extrude the composite masterbatch at 200±5°C, spin the mixture, draw and cool it to form it, and cut it to obtain the polyurethane bristle material.

[0040] Example 3, preparing a polyurethane bristle material for a cleaning brush, the specific implementation process is as follows:

[0041] (1) Preparation of surface modifier

[0042] Step A1: Mix diallylamine, alkyl dithiol, benzoin dimethyl ether, azobisisobutyronitrile and dioxane, heat to 90°C, stir at 60 rpm and 180 W / m 2The reaction was carried out under ultraviolet irradiation for 3.5 hours, and then hydroxyethyl methacrylate was added to continue the reaction for 1.4 hours, wherein the dosage ratio of diallylamine, alkyl dithiol, hydroxyethyl methacrylate, benzoin dimethyl ether, azobisisobutyronitrile and dioxane was 0.1 mol: 0.11 mol: 28 mmol: 0.18 g: 0.11 g: 70 mL, and the alkyl dithiol was 1,3-propanedithiol and 1,10-decanedithiol in a molar ratio of 2:1. After the reaction was completed, the dioxane was removed by reduced pressure rotary evaporation to obtain an intermediate.

[0043] Step A2: Take the intermediate, triethylamine and anhydrous toluene, mix them, control the temperature at 15°C in an ice-water bath, introduce dry nitrogen for protection, slowly add p-fluorobenzoyl chloride to react for 2.3 hours, then raise the temperature to 75°C and continue the reaction for 1.3 hours, wherein the amount ratio of the intermediate, p-fluorobenzoyl chloride, triethylamine and anhydrous toluene is 10g:10mmol:4mL:40mL. After the reaction is completed, remove toluene by rotary evaporation to obtain a surface modifier.

[0044] (2) Preparation of polyurethane bristle materials

[0045] Ingredients: The raw materials are taken by weight, 100 parts of thermoplastic polyurethane elastomer, 1180A polyester elastomer is used in the implementation process, provided by BASF Corporation; 5.2 parts of surface modifier, prepared by this embodiment; 11 parts of metal oxide filler, 500 mesh alumina powder is used in the implementation process, provided by Gongyi Xinyuan Friction Material Co., Ltd.; 0.7 parts of lubricant, industrial grade erucic acid amide is used in the implementation process, provided by Haimen Hualong Oil Additive Factory Co., Ltd.; 0.11 parts of antioxidant, antioxidant 1010 and antioxidant 168 are compounded in a weight ratio of 2:1 in the implementation process, both provided by BASF Corporation.

[0046] Step S1: Add the above raw materials into a high-speed mixer and mix at 600 rpm for 30 minutes, then transfer to a mixing kettle and mix at 170° C. for 14 minutes. When the torque tends to be stable, the material is discharged and pelletized to prepare a composite masterbatch.

[0047] Step S2: melt-extrude the composite masterbatch at 200±5°C, spin the mixture, draw and cool it to form it, and cut it to obtain the polyurethane bristle material.

[0048] Example 4, preparing a polyurethane bristle material for a cleaning brush, the specific implementation process is as follows:

[0049] (1) Preparation of surface modifier

[0050] Step A1: Mix diallylamine, alkyl dithiol, benzoin dimethyl ether, azobisisobutyronitrile and dioxane, heat to 90°C, stir at 60 rpm and 200 W / m 2The reaction was carried out under ultraviolet irradiation for 3.2 hours, and then hydroxyethyl methacrylate was added to continue the reaction for 1.5 hours, wherein the dosage ratio of diallylamine, alkyl dithiol, hydroxyethyl methacrylate, benzoin dimethyl ether, azobisisobutyronitrile and dioxane was 0.1 mol: 0.12 mol: 25 mmol: 0.2 g: 0.12 g: 70 mL, and the alkyl dithiol was 1,3-propanedithiol, 1,8-octanedithiol and 1,10-decanedithiol in a molar ratio of 1:2:1. After the reaction was completed, the dioxane was removed by reduced pressure rotary evaporation to obtain an intermediate.

[0051] Step A2: Take the intermediate, triethylamine and anhydrous toluene, mix them, control the temperature at 15°C in an ice-water bath, introduce dry nitrogen for protection, slowly add p-fluorobenzoyl chloride to react for 2.5 hours, then raise the temperature to 70°C and continue the reaction for 1.3 hours, wherein the amount ratio of the intermediate, p-fluorobenzoyl chloride, triethylamine and anhydrous toluene is 10g:12mmol:5mL:45mL. After the reaction is completed, remove toluene by rotary evaporation to obtain a surface modifier.

[0052] (2) Preparation of polyurethane bristle materials

[0053] Ingredients: The raw materials are taken by weight, 100 parts of thermoplastic polyurethane elastomer, 1180A polyester elastomer is used in the implementation process, provided by BASF Corporation; 5 parts of surface modifier, prepared by this embodiment; 10.5 parts of metal oxide filler, 500 mesh alumina powder is used in the implementation process, provided by Gongyi Xinyuan Friction Material Co., Ltd.; 0.6 parts of lubricant, industrial grade erucic acid amide is used in the implementation process, provided by Haimen Hualong Oil Additive Factory Co., Ltd.; 0.11 parts of antioxidant, antioxidant 1010 and antioxidant 168 are compounded in a weight ratio of 2:1 in the implementation process, both provided by BASF Corporation.

[0054] Step S1: Add the above raw materials into a high-speed mixer and mix at 600 rpm for 30 minutes, then transfer to a mixing kettle and mix at 170° C. for 13 minutes. When the torque tends to be stable, cut the material into pellets to prepare composite masterbatch.

[0055] Step S2: melt-extrude the composite masterbatch at 200±5°C, spin the mixture, draw and cool it to form it, and cut it to obtain the polyurethane bristle material.

[0056] Comparative Example

[0057] This comparative example refers to Example 4, except that the surface modifier is replaced with copolymerized polyvinylidene fluoride PVDF-HFP powder of the same weight portion, with a brand number of 2750-00, and the rest of the implementation process is exactly the same.

[0058] Take samples from the above bristle materials and perform tensile performance test according to GB / T 1040.2-2022 standard; perform bending performance test according to GB19342-2013 standard;

[0059] In order to facilitate the detection of the surface properties of the bristle material, the composite masterbatch prepared above was hot-pressed into a sheet sample at 200°C and a pressure of 1.5MPa using a flat vulcanizer; the sampling was tested for surface friction performance according to GB / T 3960-2016 standard; the surface water contact angle was tested according to GB / T 30693-2014 standard; the above samples were placed in a 5% sulfuric acid solution, a 5% sodium hydroxide solution and a 20% ethanol solution by volume, respectively, and immersed at room temperature for 72 hours, and the weight loss rate before and after immersion was weighed and calculated to characterize the corrosion resistance; the specific test results are shown in Table 1:

[0060] Table 1

[0061]

[0062] It can be seen from the test results in Table 1 that the bristle material prepared in the embodiment has excellent mechanical properties and a high bending recovery rate compared to the comparative example, which is beneficial to the stability of the bristle structure and maintains good corrosion resistance in acidic and alkaline and solvent environments.

[0063] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0064] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A polyurethane bristle material for a cleaning brush, characterized in that: The composition comprises, by weight: 100 parts of thermoplastic polyurethane elastomer, 4.6-5.5 parts of surface modifier, 9-12 parts of metal oxide filler, 0.6-0.7 parts of lubricant and 0.1-0.13 parts of antioxidant; The surface modifier is prepared by the following method: Step A1: diallylamine, alkyl dithiol, benzoin dimethyl ether, azobisisobutyronitrile and dioxane are mixed, heated to 85-95°C, stirred and irradiated with ultraviolet light for 3-4 hours, and then hydroxyethyl methacrylate is added to continue the reaction for 1.2-1.6 hours. After the reaction is completed, the dioxane is removed by vacuum rotary evaporation to obtain an intermediate; Step A2: Mix the intermediate, triethylamine and anhydrous toluene, control the temperature in an ice-water bath to no higher than 20°C, introduce dry nitrogen for protection, slowly add p-fluorobenzoyl chloride to react for 2-2.5h, then raise the temperature to 70-80°C and continue the reaction for 1-1.5h. After the reaction is completed, remove toluene by rotary evaporation to obtain a surface modifier.

2. The polyurethane bristle material for a cleaning brush according to claim 1, characterized in that: The usage ratio of diallylamine, alkyl dithiol, hydroxyethyl methacrylate, benzoin dimethyl ether, azobisisobutyronitrile and dioxane is 0.1 mol: 0.11-0.12 mol: 25-30 mmol: 0.15-0.22 g: 0.1-0.13 g: 60-75 mL.

3. The polyurethane bristle material for a cleaning brush according to claim 2, characterized in that: The alkyldithiol is one or more of 1,3-propanedithiol, 1,8-octanedithiol and 1,10-decanedithiol.

4. The polyurethane bristle material for a cleaning brush according to claim 2, characterized in that: The usage ratio of the intermediate, p-fluorobenzoyl chloride, triethylamine and anhydrous toluene is 10 g: 8-14 mmol: 3-5 mL: 35-50 mL.

5. The polyurethane bristle material for a cleaning brush according to claim 1, characterized in that: Thermoplastic polyurethane elastomer is a polyester polyurethane.

6. The polyurethane bristle material for a cleaning brush according to claim 1, characterized in that: The metal oxide filler is alumina micropowder with a fineness of not less than 500 meshes.

7. The polyurethane bristle material for a cleaning brush according to claim 1, characterized in that: The lubricant is erucamide.

8. The polyurethane bristle material for a cleaning brush according to claim 1, characterized in that: The antioxidant is compounded by antioxidant 1010 and antioxidant 168.

9. A method for preparing a polyurethane bristle material for a cleaning brush according to any one of claims 1 to 8, characterized in that: The steps include: Step S1: Mix all the raw materials in a high-speed mixer, transfer them into a mixer and mix them at 170° C. until the torque is stable, and cut the materials into pellets to prepare composite masterbatch; Step S2: melt-extrude the composite masterbatch at 200±5°C to form a filament, draw and cool it to form it, and cut it to obtain a polyurethane brush bristle material.

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