Preparation process of high-strength ultraviolet-resistant rubber composite material

Abstract

This invention discloses a preparation process for a high-strength, UV-resistant rubber composite material, comprising the following steps: (1) uniformly mixing EPDM rubber, styrene-butadiene rubber, UV absorber, and modified nanofiller; (2) adding silane coupling agent, plasticizer, antioxidant, and anti-aging agent, and continuing to mix until uniform; (3) melt-kneading the mixture, extruding and granulating, and then cooling; (4) adding vulcanizing agent and vulcanization accelerator for vulcanization treatment to form a cross-linked structure; after vulcanization, the final high-strength, UV-resistant rubber composite material is obtained. The rubber composite material prepared by the method of this invention has high UV resistance while also possessing good mechanical strength.

Description

Technical Field

[0001] This invention relates to the field of rubber materials technology, and specifically to a preparation process for a high-strength, UV-resistant rubber composite material. Background Technology

[0002] With the advancement of science and technology and the development of industry, the application of rubber composite materials in various fields is becoming increasingly widespread. Especially in outdoor, chemical, and pipeline connection environments, rubber composite materials not only need to possess high strength but also must have good resistance to ultraviolet (UV) aging. Ultraviolet (UV) radiation is one of the main factors causing material aging in the natural environment. Rubber materials exposed to UV radiation for a long time are prone to surface cracking, decreased elasticity, and changes in hardness, thus affecting their service life and performance.

[0003] In existing rubber composite material manufacturing processes, UV stabilizers are typically added to improve the material's anti-aging properties. However, these additives often only delay the aging process to a certain extent and cannot fundamentally solve the problems caused by UV radiation. Furthermore, the addition of some additives may affect the material's mechanical and processing properties, leading to an overall decline in performance.

[0004] Existing patents propose a method of grafting UV absorbers with specific structures onto rubber molecular chains. While this method can improve the material's UV resistance, the preparation process is complex and costly, hindering large-scale industrial production. Another method involves physical blending, mixing the UV absorber with the rubber matrix. However, this may result in uneven dispersion of the UV absorber within the rubber matrix, thus affecting its anti-aging effect.

[0005] Currently, while rubber composite materials on the market exhibit some UV resistance, the anti-aging properties of most products are still insufficient, or they may lead to a decline in other properties of the rubber material. Therefore, developing a rubber composite material that possesses both high strength and excellent UV resistance is particularly important. Based on this, this invention proposes a preparation process for a high-strength, UV-resistant rubber composite material. Summary of the Invention

[0006] The purpose of this invention is to provide a preparation process for a high-strength, UV-resistant rubber composite material. The prepared rubber composite material can maintain its mechanical properties while also possessing excellent UV resistance.

[0007] This invention provides a preparation process for a high-strength, UV-resistant rubber composite material, comprising the following steps:

[0008] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0009] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0010] (3) The mixture is melt-blended, extruded and granulated, and then cooled;

[0011] (4) Add vulcanizing agent and vulcanization accelerator to vulcanize and form a cross-linked structure; after vulcanization, the final high-strength UV-resistant rubber composite material is obtained.

[0012] Furthermore, the high-strength UV-resistant rubber comprises the following raw materials in parts by weight: 70-80 parts of EPDM rubber, 20-30 parts of styrene-butadiene rubber, 2-3 parts of UV absorber, 5-10 parts of modified nanofiller, 6-8 parts of silane coupling agent, 2-3 parts of plasticizer, 0.5-1 part of antioxidant, 0.5-1 part of anti-aging agent, 3-4 parts of vulcanizing agent, and 1-1.4 parts of vulcanization accelerator.

[0013] Furthermore, the ultraviolet absorber includes any one of UV-326, UV-329, UV-531, and UV-81.

[0014] Further, the preparation method of the modified nanofiller includes: mixing ZnSO4 aqueous solution and MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and then calcining at a temperature of 350-450℃ to obtain Zn@Mn composite oxide powder, adding the Zn@Mn composite oxide powder to an ethanol solution of silane coupling agent KH550, stirring at a temperature of 80-90℃ and a rotation speed of 500-600 r / min for 3-4 h, centrifuging and drying to obtain the modified nanofiller.

[0015] Further, the molar ratio of ZnSO4, MnCl2, polyethylene glycol and sodium hydroxide is (0.4-0.6):(0.04-0.06):(0.2-0.3):(1.4-1.6).

[0016] Furthermore, the weight ratio of the Zn@Mn composite oxide powder, silane coupling agent, and ethanol is (5-7):(1-2):(80-90).

[0017] Furthermore, the silane coupling agent includes any one of KH550, KH560, and KH570.

[0018] Furthermore, the plasticizer comprises paraffin oil and dioctyl azelate in a weight ratio of 1:(3-4).

[0019] Furthermore, the antioxidant includes antioxidant 1010 and / or antioxidant 1076.

[0020] Furthermore, the antioxidant includes any one of antioxidant 264, antioxidant 2246, and antioxidant 445.

[0021] Furthermore, the vulcanizing agent is dicumyl peroxide.

[0022] Furthermore, the vulcanization accelerator is hexamethylenetetramine.

[0023] Furthermore, in step (3), the melting and mixing temperature is 175-185℃ and the rotation speed is 700-800rpm.

[0024] Furthermore, in step (4), the vulcanization treatment temperature is 160-170℃, the pressure is 5-6MPa, and the time is 15-20min.

[0025] The beneficial effects of this invention are as follows:

[0026] This invention provides a process for preparing a high-strength, UV-resistant rubber composite material, using ethylene propylene diene monomer (EPDM) rubber and styrene-butadiene rubber (SBR) as base materials, which provides the composite material with the main mechanical properties and elasticity. EPDM rubber exhibits excellent weather resistance, ozone resistance, and UV resistance, while SBR provides good processability and abrasion resistance. The combination of the two allows the composite material to maintain high strength while possessing good overall performance.

[0027] This invention utilizes modified nanofillers, specifically silane coupling agents-modified manganese-doped zinc oxide nanomaterials, as raw materials. By doping manganese (Mn) into the ZnO lattice, the original optical, magnetic, and electrical properties of ZnO can be altered. This doping has a positive impact on improving the UV resistance of rubber materials. ZnO itself is an oxide material with excellent UV shielding properties; it can effectively absorb and reflect ultraviolet light, thereby protecting rubber materials from UV damage.

[0028] When Mn is doped into the lattice of ZnO, it alters the band structure of ZnO, affecting its light absorption, reflection, and transmission properties. This change may give Mn-doped ZnO quantum dots a stronger absorption capacity in the ultraviolet (UV) region, effectively blocking or absorbing UV radiation; these quantum dots can act as UV absorbers or scattering centers. Their ability to absorb or scatter UV radiation reduces the direct irradiation and damaging effects of UV radiation on rubber materials. Furthermore, after absorbing UV radiation, the energy from Mn-doped ZnO quantum dots can be converted and dissipated through energy level transitions and relaxation processes within the quantum dots. This energy conversion mechanism helps convert UV energy into harmless heat or other forms of energy, further reducing the destructive effects of UV radiation on rubber materials.

[0029] Furthermore, this invention utilizes a silane coupling agent to modify the manganese-doped zinc oxide nanomaterial, thereby enhancing the interfacial bonding force between the filler and the rubber substrate. This network structure can significantly improve the mechanical properties of rubber, such as tensile strength, fracture strength, and hardness, enabling the composite material to withstand greater external forces and deformations. It also helps to form a denser composite structure, further enhancing the UV resistance of the composite material.

[0030] This invention utilizes silane coupling agents in two ways: firstly, during the preparation of modified nanofillers, and secondly, during the mixing of raw materials. Firstly, through chemical bonding, the silane coupling agent forms an organosilicon film on the surface of the nanomaterial. This film not only alters the surface properties of the nanomaterial but also improves its compatibility with the rubber matrix. The modifying effect of the silane coupling agent improves the dispersion of the nanomaterial in the rubber matrix, reduces agglomeration, and thus enhances the overall performance of the rubber composite material. Secondly, when the silane coupling agent is added as a raw material in a compound formulation, the organic functional groups in its molecular structure can chemically react with the functional groups in the rubber matrix to form chemical bonds. This chemical bonding results in a tight bond between the nanomaterial and the rubber matrix, thereby improving the structural stability and mechanical strength of the rubber composite material. Thirdly, the silane coupling agent forms a stable silicon-oxygen bond structure in the rubber matrix, equivalent to forming a dense protective layer on the surface of the rubber composite material. This structure provides some shielding against ultraviolet radiation, thus reducing the damage caused by ultraviolet rays to the rubber matrix.

[0031] This invention successfully prepared a rubber composite material with both high mechanical properties and excellent UV resistance by rationally selecting and proportioning raw materials, preparing and adding modified nanofillers, utilizing the synergistic effect of additives, and optimizing the preparation process. Detailed Implementation

[0032] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. It should be noted that the polyethylene glycol in the present invention is polyethylene glycol 400.

[0033] Example 1

[0034] This embodiment provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0035] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0036] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0037] (3) The mixture is melt-blended, extruded and granulated and then cooled; the melt-blending temperature is 180℃ and the rotation speed is 750rpm.

[0038] (4) Add vulcanizing agent and vulcanization accelerator to vulcanize and form a cross-linked structure; the vulcanization temperature is 165℃, the pressure is 5.5MPa, and the time is 17min.

[0039] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0040] The composition includes 75 parts of EPDM rubber, 25 parts of styrene-butadiene rubber, 2.5 parts of ultraviolet absorber, 7.5 parts of modified nanofiller, 7 parts of silane coupling agent, 2.5 parts of plasticizer, 0.75 parts of antioxidant, 0.75 parts of anti-aging agent, 3.5 parts of vulcanizing agent and 1.2 parts of vulcanization accelerator.

[0041] The ultraviolet absorber is UV-326; the silane coupling agent is KH550; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:3; the antioxidant is antioxidant 1010; the anti-aging agent is anti-aging agent 264; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0042] The preparation method of the modified nanofiller includes: mixing ZnSO4 aqueous solution and MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and calcining at 400℃ to obtain Zn@Mn composite oxide powder, adding Zn@Mn composite oxide powder to an ethanol solution of silane coupling agent KH550, stirring at 85℃ and 550 r / min for 3.5 h, centrifuging and drying to obtain the modified nanofiller; the molar ratio of ZnSO4, MnCl2, polyethylene glycol and sodium hydroxide is 0.5:0.05:0.25:1.5; the weight ratio of Zn@Mn composite oxide powder, silane coupling agent and ethanol is 6:1.5:85.

[0043] Example 2

[0044] This embodiment provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0045] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0046] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0047] (3) The mixture is melt-blended, extruded and granulated, and then cooled; the melt-blending temperature is 175℃ and the rotation speed is 700rpm;

[0048] (4) Add vulcanizing agent and vulcanization accelerator for vulcanization treatment to form a cross-linked structure; the vulcanization treatment temperature is 160℃, the pressure is 5MPa, and the time is 15min;

[0049] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0050] The composition includes 70 parts of EPDM rubber, 30 parts of styrene-butadiene rubber, 2 parts of ultraviolet absorber, 5 parts of modified nanofiller, 6 parts of silane coupling agent, 2 parts of plasticizer, 0.5 parts of antioxidant, 0.5 parts of anti-aging agent, 3 parts of vulcanizing agent and 1 part of vulcanization accelerator.

[0051] The ultraviolet absorber is UV-329; the silane coupling agent is KH560; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:4; the antioxidant is antioxidant 1076; the anti-aging agent is anti-aging agent 2246; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0052] The preparation method of the modified nanofiller includes: mixing ZnSO4 aqueous solution and MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and then calcining at 350℃ to obtain Zn@Mn composite oxide powder, adding the Zn@Mn composite oxide powder to an ethanol solution of silane coupling agent KH550, stirring at 80℃ and 500 r / min for 4 h, centrifuging and drying to obtain the modified nanofiller; the molar ratio of ZnSO4, MnCl2, polyethylene glycol and sodium hydroxide is 0.5:0.05:0.25:1.5; the weight ratio of Zn@Mn composite oxide powder, silane coupling agent and ethanol is 5:1:80.

[0053] Example 3

[0054] This embodiment provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0055] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0056] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0057] (3) The mixture is melt-blended, extruded and granulated, and then cooled; the melt-blending temperature is 185℃ and the rotation speed is 800rpm;

[0058] (4) Add vulcanizing agent and vulcanization accelerator for vulcanization treatment to form a cross-linked structure; the vulcanization treatment temperature is 170℃, the pressure is 6MPa, and the time is 20min;

[0059] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0060] The composition includes 80 parts of EPDM rubber, 20 parts of styrene-butadiene rubber, 3 parts of ultraviolet absorber, 10 parts of modified nanofiller, 8 parts of silane coupling agent, 3 parts of plasticizer, 1 part of antioxidant, 1 part of anti-aging agent, 4 parts of vulcanizing agent and 1.4 parts of vulcanization accelerator.

[0061] The ultraviolet absorber is UV-531; the silane coupling agent is KH570; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:4; the antioxidant is antioxidant 1010; the anti-aging agent is anti-aging agent 445; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0062] The preparation method of the modified nanofiller includes: mixing ZnSO4 aqueous solution and MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and then calcining at 450℃ to obtain Zn@Mn composite oxide powder, adding the Zn@Mn composite oxide powder to an ethanol solution of silane coupling agent KH550, stirring at 90℃ and 600 r / min for 3 h, centrifuging and drying to obtain the modified nanofiller; the molar ratio of ZnSO4, MnCl2, polyethylene glycol and sodium hydroxide is 0.5:0.05:0.25:1.5; the weight ratio of Zn@Mn composite oxide powder, silane coupling agent and ethanol is 7:2:90.

[0063] Example 4

[0064] This embodiment provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0065] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0066] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0067] (3) The mixture is melt-blended, extruded and granulated and then cooled; the melt-blending temperature is 180℃ and the rotation speed is 750rpm.

[0068] (4) Add vulcanizing agent and vulcanization accelerator for vulcanization treatment to form a cross-linked structure; the vulcanization treatment temperature is 165℃, the pressure is 5.5MPa, and the time is 17.5min;

[0069] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0070] The composition includes 75 parts of EPDM rubber, 25 parts of styrene-butadiene rubber, 3 parts of ultraviolet absorber, 10 parts of modified nanofiller, 6 parts of silane coupling agent, 3 parts of plasticizer, 0.5 parts of antioxidant, 1 part of anti-aging agent, 3 parts of vulcanizing agent and 1.4 parts of vulcanization accelerator.

[0071] The ultraviolet absorber is UV-81; the silane coupling agent is KH550; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:3.5; the antioxidant is antioxidant 1076; the anti-aging agent is anti-aging agent 445; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0072] The preparation method of the modified nanofiller includes: mixing ZnSO4 aqueous solution and MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and calcining at 450℃ to obtain Zn@Mn composite oxide powder, adding Zn@Mn composite oxide powder to an ethanol solution of silane coupling agent KH550, stirring at 90℃ and 500 r / min for 4 h, centrifuging and drying to obtain the modified nanofiller; the molar ratio of ZnSO4, MnCl2, polyethylene glycol and sodium hydroxide is 0.5:0.05:0.25:1.5; the weight ratio of Zn@Mn composite oxide powder, silane coupling agent and ethanol is 6:2:85.

[0073] Comparative Example 1

[0074] This comparative example provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0075] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0076] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0077] (3) The mixture is melt-blended, extruded and granulated and then cooled; the melt-blending temperature is 180℃ and the rotation speed is 750rpm.

[0078] (4) Add vulcanizing agent and vulcanization accelerator to vulcanize and form a cross-linked structure; the vulcanization temperature is 165℃, the pressure is 5.5MPa, and the time is 17min.

[0079] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0080] The composition includes 75 parts of EPDM rubber, 25 parts of styrene-butadiene rubber, 2.5 parts of ultraviolet absorber, 7.5 parts of modified nanofiller, 7 parts of silane coupling agent, 2.5 parts of plasticizer, 0.75 parts of antioxidant, 0.75 parts of anti-aging agent, 3.5 parts of vulcanizing agent and 1.2 parts of vulcanization accelerator.

[0081] The ultraviolet absorber is UV-326; the silane coupling agent is KH550; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:3; the antioxidant is antioxidant 1010; the anti-aging agent is anti-aging agent 264; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0082] The preparation method of the modified nanofiller includes: adding ZnSO4 aqueous solution to polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and calcining at 400℃ to obtain zinc oxide powder, adding the zinc oxide powder to an ethanol solution of silane coupling agent KH550, stirring at 85℃ and 550 r / min for 3.5 h, centrifuging and drying to obtain the modified nanofiller; the molar ratio of ZnSO4, polyethylene glycol and sodium hydroxide is 0.55:0.25:1.5; the weight ratio of zinc oxide powder, silane coupling agent and ethanol is 6:1.5:85.

[0083] Comparative Example 2

[0084] This comparative example provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0085] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0086] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0087] (3) The mixture is melt-blended, extruded and granulated and then cooled; the melt-blending temperature is 180℃ and the rotation speed is 750rpm.

[0088] (4) Add vulcanizing agent and vulcanization accelerator to vulcanize and form a cross-linked structure; the vulcanization temperature is 165℃, the pressure is 5.5MPa, and the time is 17min.

[0089] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0090] The composition includes 75 parts of EPDM rubber, 25 parts of styrene-butadiene rubber, 2.5 parts of ultraviolet absorber, 7.5 parts of modified nanofiller, 7 parts of silane coupling agent, 2.5 parts of plasticizer, 0.75 parts of antioxidant, 0.75 parts of anti-aging agent, 3.5 parts of vulcanizing agent and 1.2 parts of vulcanization accelerator.

[0091] The ultraviolet absorber is UV-326; the silane coupling agent is KH550; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:3; the antioxidant is antioxidant 1010; the anti-aging agent is anti-aging agent 264; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0092] The preparation method of the modified nanofiller includes: mixing MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and calcining at 400℃ to obtain manganese oxide powder, adding manganese oxide to an ethanol solution of silane coupling agent KH550, stirring at 85℃ and 550 r / min for 3.5 h, centrifuging and drying to obtain the modified nanofiller; the molar ratio of MnCl2, polyethylene glycol and sodium hydroxide is 0.55:0.25:1.5; the weight ratio of manganese oxide, silane coupling agent and ethanol is 6:1.5:85.

[0093] Comparative Example 3

[0094] This comparative example provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0095] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0096] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0097] (3) The mixture is melt-blended, extruded and granulated and then cooled; the melt-blending temperature is 180℃ and the rotation speed is 750rpm.

[0098] (4) Add vulcanizing agent and vulcanization accelerator to vulcanize and form a cross-linked structure; the vulcanization temperature is 165℃, the pressure is 5.5MPa, and the time is 17min.

[0099] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0100] The composition includes 75 parts of EPDM rubber, 25 parts of styrene-butadiene rubber, 2.5 parts of ultraviolet absorber, 7.5 parts of modified nanofiller, 7 parts of silane coupling agent, 2.5 parts of plasticizer, 0.75 parts of antioxidant, 0.75 parts of anti-aging agent, 3.5 parts of vulcanizing agent and 1.2 parts of vulcanization accelerator.

[0101] The ultraviolet absorber is UV-326; the silane coupling agent is KH550; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:3; the antioxidant is antioxidant 1010; the anti-aging agent is anti-aging agent 264; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0102] The preparation method of the modified nanofiller includes: adding titanium dioxide powder to an ethanol solution of silane coupling agent KH550, stirring for 3.5 h at a temperature of 85℃ and a rotation speed of 550 r / min, centrifuging and drying to obtain the modified nanofiller; the weight ratio of titanium dioxide powder, silane coupling agent and ethanol is 6:1.5:85.

[0103] Comparative Example 4

[0104] This comparative example provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0105] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and nanofiller evenly;

[0106] (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0107] (3) The mixture is melt-blended, extruded and granulated and then cooled; the melt-blending temperature is 180℃ and the rotation speed is 750rpm.

[0108] (4) Add vulcanizing agent and vulcanization accelerator to vulcanize and form a cross-linked structure; the vulcanization temperature is 165℃, the pressure is 5.5MPa, and the time is 17min.

[0109] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0110] The composition includes 75 parts of EPDM rubber, 25 parts of styrene-butadiene rubber, 2.5 parts of ultraviolet absorber, 7.5 parts of nanofiller, 7 parts of silane coupling agent, 2.5 parts of plasticizer, 0.75 parts of antioxidant, 0.75 parts of anti-aging agent, 3.5 parts of vulcanizing agent and 1.2 parts of vulcanization accelerator.

[0111] The ultraviolet absorber is UV-326; the silane coupling agent is KH550; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:3; the antioxidant is antioxidant 1010; the anti-aging agent is anti-aging agent 264; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0112] The preparation method of the modified nanofiller includes: mixing ZnSO4 aqueous solution and MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and then calcining at a temperature of 400℃ to obtain Zn@Mn composite oxide powder, wherein the molar ratio of ZnSO4, MnCl2, polyethylene glycol and sodium hydroxide is 0.5:0.05:0.25:1.5.

[0113] Comparative Example 5

[0114] This comparative example provides a preparation process for a high-strength, UV-resistant rubber composite material, the steps of which include:

[0115] (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly;

[0116] (2) Add plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform;

[0117] (3) The mixture is melt-blended, extruded and granulated and then cooled; the melt-blending temperature is 180℃ and the rotation speed is 750rpm.

[0118] (4) Add vulcanizing agent and vulcanization accelerator to vulcanize and form a cross-linked structure; the vulcanization temperature is 165℃, the pressure is 5.5MPa, and the time is 17min.

[0119] (5) After vulcanization, the composite material is cut to obtain the final high-strength UV-resistant rubber composite material.

[0120] The composition includes 75 parts of EPDM rubber, 25 parts of styrene-butadiene rubber, 2.5 parts of ultraviolet absorber, 7.5 parts of modified nanofiller, 2.5 parts of plasticizer, 0.75 parts of antioxidant, 0.75 parts of anti-aging agent, 3.5 parts of vulcanizing agent and 1.2 parts of vulcanization accelerator.

[0121] The ultraviolet absorber is UV-326; the silane coupling agent is KH550; the plasticizer includes paraffin oil and dioctyl azelate in a weight ratio of 1:3; the antioxidant is antioxidant 1010; the anti-aging agent is anti-aging agent 264; the vulcanizing agent is dicumyl peroxide; and the vulcanization accelerator is hexamethylenetetramine.

[0122] The preparation method of the modified nanofiller includes: mixing ZnSO4 aqueous solution and MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and calcining at 400℃ to obtain Zn@Mn composite oxide powder, adding Zn@Mn composite oxide powder to an ethanol solution of silane coupling agent KH550, stirring at 85℃ and 550 r / min for 3.5 h, centrifuging and drying to obtain the modified nanofiller; the molar ratio of ZnSO4, MnCl2, polyethylene glycol and sodium hydroxide is 0.5:0.05:0.25:1.5; the weight ratio of Zn@Mn composite oxide powder, silane coupling agent and ethanol is 6:1.5:85.

[0123] The rubber composite materials obtained in Examples 1-4 and Comparative Examples 1-5 were tested;

[0124] (1) Tensile strength: Tested in accordance with the national standard GB / T528, the unit is MPa;

[0125] (2) Elongation at break: Tested in accordance with the national standard GB / T528, the unit is %;

[0126] (3) UV aging resistance: Accelerated aging tests were conducted using a UV lamp weathering test chamber. The samples were irradiated for 200 hours each with UV lamps of wavelengths of 200–275 nm, 275–320 nm, and 320–400 nm, respectively, with a UV light intensity of 20 W / cm². 2 The sample was placed 30 cm away from the ultraviolet light to test the retention rate of tensile strength and elongation at break.

[0127] The test results are shown in Table 1 below:

[0128] Table 1

[0129]

[0130] Finally, it should be noted that the applicant declares that while the above embodiments illustrate the product and detailed preparation method of the present invention, the present invention is not limited to the above-described product and detailed preparation method, that is, it does not mean that the present invention must rely on the above-described product and detailed preparation method to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of excipients, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0131] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention. These simple modifications all fall within the protection scope of the present invention.

[0132] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0133] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A preparation process for a high-strength, UV-resistant rubber composite material, characterized by the following steps: include: (1) Mix EPDM rubber, styrene-butadiene rubber, ultraviolet absorber and modified nanofiller evenly; (2) Add silane coupling agent, plasticizer, antioxidant and anti-aging agent, and continue mixing until uniform; (3) The mixture is melt-blended, extruded and granulated, and then cooled; (4) Add vulcanizing agent and vulcanization accelerator for vulcanization treatment to form a cross-linked structure; after vulcanization, the final high-strength UV-resistant rubber composite material is obtained. The high-strength, UV-resistant rubber composite material comprises the following raw materials in parts by weight: 70-80 parts EPDM rubber, 20-30 parts styrene-butadiene rubber, 2-3 parts UV absorber, 5-10 parts modified nanofiller, 6-8 parts silane coupling agent, 2-3 parts plasticizer, 0.5-1 part antioxidant, 0.5-1 part anti-aging agent, 3-4 parts vulcanizing agent, and 1-1.4 parts vulcanization accelerator; the silane coupling agent includes any one of KH550, KH560, and KH570. The preparation method of the modified nanofiller includes: mixing ZnSO4 aqueous solution and MnCl2 aqueous solution, adding polyethylene glycol and NaOH aqueous solution, stirring in an ice-water bath to obtain a white suspension, centrifuging and then calcining at a temperature of 350-450℃ to obtain Zn@Mn composite oxide powder, adding Zn@Mn composite oxide powder to an ethanol solution of silane coupling agent KH550, stirring at a temperature of 80-90℃ and a rotation speed of 500-600 r / min for 3-4 h, centrifuging and drying to obtain the modified nanofiller; The molar ratio of ZnSO4, MnCl2, polyethylene glycol, and sodium hydroxide is (0.4-0.6):(0.04-0.06):(0.2-0.3):(1.4-1.6).

2. The preparation process of a high-strength, UV-resistant rubber composite material according to claim 1, characterized in that, The ultraviolet absorber includes any one of UV-326, UV-329, UV-531, and UV-81.

3. The preparation process of a high-strength, UV-resistant rubber composite material according to claim 1, characterized in that, In the preparation method of the modified nanofiller, the weight ratio of Zn@Mn composite oxide powder, silane coupling agent KH550 and ethanol is (5-7):(1-2):(80-90).

4. The preparation process of a high-strength, UV-resistant rubber composite material according to claim 1, characterized in that, The plasticizer comprises paraffin oil and dioctyl azelate in a weight ratio of 1:(3-4); the antioxidant comprises antioxidant 1010 and / or antioxidant 1076; the antioxidant comprises any one of antioxidant 264, antioxidant 2246 and antioxidant 445.

5. The preparation process of a high-strength, UV-resistant rubber composite material according to claim 1, characterized in that, The vulcanizing agent is dicumyl peroxide, and the vulcanization accelerator is hexamethylenetetramine.

6. The preparation process of a high-strength, UV-resistant rubber composite material according to claim 1, characterized in that, The melting and mixing temperature in step (3) is 175-185℃ and the rotation speed is 700-800rpm.

7. The preparation process of a high-strength, UV-resistant rubber composite material according to claim 1, characterized in that, The vulcanization treatment in step (4) is carried out at a temperature of 160-170℃, a pressure of 5-6MPa, and a time of 15-20min.

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