Hydrogenated nitrile rubber wear-resistant composition and method for preparing same, polyolefin composite and method for preparing same

Abstract

This invention belongs to the field of materials technology and discloses a hydrogenated nitrile butadiene rubber wear-resistant composition and its preparation method, as well as a polyolefin composite material and its preparation method. The composition contains: component A: hydrogenated nitrile butadiene rubber; component B: wear-resistant filler; component C: modifier, which is a graft-modified polyolefin containing functional groups. Based on a total content of 100 wt% for components A, B, and C, the content of component A is 10-80 wt%, the content of component B is 10-60 wt%, and the content of component C is 1-30 wt%. The composite material contains: component I: the above-mentioned hydrogenated nitrile butadiene rubber wear-resistant composition; component II: polyolefin, which is polypropylene or polyethylene, and is of the same type as the polyolefin used in the modifier in component I. The composite material of this invention exhibits excellent impact and wear resistance properties, with a room temperature impact strength exceeding 20 kJ / m. 2 The wear and tear is less than 40mg.

Description

Technical Field

[0001] This invention belongs to the field of materials technology, specifically relating to a hydrogenated nitrile butadiene rubber wear-resistant composition and its preparation method, as well as a polyolefin composite material modified by the hydrogenated nitrile butadiene rubber wear-resistant composition and its preparation method. Background Technology

[0002] Hydrogenated nitrile butadiene rubber (HNBR) is widely used due to its excellent impact resistance, abrasion resistance, high temperature resistance, and corrosion resistance. The acrylonitrile units in its molecular chain provide excellent oil resistance and high tensile strength, while the hydrogenated butadiene units, similar to ethylene propylene rubber (EPR) segments, offer good heat resistance, aging resistance, abrasion resistance, and low-temperature performance. However, because it is difficult to plasticize and is incompatible with most plastics, it is relatively difficult to apply in the field of modified plastics or in the preparation of polymer composites.

[0003] Polyolefins generally refer to a class of thermoplastic resins obtained by the individual polymerization or copolymerization of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene, as well as certain cyclic olefins. They are a class of polymeric materials with large production volumes and wide applications. Polyethylene (PE) and polypropylene (PP) are the most important among them. However, these materials often have poor abrasion resistance, limiting their application range.

[0004] Combining the superior properties of HNBR with common polyolefins (such as PE and PP) could significantly improve the overall performance of PE and PP. However, HNBR is a polar polymer with poor compatibility with non-polar polymers like PE and PP. Conventional methods struggle to form an effective dispersed phase of rubber and inorganic fillers within the polyolefin matrix, resulting in suboptimal mechanical properties of the composite material. Furthermore, while HNBR exhibits good abrasion resistance, composites obtained by direct blending with polyolefins show poor abrasion resistance because HNBR and polyolefins form a phase-separated structure, preventing the HNBR particles within the composite from utilizing their abrasion-resistant characteristics.

[0005] No relevant patents or literature have been found regarding wear-resistant HNBR / polyolefin composite materials. Therefore, there is an urgent need to develop a wear-resistant HNBR / polyolefin composite material with excellent performance. Summary of the Invention

[0006] Based on the above-mentioned situation of the prior art, the purpose of the present invention is to provide a hydrogenated nitrile butadiene rubber wear-resistant composition and its preparation method, and a polyolefin composite material and its preparation method. The polyolefin composite material has excellent wear resistance and impact resistance through modification with the hydrogenated nitrile butadiene rubber wear-resistant composition.

[0007] A first aspect of the present invention provides a hydrogenated nitrile butadiene rubber abrasion-resistant composition, the composition comprising:

[0008] Component A: Hydrogenated butyronitrile;

[0009] Component B: Wear-resistant filler;

[0010] Component C: Modifier, wherein the modifier is a graft-modified polyolefin containing functional groups;

[0011] Based on a total content of 100 wt% for components A, B, and C, the content of component A is 10-80 wt%, the content of component B is 10-60 wt%, and the content of component C is 1-30 wt%.

[0012] A second aspect of the present invention provides a method for preparing the above-described hydrogenated nitrile butadiene rubber abrasion-resistant composition, the method comprising:

[0013] 1) Mix and melt hydrogenated nitrile butyrate and modifier, then add wear-resistant filler and mix evenly;

[0014] 2) After crushing the mixture obtained in step 1), add a vulcanizing agent, and after dynamic vulcanization, extrude and granulate to obtain the composition.

[0015] A third aspect of the present invention provides a polyolefin composite material comprising:

[0016] Component I: The above-mentioned hydrogenated nitrile butadiene rubber abrasion-resistant composition;

[0017] Component II: Polyolefin, wherein the polyolefin is polypropylene or polyethylene and is of the same type as the polyolefin of the modifier in Component I;

[0018] Based on a total content of 100 wt% for components I and II, the content of component I is 5-60 wt% and the content of component II is 40-95 wt%.

[0019] A fourth aspect of the present invention provides a method for preparing the above-described polyolefin composite material, the method comprising:

[0020] (1) Mix the hydrogenated butadiene nitrile rubber abrasion-resistant composition and polyolefin evenly;

[0021] (2) The mixture obtained in step (1) is extruded and granulated to obtain a composite material.

[0022] This invention, by introducing appropriate hydrogenated nitrile butadiene rubber, wear-resistant fillers, and modifiers into polyolefins, enables the preparation of hydrogenated nitrile butadiene rubber wear-resistant compositions without the need for organic solvent blending. These compositions exhibit stable phase structures, uniform filler dispersion, and good compatibility among different components. When used in composite materials modified from polyolefins, these wear-resistant compositions demonstrate excellent impact and wear resistance, with room temperature impact strength exceeding 20 kJ / m.2 With a mass wear rate of less than 40mg, it has a wider range of applications. The preparation method of this invention is safe and environmentally friendly, and it is convenient and effective in improving the material's performance.

[0023] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0024] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0025] According to a first aspect of the present invention, a hydrogenated nitrile butadiene rubber abrasion-resistant composition is provided, the composition comprising:

[0026] Component A: Hydrogenated butyronitrile;

[0027] Component B: Wear-resistant filler;

[0028] Component C: Modifier, wherein the modifier is a graft-modified polyolefin containing functional groups;

[0029] Based on a total content of 100 wt% for components A, B, and C, the content of component A is 10-80 wt%, the content of component B is 10-60 wt%, and the content of component C is 1-30 wt%.

[0030] In this invention, the Mooney viscosity at Z100℃ (1+4) of the hydrogenated butyronitrile can be 50-90, where Z is the rotational viscosity, 1 is the preheating time of 1 min, 4 is the rotation time of 4 min, and 100℃ is the test temperature of 100℃; the acrylonitrile content of the hydrogenated butyronitrile can be 20-50%, for example, but not limited to 30-36%; and the saturation of the hydrogenated butyronitrile can be 85-99%, for example, but not limited to 85-93%, 87-93%, and 88-97%.

[0031] According to the present invention, the wear-resistant filler may be ceramic powder and / or fiber powder.

[0032] Specifically, the ceramic powder may be selected from at least one of silicon dioxide, titanium dioxide and aluminum oxide, with an average particle size of 1-100 μm;

[0033] The fiber powder can be selected from at least one of ultra-high molecular weight polyethylene fiber, carbon fiber and glass fiber, with an average fiber diameter of 1-50 μm and a length of 1-20 mm.

[0034] In this invention, the polyolefin of the modifier can be polypropylene or polyethylene. The functional groups of the modifier can be selected from at least one of maleic anhydride (MAH), styrene (St), glycidyl methacrylate (GMA), methyl methacrylate (MMA), and butyl acrylate.

[0035] The grafting rate of the modifier can be 0.5-5 wt%, preferably 0.8-4 wt%, and more preferably 0.8-3 wt%.

[0036] Preferably, based on a total content of 100 wt% for components A, B, and C, the content of component A is 20-70 wt%, the content of component B is 20-60 wt%, and the content of component C is 5-30 wt%. More preferably, based on a total content of 100 wt% for components A, B, and C, the content of component A is 30-60 wt%, the content of component B is 20-50 wt%, and the content of component C is 5-20 wt%.

[0037] According to the present invention, the composition further comprises component D: a processing aid, wherein the processing aid is an antioxidant and / or an anti-aging agent, and the content of component D is 0.1-1 wt% of the total content of components A, B, and C. The antioxidant can be any antioxidant or anti-aging agent conventionally used in the processing of this art; specific selection can be made according to existing technology, and will not be elaborated here. The specific dosage also adopts conventional dosage.

[0038] According to a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned hydrogenated nitrile butadiene rubber abrasion-resistant composition, the method comprising:

[0039] 1) Mix and melt hydrogenated nitrile butyrate and modifier, then add wear-resistant filler and mix evenly;

[0040] 2) After crushing the mixture obtained in step 1), add a vulcanizing agent, and after dynamic vulcanization, extrude and granulate to obtain the composition.

[0041] Preferably, antioxidants and anti-aging agents are added when hydrogenated nitrile butadiene and the modifier are mixed in step 1). This is a routine operation in the processing of this art.

[0042] In this invention, the melting and mixing in step 1) can be carried out in equipment conventionally used in the field, such as in an internal mixer. The melting and mixing are carried out in the stirring state of the internal mixer. The melting temperature is 150-230℃, the stirring speed is 30-60r / min, and the mixing time is 3-10min. The mixing time is the stirring time after the wear-resistant filler is added. The wear-resistant filler is added after the torque is stable.

[0043] This step enables the hydrogenated nitrile butadiene rubber and abrasion-resistant filler to be uniformly mixed with hydrogenated nitrile butadiene rubber under high-temperature shear. The modifier can increase the interfacial bonding force between the abrasion-resistant filler and hydrogenated nitrile butadiene rubber, increase compatibility, and further improve compatibility when applied to the modification of polyolefins.

[0044] According to the present invention, the dynamic vulcanization in step 2) can be completed in a twin-screw extruder, and the material is directly extruded and granulated after dynamic vulcanization. The temperature of dynamic vulcanization is 160-230°C. The vulcanizing agent used in step 2) can be a vulcanizing agent conventionally used in the art.

[0045] According to a third aspect of the present invention, a polyolefin composite material is provided, the composite material comprising:

[0046] Component I: The above-mentioned hydrogenated nitrile butadiene rubber abrasion-resistant composition;

[0047] Component II: Polyolefin, wherein the polyolefin is polypropylene or polyethylene and is of the same type as the polyolefin of the modifier in Component I;

[0048] Based on a total content of 100 wt% for components I and II, the content of component I is 5-60 wt% and the content of component II is 40-95 wt%.

[0049] Preferably, the composite material further contains component III: an antioxidant, wherein the content of component III is 0.1-1 wt% of the total content of components I and II. The type and amount of antioxidant can be conventionally selected according to existing technology.

[0050] In this invention, the polyolefin can be polypropylene or polyethylene; the polypropylene can be copolymerized polypropylene with a melt index of 1-30 g / 10 min, preferably 3-15 g / 10 min; the polyethylene can be HDPE with a melt index of 0.02-20 g / 10 min, preferably 0.04-15 g / 10 min. The comonomer of the polyolefin in this invention is not limited.

[0051] According to a fourth aspect of the present invention, the present invention provides a method for preparing the above-described polyolefin composite material, the method comprising:

[0052] (1) Mix the hydrogenated butadiene nitrile rubber abrasion-resistant composition and polyolefin evenly;

[0053] (2) The mixture obtained in step (1) is extruded and granulated to obtain a composite material.

[0054] Preferably, an antioxidant is added when the hydrogenated nitrile rubber abrasion-resistant composition and the polyolefin are mixed in step (1). This is a routine operation in the processing of this art.

[0055] In step (1) of this invention, the mixing speed is 100-3000 r / min and the mixing time is 1-10 min.

[0056] This step enables the molten polyolefin and hydrogenated nitrile rubber wear-resistant composition to be uniformly mixed under high-temperature shear. The modifier is a graft-modified polyolefin containing functional groups, which is beneficial to the compatibility of different components, increases the interfacial bonding force of polyolefin, wear-resistant filler and hydrogenated nitrile rubber, increases compatibility and reduces the mechanical property degradation caused by phase separation.

[0057] In step (2), the extrusion granulation temperature is 130-230℃.

[0058] The substances and parameters not limited in this invention can be selected according to existing technology, which is a conventional technical means in this field.

[0059] The present invention will be further described below with reference to embodiments. However, the invention is not limited to these embodiments.

[0060] In the following embodiments and comparative examples, the data were obtained using the following methods:

[0061] 1. Impact strength was tested according to GB / T 1843-2008 "Determination of Impact Strength of Plastic Cantilever Beams".

[0062] 2. Tensile strength and elongation at break were tested according to GB / T 1040.1-2018 "Determination of tensile properties of plastics".

[0063] 3. Mass wear was tested according to GB / T 3960-2016 "Test Method for Sliding Friction and Wear of Plastics".

[0064] The hydrogenated nitrile rubber, abrasion-resistant filler, modifier, and polyolefin used in the examples and comparative examples are all commercial products, and substances with the same parameters are the same substances.

[0065] Example 1

[0066] First, 60 wt% of hydrogenated nitrile butadiene (99% saturation, 36% acrylonitrile content, Mooney viscosity 65), 20 wt% of modifier (PP-g-(MAH-St), grafting rate 1.5 wt%), 0.2 wt% of antioxidant B225 (measured based on the total amount of hydrogenated nitrile butadiene, modifier, and wear-resistant filler) and 0.1 wt% of antioxidant RD (measured based on the total amount of hydrogenated nitrile butadiene, modifier, and wear-resistant filler) were added to an internal mixer and melted at 180°C. The stirring speed was 40 r / min. After the torque stabilized, 20 wt% of wear-resistant filler (containing 50 wt% spherical alumina with an average particle size of 10 μm and 50 wt% carbon fiber with an average diameter of 6 μm and a length of 1-10 mm, each component measured based on the total amount of wear-resistant filler) was added. The mixing time was 6 min, and the mixture was thoroughly mixed. The mixture obtained by mixing in an internal mixer is crushed, and then peroxide vulcanizing agent F-40 (produced by Arkema Group, measured based on the amount of the mixture) is added. After dynamic vulcanization at 160-230℃ using a twin-screw extruder, it is extruded and granulated to obtain a hydrogenated nitrile rubber wear-resistant composition.

[0067] 50 wt% of the above-mentioned hydrogenated nitrile butadiene rubber abrasion-resistant composition, 50 wt% of polyolefin (copolypropylene, melt index 10 g / 10 min), and 0.1 wt% of antioxidant B225 (measured based on the total amount of hydrogenated nitrile butadiene rubber abrasion-resistant composition and polyolefin) were mixed evenly in a high-speed mixer at a speed of 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-230℃ to obtain the polyolefin composite material.

[0068] Example 2

[0069] Same as Example 1, except that: when preparing the polyolefin composite material, 40 wt% of hydrogenated nitrile butadiene rubber wear-resistant composition and 60 wt% polyolefin (copolymer polypropylene, melt index 10 g / 10 min) were used.

[0070] Example 3

[0071] Same as Example 1, except that: when preparing the polyolefin composite material, 30 wt% of hydrogenated nitrile butadiene rubber wear-resistant composition and 70 wt% polyolefin (copolymer polypropylene, melt index 10 g / 10 min) were used.

[0072] Example 4

[0073] First, 50 wt% of hydrogenated nitrile butadiene (99% saturation, 36% acrylonitrile content, Mooney viscosity 65), 25 wt% of modifier (PP-g-(MAH-St), grafting rate 1.5 wt%), 0.2 wt% of antioxidant B225 (measured based on the total amount of hydrogenated nitrile butadiene, modifier, and wear-resistant filler) and 0.1 wt% of antioxidant RD (measured based on the total amount of hydrogenated nitrile butadiene, modifier, and wear-resistant filler) were added to an internal mixer and melted at 180°C. The stirring speed was 40 r / min. After the torque stabilized, 25 wt% of wear-resistant filler (containing 50 wt% spherical alumina with an average particle size of 10 μm and 50 wt% carbon fiber with an average diameter of 6 μm and a length of 1-10 mm, with each component measured based on the total amount of wear-resistant filler) was added. The mixing time was 6 min, and the mixture was thoroughly mixed. The mixture obtained by mixing in an internal mixer is crushed, and then peroxide vulcanizing agent F-40 (produced by Arkema Group, measured based on the amount of the mixture) is added. After dynamic vulcanization at 160-230℃ using a twin-screw extruder, it is extruded and granulated to obtain a hydrogenated nitrile rubber wear-resistant composition.

[0074] 40 wt% of the above-mentioned hydrogenated nitrile butadiene rubber abrasion-resistant composition, 60 wt% of polyolefin (copolypropylene, melt index 10 g / 10 min), and 0.1 wt% of antioxidant B225 (measured based on the total amount of hydrogenated nitrile butadiene rubber abrasion-resistant composition and polyolefin) were mixed evenly in a high-speed mixer at a speed of 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-230℃ to obtain the polyolefin composite material.

[0075] Example 5

[0076] Same as Example 4, except that: when preparing the polyolefin composite material, 30 wt% of hydrogenated nitrile butadiene rubber wear-resistant composition and 70 wt% polyolefin (copolymer polypropylene, melt index 10 g / 10 min) were used.

[0077] Example 6

[0078] First, 50 wt% of hydrogenated nitrile butadiene (99% saturation, 36% acrylonitrile content, Mooney viscosity 65), 25 wt% of modifier (PE-g-MAH, grafting rate 1.0 wt%), 0.2 wt% of antioxidant (antioxidant B225, measured based on the total amount of hydrogenated nitrile butadiene, modifier, and wear-resistant filler) and 0.1 wt% of antioxidant RD (measured based on the total amount of hydrogenated nitrile butadiene, modifier, and wear-resistant filler) were added to a mixer and melted at 180°C. The stirring speed was 40 r / min. After the torque stabilized, 25 wt% of wear-resistant filler (containing 50 wt% spherical alumina with an average particle size of 10 μm and 50 wt% carbon fiber with an average diameter of 6 μm and a length of 1-10 mm, each component measured based on the total amount of wear-resistant filler) was added. The mixing time was 6 min, and the mixture was thoroughly mixed. The mixture obtained by mixing in an internal mixer is crushed, and then peroxide vulcanizing agent F-40 (produced by Arkema Group, measured based on the amount of the mixture) is added. After dynamic vulcanization at 160-210℃ using a twin-screw extruder, it is extruded and granulated to obtain a hydrogenated nitrile rubber wear-resistant composition.

[0079] 50 wt% of the above-mentioned hydrogenated nitrile butadiene rubber abrasion-resistant composition, 50 wt% of polyolefin (HDPE, melt index 0.05 g / 10 min), and 0.1 wt% of antioxidant (antioxidant B225, measured based on the total amount of hydrogenated nitrile butadiene rubber abrasion-resistant composition and polyolefin) were mixed evenly in a high-speed mixer at a speed of 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-210℃ to obtain the polyolefin composite material.

[0080] Example 7

[0081] Same as Example 6, except that: when preparing the polyolefin composite material, 40 wt% of hydrogenated nitrile butadiene rubber wear-resistant composition and 60 wt% polyolefin (HDPE, melt index 0.05 g / 10 min) were used.

[0082] Example 8

[0083] Same as Example 1, except that the modifier is PP-g-MAH and the grafting rate is 1.0 wt%.

[0084] Example 9

[0085] Same as Example 1, except that the modifier is PP-g-St and the grafting rate is 1.0 wt%.

[0086] Comparative Example 1

[0087] First, 50 wt% of modifier (PP-g-(MAH-St), grafting rate 1.5 wt%), 0.2 wt% antioxidant B225 (measured based on the total amount of modifier and wear-resistant filler) and 0.1 wt% antioxidant RD (measured based on the total amount of modifier and wear-resistant filler) are added to an internal mixer and melted at 180°C. The stirring speed is 40 r / min. After the torque stabilizes, 50 wt% wear-resistant filler (containing 50 wt% spherical alumina with an average particle size of 10 μm and 50 wt% carbon fiber with an average diameter of 6 μm and a length of 1-10 mm, each component is measured based on the total amount of wear-resistant filler) is added. The mixing time is 6 min, and the mixture is homogeneous. The mixture obtained by mixing in an internal mixer is crushed, and then peroxide vulcanizing agent F-40 (produced by Arkema Group, measured based on the amount of the mixture) is added. After dynamic vulcanization at 160-230℃ using a twin-screw extruder, the mixture is extruded and granulated to obtain the composition.

[0088] 40 wt% of the above composition, 60 wt% of polyolefin (copolypropylene, melt index 10 g / 10 min), and 0.1 wt% of antioxidant B225 (measured based on the total amount of composition and polyolefin) were mixed uniformly in a high-speed mixer at 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-230℃ to obtain the polyolefin composite material.

[0089] Comparative Example 2

[0090] First, 80 wt% of hydrogenated nitrile butadiene rubber (99% saturation, 36% acrylonitrile content, Mooney viscosity 65), 20 wt% of modifier (PP-g-(MAH-St), grafting rate 1.5 wt%), 0.2 wt% of antioxidant B225 (measured based on the total amount of hydrogenated nitrile butadiene rubber and modifier), and 0.1 wt% of antioxidant RD (measured based on the total amount of hydrogenated nitrile butadiene rubber and modifier) ​​were added to a Banbury mixer and melted at 180°C. The stirring speed was 40 r / min, and the mixing time was 6 min, until homogeneous. The mixture obtained from the Banbury mixer was crushed, and peroxide vulcanizing agent F-40 (manufactured by Arkema Group, measured based on the amount in the mixture) was added. The mixture was then dynamically vulcanized using a twin-screw extruder at 160-230°C, followed by extrusion granulation to obtain the composition.

[0091] 40 wt% of the above composition, 60 wt% of polyolefin (copolypropylene, melt index 10 g / 10 min), and 0.1 wt% of antioxidant B225 (measured based on the total amount of composition and polyolefin) were mixed uniformly in a high-speed mixer at 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-230℃ to obtain the polyolefin composite material.

[0092] Comparative Example 3

[0093] First, 80 wt% hydrogenated nitrile butadiene (99% saturation, 36% acrylonitrile content, Mooney viscosity 65), 0.2 wt% antioxidant B225 (measured based on the amount of hydrogenated nitrile butadiene), and 0.1 wt% antioxidant RD (measured based on the amount of hydrogenated nitrile butadiene) were added to an internal mixer and melted at 180°C. The stirring speed was 40 r / min. After the torque stabilized, 20 wt% wear-resistant filler (containing 50 wt% spherical alumina with an average particle size of 10 μm and 50 wt% carbon fiber with an average diameter of 6 μm and a length of 1-10 mm, with each component measured based on the total amount of wear-resistant filler) was added. The mixing time was 6 min, and the mixture was thoroughly mixed. The mixture obtained by mixing in an internal mixer is crushed, and then peroxide vulcanizing agent F-40 (produced by Arkema Group, measured based on the amount of the mixture) is added. After dynamic vulcanization at 160-230℃ using a twin-screw extruder, the mixture is extruded and granulated to obtain the composition.

[0094] 40 wt% of the above composition, 60 wt% of polyolefin (copolypropylene, melt index 10 g / 10 min), and 0.1 wt% of antioxidant (antioxidant B225, measured based on the total amount of composition and polyolefin) were mixed uniformly in a high-speed mixer at 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-230℃ to obtain the polyolefin composite material.

[0095] Comparative Example 4

[0096] 40 wt% of modifier (PP-g-(MAH-St), grafting rate 1.5 wt%), 60 wt% of polyolefin (copolypropylene, melt index 10 g / 10 min), and 0.1 wt% of antioxidant B225 (measured based on the total amount of modifier and polyolefin) were mixed uniformly in a high-speed mixer at 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-230℃ to obtain the polyolefin composite material.

[0097] Comparative Example 5

[0098] First, 75 wt% hydrogenated nitrile butadiene rubber (99% saturation, 36% acrylonitrile content, Mooney viscosity 65), 25 wt% modifier (PE-g-MAH, grafting rate 1.0 wt%), 0.2 wt% antioxidant B225 (measured based on the total amount of hydrogenated nitrile butadiene rubber and modifier), and 0.1 wt% antioxidant RD (measured based on the total amount of hydrogenated nitrile butadiene rubber and modifier) ​​were added to a mixer and melted at 180°C. The stirring speed was 40 r / min, and the mixing time was 6 min, until homogeneous. The mixture obtained from the mixer was crushed, and peroxide vulcanizing agent F-40 (manufactured by Arkema Group, measured based on the amount in the mixture) was added. The mixture was then dynamically vulcanized using a twin-screw extruder at 160-210°C, followed by extrusion granulation to obtain the composition.

[0099] 40 wt% of the above composition, 60 wt% of polyolefin (HDPE, melt index 0.05 g / 10 min), and 0.1 wt% of antioxidant B225 (measured based on the total amount of composition and polyolefin) were mixed uniformly in a high-speed mixer at 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-210 °C to obtain the polyolefin composite material.

[0100] Comparative Example 6

[0101] First, 25 wt% of modifier (PE-g-MAH, grafting rate 1.0 wt%), 0.2 wt% antioxidant B225 (measured based on the total amount of modifier and wear-resistant filler) and 0.1 wt% antioxidant RD (measured based on the total amount of modifier and wear-resistant filler) were added to an internal mixer and melted at 180°C. The stirring speed was 40 r / min. After the torque stabilized, 75 wt% wear-resistant filler (containing 50 wt% spherical alumina with an average particle size of 10 μm and 50 wt% carbon fiber with an average diameter of 6 μm and a length of 1-10 mm, with each component measured based on the total amount of wear-resistant filler) was added. The mixing time was 6 min, and the mixture was thoroughly mixed. The mixture obtained by mixing in an internal mixer is crushed, and then peroxide vulcanizing agent F-40 (produced by Arkema Group, measured based on the amount of the mixture) is added. After dynamic vulcanization at 160-210℃ using a twin-screw extruder, the mixture is extruded and granulated to obtain the composition.

[0102] 40 wt% of the above composition, 60 wt% of polyolefin (HDPE, melt index 0.05 g / 10 min), and 0.1 wt% of antioxidant B225 (measured based on the total amount of composition and polyolefin) were mixed uniformly in a high-speed mixer at 1000 r / min for 3 min. The uniformly mixed mixture was fed into a twin-screw extruder and extruded and granulated at 160-210 °C to obtain the polyolefin composite material.

[0103] The main raw material composition of the composite materials prepared in each embodiment and comparative example is shown in Table 1, and the properties of the composite materials are shown in Table 2.

[0104] Table 1

[0105]

[0106] Table 2

[0107]

[0108] Comparing Examples 1-5 with Comparative Examples 1-2, it is evident that the wear resistance of the composite materials prepared without hydrogenated nitrile butadiene rubber or wear-resistant fillers is unsatisfactory. This is because hydrogenated nitrile butadiene rubber and wear-resistant fillers synergistically improve the wear resistance of the composite material, allowing the butadiene units in the hydrogenated nitrile butadiene rubber molecular chain and the wear-resistant fillers to better exert their wear-resistant properties in the composite material. Meanwhile, Comparative Example 1, which does not contain hydrogenated nitrile butadiene rubber, exhibits very low impact resistance and elongation at break, failing to achieve the goal of improving wear resistance and mechanical properties.

[0109] Comparing Examples 1-5 with Comparative Example 3, it can be seen that when the wear-resistant composition does not contain a modifier, the mechanical properties of the composite material decrease significantly. This is mainly because by using an appropriate blending method and adding a modifier, the hydrogenated nitrile butadiene, wear-resistant filler and polypropylene can be effectively mixed uniformly. The modifier improves the interfacial bonding force between the rubber phase, wear-resistant filler and polypropylene matrix, and the dynamic vulcanization process further improves the mechanical properties of the composite material.

[0110] Comparing Examples 1-5 with Comparative Example 4, it can be seen that the main components contributing to the wear resistance of the composite material are hydrogenated nitrile rubber and wear-resistant fillers, while the main function of the modifier is to improve the compatibility between different components.

[0111] Comparing Examples 6-7 and Comparative Examples 5-6, it is evident that the wear resistance of the polyethylene composites prepared without hydrogenated nitrile rubber or wear-resistant fillers is unsatisfactory. This is because hydrogenated nitrile rubber and wear-resistant fillers synergistically improve the wear resistance of the composites. Specifically, Comparative Example 5, lacking wear-resistant fillers, fails to meet the requirements for high wear resistance and exhibits low tensile strength; Comparative Example 6, lacking hydrogenated nitrile rubber, demonstrates poor toughness and wear resistance, and its elongation at break and impact strength do not meet the application requirements.

[0112] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A hydrogenated nitrile rubber wear composition characterized in that, The composition consists of the following components: Component A: Hydrogenated butyronitrile; Component B: Wear-resistant filler; Component C: Modifier, wherein the modifier is a graft-modified polyolefin containing functional groups; Component D: Processing aids, wherein the processing aids are antioxidants and / or anti-aging agents; And vulcanizing agents; Based on a total content of 100 wt% for components A, B, and C, the content of component A is 30-60 wt%; the content of component B is 20-50 wt%; and the content of component C is 5-20 wt%. The wear-resistant filler is ceramic powder and / or fiber powder; the ceramic powder is selected from at least one of silicon dioxide, titanium dioxide and aluminum oxide, with an average particle size of 1-100 μm; the fiber powder is selected from at least one of ultra-high molecular weight polyethylene fiber, carbon fiber and glass fiber, with an average fiber diameter of 1-50 μm and a length of 1-20 mm. The polyolefin of the modifier is polypropylene or polyethylene; The functional groups of the modifier are selected from at least one of maleic anhydride, styrene, glycidyl methacrylate, methyl methacrylate and butyl acrylate. The grafting rate of the modifier is 0.5-5 wt%.

2. The hydrogenated nitrile rubber wear composition of claim 1, wherein, The hydrogenated nitrile butadiene has a Mooney viscosity of 50-90, an acrylonitrile content of 20-50%, and a saturation of 85-99%.

3. The hydrogenated nitrile butadiene rubber wear-resistant composition according to claim 1, wherein, The grafting rate of the modifier is 0.8-4 wt%.

4. The hydrogenated nitrile rubber wear composition of claim 3, wherein, The grafting rate of the modifier is 0.8-3 wt%.

5. The hydrogenated nitrile rubber wear composition of claim 1, wherein, The content of component D is 0.1-1 wt% of the total content of components A, B and C.

6. Process for the production of the hydrogenated nitrile rubber wear composition according to any one of claims 1 to 5, characterized in that, The preparation method includes: 1) Mix and melt hydrogenated nitrile butyrate and modifier, then add wear-resistant filler and mix evenly; 2) After crushing the mixture obtained in step 1), add a vulcanizing agent, perform dynamic vulcanization, and then extrude and granulate to obtain the composition; In step 1), antioxidants and anti-aging agents are added when hydrogenated nitrile butadiene and modifier are mixed.

7. The process for preparing a hydrogenated nitrile rubber wear composition according to claim 6, wherein, In step 1), the melting temperature is 150-230℃, the stirring speed is 30-60 r / min, and the mixing time is 3-10 min; The temperature for dynamic vulcanization in step 2) is 160-230℃.

8. A polyolefin composite material, characterized in that, The composite material contains: Component I: The hydrogenated nitrile butadiene rubber abrasion-resistant composition according to any one of claims 1-5; Component II: Polyolefin, wherein the polyolefin is polypropylene or polyethylene, and is of the same type as the polyolefin of the modifier in Component I; Based on a total content of 100wt% for components I and II, the content of component I is 5-60wt% and the content of component II is 40-95wt%.

9. The polyolefin composite of claim 8, wherein, The composite material also contains component III: an antioxidant, the content of component III being 0.1-1 wt% of the total content of components I and II.

10. The process for the production of a polyolefin composite according to claim 8 or 9, characterized in that, The preparation method includes: (1) Mix the hydrogenated butadiene nitrile rubber abrasion-resistant composition and polyolefin evenly; (2) The mixture obtained in step (1) is extruded and granulated to obtain a composite material.

11. The method of making a polyolefin composite of claim 10, wherein, In step (1), an antioxidant is added when the hydrogenated nitrile rubber wear-resistant composition and the polyolefin are mixed.

12. The method of making a polyolefin composite of claim 10, wherein, In step (1), the mixing speed is 100-3000 r / min and the mixing time is 1-10 min; In step (2), the extrusion granulation temperature is 130-230℃.

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