A hose rubber material composition, mixing method and hose prepared therefrom

Abstract

The present invention relates to the technical field of hose preparation, and in particular to a hose rubber composition, a mixing method and a hose prepared by the same. The composition adopts high shear mechanical desulfurization technology and recycled rubber with compound chemical additives, which can reduce costs and improve environmental benefits while ensuring the mechanical properties of the rubber, thereby providing an environmentally friendly hose material with excellent performance. This innovative formula not only effectively utilizes waste rubber resources and reduces the pollution of waste to the environment, but also realizes the preparation of high-performance hose products.

Description

Technical Field

[0001] The invention relates to the technical field of hose preparation, and in particular to a hose rubber material composition, a mixing method and a hose prepared thereby. Background Art

[0002] With the development of industrial technology, rubber products have been widely used in various types of machinery and equipment. Among them, hoses, as one of the important industrial consumables, are widely used in the transportation of liquids, gases and other media. Hoses play a vital role in industrial production, automobile manufacturing, agriculture and other fields, and their performance requirements are very high, especially their wear resistance, aging resistance and mechanical properties. In order to ensure the stability of hoses under complex working conditions, the rubber materials of traditional hoses are usually prepared with synthetic rubbers such as natural rubber and styrene-butadiene rubber, supplemented with auxiliary materials such as reinforcing agents, vulcanizers, and plasticizers.

[0003] However, with the global emphasis on resource utilization and environmental protection, the production of rubber products faces huge environmental and economic pressures. The traditional new rubber preparation process consumes a large amount of natural rubber and synthetic rubber, resulting in high production costs, and a large number of discarded rubber products (such as waste tires, scrapped rubber hoses, etc.) are not effectively recycled, which brings a great burden to the environment. Therefore, how to efficiently utilize waste rubber resources to produce high-performance rubber products has become an important research direction in the industry.

[0004] In recent years, recycled rubber technology has gradually become the focus of the rubber industry. By desulfurizing and regenerating waste rubber, the plasticity of rubber can be effectively restored, production costs can be reduced, and the impact on the environment can be reduced. Traditional rubber recycling processes usually use chemical desulfurization or high-temperature cracking, which are inefficient and prone to secondary pollution. Summary of the invention

[0005] The present invention aims at the contradiction between high performance and environmental protection requirements in current rubber hose products, and proposes an innovative rubber composition using recycled rubber. The composition uses recycled rubber with high shear mechanical desulfurization technology and compound chemical additives, which can reduce costs and improve environmental benefits while ensuring the mechanical properties of the rubber, thereby providing an environmentally friendly rubber hose material with excellent performance. This innovative formula not only effectively utilizes waste rubber resources and reduces the pollution of waste to the environment, but also realizes the preparation of high-performance rubber hose products.

[0006] In order to achieve the above-mentioned purpose, the present invention adopts the following technical solutions: A hose rubber composition is prepared by mixing the following raw materials per 100 parts of rubber: Natural rubber: 30-50 parts; Recycled rubber: 20-40 parts; Styrene butadiene rubber: 20-30 parts; Carbon black: 40-60 parts; White carbon black: 10-20 parts; Silane coupling agent Si69: 2-4 parts; Zinc oxide: 3-5 parts; Stearic acid: 1-2 parts; Sulfur: 1.5-2.5 parts; Vulcanization accelerator: 1.0-2.0 parts; Anti-aging agent: 1.0-2.0 parts; Plasticizer: 5-10 parts; The regenerated rubber is treated with waste rubber through high shear mechanical desulfurization equipment, and the mechanical desulfurization treatment is carried out under the conditions of a shear rate of 500-1500rpm, a temperature of 140-180°C, and a pressure of 2-5 MPa, and the treatment time is 15-30 minutes; a compound chemical desulfurization aid is added during the treatment, and the compound chemical desulfurization aid includes, based on 100 parts of waste rubber, 1-butyl-3-methylimidazole hexafluorophosphate: 1.0-2.0 phr; chemical desulfurizer: 1.0-3.0 phr; plasticizer: 2.0-4.0 phr; compatibilizer: 0.5-1.5 phr.

[0007] The waste rubber described in the present invention mainly includes waste automobile tires, waste engineering vehicle tires, conveyor belts, and scraps and waste generated in the production process of rubber products.

[0008] Preferably, the high shear mechanical desulfurization equipment is a twin-screw extruder or a high shear internal mixer.

[0009] Preferably, the chemical desulfurizer is a combination of dibenzothiazole disulfide and a thiol compound; preferably, the thiol compound includes a mixture of one or more of thioglycolic acid, dipropionic acid disulfide, 2-mercaptoethanol, mercaptoethylamine, thioacetamide and mercaptobenzothiazole.

[0010] Preferably, the plasticizer is epoxidized vegetable oil or a citrate plasticizer; preferably, the citrate plasticizer is selected from one or a mixture of triethyl citrate, triethyl acetyl citrate, tributyl citrate, acetyl tributyl citrate, triisononyl citrate, tri(2-ethylhexyl) citrate, and triisooctyl citrate.

[0011] Preferably, the compatibilizer is one or more of a silane coupling agent, a titanate coupling agent, and a zirconate coupling agent; preferably, the compatibilizer is a silane coupling agent Si69.

[0012] Preferably, the plasticizer is selected from aromatic oil, terpene resin, epoxidized soybean oil or a combination thereof.

[0013] Preferably, the vulcanization accelerator is selected from one or more of accelerator CZ, accelerator DM, and accelerator TMTD; the antioxidant is selected from one or two of antioxidant 4010 and antioxidant RD.

[0014] Preferably, the carbon black is N330 type, and the white carbon black is fumed white carbon black.

[0015] Furthermore, the present invention also provides a mixing method for the hose rubber composition, which comprises the following steps: a) Adding waste rubber and compound chemical desulfurization aid into high shear mechanical desulfurization equipment for mechanical desulfurization treatment, the desulfurization conditions are temperature 140-180°C, shear rate 500-1500 rpm, pressure 2-5 MPa, and time 15-30 minutes; b) Recycled rubber and natural rubber are mixed in proportion, and carbon black, white carbon black, softener and ingredients other than vulcanizer and vulcanization accelerator are added; the mixture is kneaded in an internal mixer at 140-160°C for 5-10 minutes to ensure that all ingredients are fully mixed and uniformly formed into a homogeneous rubber compound; c) The vulcanizing agent and the vulcanization accelerator are continuously mixed in the internal mixer to form a homogeneous rubber compound; d) Extruding and tableting to obtain the hose rubber composition.

[0016] Furthermore, the present invention also provides a rubber hose, which is prepared by vulcanizing the rubber hose composition.

[0017] The present invention adopts the above-mentioned technical solution, and by using high shear mechanical desulfurization technology and compound chemical additives to recycle rubber, it can reduce costs and improve environmental benefits while ensuring the mechanical properties of the rubber material, thereby providing an environmentally friendly hose material with excellent performance. This innovative formula not only effectively utilizes waste rubber resources and reduces the pollution of waste to the environment, but also realizes the preparation of high-performance hose products. Specifically, it has the following significant technical effects: 1. Efficient desulfurization, improving the regeneration performance of waste rubber: Through high-shear mechanical desulfurization technology combined with compound chemical desulfurization additives, the vulcanization cross-linking bonds in waste rubber are effectively destroyed to restore its plasticity. Compared with traditional chemical or mechanical treatment methods, the present invention achieves efficient desulfurization under mild conditions (temperature 140-180°C, shear rate 500-1500 rpm), reduces energy consumption and the use of chemicals, and significantly improves the recycling effect of waste rubber.

[0018] 2. Synergistic effect of compound chemical desulfurization aid: The compound chemical desulfurization aid in the present invention includes 1-butyl-3-methylimidazolium hexafluorophosphate, chemical desulfurizer, plasticizer and compatibilizer, which further improves the desulfurization efficiency through synergistic effect. In particular, 1-butyl-3-methylimidazolium hexafluorophosphate can not only effectively break the vulcanization cross-linking bonds of rubber, but also improve the compatibility of waste rubber and new rubber, ensuring the uniformity and processing performance of the mixed rubber.

[0019] 3. Enhance compatibility and improve mechanical properties: The present invention effectively improves the compatibility of waste rubber and new rubber (such as natural rubber or synthetic rubber) during the mixing process by adding a compatibilizer (such as silane coupling agent Si69), ensuring the uniform combination of waste rubber and new rubber materials, avoiding the phenomenon of mutual stratification or uneven mixing of rubber, and further improving the mechanical properties of the final product.

[0020] 4. Significant environmental benefits: The present invention reduces dependence on new rubber and reduces resource consumption in the production process of rubber products by recycling waste rubber. At the same time, the compound chemical additive system used has green and environmentally friendly characteristics, reduces pollution to the environment, and meets the environmental protection requirements of modern industry.

[0021] 5. Reduce production costs: Due to the use of a large amount of waste rubber as raw material, combined with efficient desulfurization treatment, the preparation method of the present invention can significantly reduce the production cost of the hose, while ensuring the high performance of the recycled rubber through reasonable formula design. This provides an economical and efficient solution for the production of hoses. DETAILED DESCRIPTION

[0022] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with 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.

[0023] Example 1 1. Recipe: Natural rubber: 40 parts Recycled rubber: 40 parts Styrene butadiene rubber: 20 parts Carbon black (N330): 50 parts White carbon black: 15 parts Silane coupling agent Si69: 3.0 parts Zinc Oxide: 4.0 parts Stearic acid: 2.0 parts Sulfur: 2.0 parts Vulcanization accelerator CZ: 1.5 parts Antioxidant 4010: 1.5 parts Plasticizer (aromatic oil): 8.0 parts 2. Preparation process: 1) Add waste rubber and compound chemical desulfurization aids to high shear mechanical desulfurization equipment. The desulfurization conditions are: 150°C, shear rate 1000 rpm, pressure 3 MPa, and treatment time 20 minutes. The compound chemical desulfurization aid includes 1.5 parts of 1-butyl-3-methylimidazolium hexafluorophosphate, 1.5 parts of dibenzothiazole disulfide, 3.0 parts of epoxidized vegetable oil, and 1.0 parts of silane coupling agent.

[0024] 2) The desulfurized recycled rubber is mixed with natural rubber and styrene-butadiene rubber, and carbon black, white carbon black, plasticizer, zinc oxide, stearic acid, etc. are added, and mixed in an internal mixer at 150°C for 7 minutes.

[0025] 3) Add sulfur and vulcanization accelerator and continue mixing.

[0026] 4) Prepare the hose compound by extrusion and vulcanize at 155℃ for 30 minutes.

[0027] Example 2 1. Recipe: Natural rubber: 50 parts Recycled rubber: 30 parts Styrene butadiene rubber: 20 parts Carbon black (N330): 55 parts White carbon black: 10 parts Silane coupling agent Si69: 2.5 parts Zinc Oxide: 3.5 parts Stearic acid: 1.5 parts Sulfur: 2.2 parts Vulcanization accelerator CZ: 1.2 parts Anti-aging agent RD: 1.5 parts Plasticizer (terpene resin): 6.0 parts 2. Preparation process: As shown in Example 1.

[0028] Example 3 1. Recipe: Natural rubber: 30 parts Recycled rubber: 50 parts Styrene butadiene rubber: 20 parts Carbon black (N330): 45 parts White carbon black: 15 parts Silane coupling agent Si69: 4.0 parts Zinc Oxide: 4.0 parts Stearic acid: 2.0 parts Sulfur: 2.0 parts Vulcanization accelerator TMTD: 1.0 part Antioxidant 4010: 1.0 part Plasticizer (epoxidized soybean oil): 7.0 parts 2. Preparation process: As shown in Example 1.

[0029] Comparative Example 1 The compound chemical desulfurization additive is replaced by the following formula: MBTS: 2.0 phr Epoxidized vegetable oil: 3.0phr Silane coupling agent Si69: 1.0phr.

[0030] Other technical solutions are shown in Example 1.

[0031] Comparative Example 2 The compound chemical desulfurization additive is replaced by the following formula: 1-Butyl-3-methylimidazolium hexafluorophosphate: 1.2 phr.

[0032] Other technical solutions are shown in Example 1.

[0033] Comparative Example 3 The compound chemical desulfurization additive is replaced by the following formula: 1-Butyl-3-methylimidazolium hexafluorophosphate: 1.5 parts Dibenzothiazyl disulfide (MBTS): 1.5 parts Epoxidized vegetable oil: 3.0 parts.

[0034] Other technical solutions are shown in Example 1.

[0035] Comparative Example 4 The waste rubber was subjected to high-temperature mechanical desulfurization without chemical desulfurization aids. The temperature was set at 180 °C, the shear rate was 1000 rpm, and the desulfurization time was 30 minutes.

[0036] Other technical solutions are shown in Example 1.

[0037] The following is the test data of the hose: Example / Comparative Example Tensile strength(MPa) Tear strength (kN / m) Elongation at break (%) Hardness (Shore A) Aging resistance (change rate %) Wear resistance (volume loss mm³) Example 1 17.5 50 450 68 3.5 95 Example 2 18.0 52 460 69 3.2 90 Example 3 18.5 55 470 70 3.0 88 Comparative Example 1 14.0 35 380 62 10.3 145 Comparative Example 2 15.5 41 403 63 6.8 123 Comparative Example 3 16.2 46 420 67 5.4 114 Comparative Example 4 13.0 33 360 60 12.4 150 Result analysis: 1. Tensile strength The tensile strengths of Examples 1-3 are 17.5 MPa, 18.0 MPa and 18.5 MPa, respectively, which are significantly higher than the 13.0 MPa to 16.2 MPa of the comparative examples. The tensile strengths of Comparative Examples 1 and 4 are the lowest, 14.0 MPa and 13.0 MPa, respectively, indicating that the mechanical properties of the rubber material that has not been optimized are weak and it is difficult to meet the high strength requirements. The high tensile strength of the examples shows that the strength of the recycled rubber can be significantly improved by optimized high shear mechanical desulfurization and compound chemical desulfurization aids, making it more suitable for bearing greater stress and high load applications.

[0038] 2. Tear strength The tear strengths of Examples 1-3 are 50-55 kN / m, respectively, much higher than the 33-46 kN / m of the comparative examples. The tear strengths of Comparative Examples 1 and 4 are 35 kN / m and 33 kN / m, respectively, which are the worst, indicating that these materials are more prone to tearing and breakage in actual use. The significant improvement in tear strength in the examples is due to the optimized formula and process, which makes the bonding force between the rubber molecular chains stronger, ensuring that the material has better tear resistance under high strain environments.

[0039] 3. Elongation at break The elongations at break of Examples 1-3 are 450%, 460% and 470% respectively, showing excellent elasticity and toughness. The elongations at break of Comparative Examples 1 and 4 are 380% and 360% respectively, indicating that these materials are easy to break under high stress and have poor flexibility. The reclaimed rubber of the Example is desulfurized, and its flexibility is significantly enhanced, ensuring that it can maintain a long service life under complex working conditions.

[0040] 4. Hardness (Shore A) The hardness of Examples 1-3 is 68, 69 and 70 Shore A, respectively, which is very suitable for high-strength applications, indicating that the material has good load-bearing and compression resistance. The hardness of the comparative examples ranges from 60-67 Shore A, especially the lowest hardness of Examples 1 and 4, which are 62 and 60 Shore A, respectively, and it is difficult to provide sufficient support under high-load conditions. The hardness of the embodiment is slightly higher, proving that the material has good strength and durability while retaining flexibility.

[0041] 5. Aging resistance The aging resistance change rates of Examples 1-3 are 3.5%, 3.2% and 3.0%, respectively, which are much lower than the 5.4%-12.4% of the comparative example. The aging resistance change rate of Comparative Example 4 is 12.4%, indicating that its aging resistance is the worst and it is prone to aging and performance degradation in long-term use. The excellent aging resistance of the examples is attributed to the use of compound chemical desulfurization additives, which effectively delay the aging process of the material and ensure that its performance remains stable in long-term use.

[0042] 6. Wear resistance The wear resistance of Examples 1-3 is very good, with volume losses of 95 mm³, 90 mm³ and 88 mm³, respectively, showing excellent wear resistance and suitable for high wear environments. The wear resistance of the comparative examples is poor, especially comparative examples 1 and 4, with volume losses of 145 mm³ and 150 mm³, respectively, showing a large wear rate and a short service life. The recycled rubber in the examples has been optimized and its wear resistance is significantly enhanced, which is particularly suitable for occasions with frequent friction and high wear.

[0043] Through the high shear mechanical desulfurization technology and compound chemical desulfurization additives in the present invention, the comprehensive performance of the recycled rubber is significantly improved. Its excellent tensile strength, aging resistance and wear resistance ensure the high durability and long service life of the hose. At the same time, the effective utilization of resources and the reduction of costs also provide a sustainable development solution for industrial production.

[0044] The above is a description of the embodiments of the present invention. Through the above description of the disclosed embodiments, professionals and technicians in the field can implement or use the present invention. Various modifications to these embodiments will be apparent to professionals and technicians in the field. The general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown in this article, but will conform to the widest range consistent with the principles and novelties disclosed herein.

Claims

1. A hose rubber composition, characterized in that: The hose rubber composition is prepared by mixing the following raw materials per 100 parts of rubber: Natural rubber: 30-50 parts; Recycled rubber: 20-40 parts; Styrene butadiene rubber: 20-30 parts; Carbon black: 40-60 parts; White carbon black: 10-20 parts; Silane coupling agent Si69: 2-4 parts; Zinc oxide: 3-5 parts; Stearic acid: 1-2 parts; Sulfur: 1.5-2.5 parts; Vulcanization accelerator: 1.0-2.0 parts; Antiaging agent: 1.0-2.0 parts; Plasticizer: 5-10 parts; The regenerated rubber is treated with waste rubber through high shear mechanical desulfurization equipment, and the mechanical desulfurization treatment is carried out under the conditions of a shear rate of 500-1500rpm, a temperature of 140-180°C, and a pressure of 2-5 MPa, and the treatment time is 15-30 minutes; A compound chemical desulfurization aid is added during the treatment, and the compound chemical desulfurization aid includes, based on 100 parts of waste rubber, 1-butyl-3-methylimidazolium hexafluorophosphate: 1.0-2.0 phr; chemical desulfurizer: 1.0-3.0 phr; plasticizer: 2.0-4.0 phr; compatibilizer: 0.5-1.5 phr.

2. The hose rubber composition according to claim 1, characterized in that: The high shear mechanical desulfurization equipment is a twin-screw extruder or a high shear internal mixer.

3. The hose rubber composition according to claim 1, characterized in that: The chemical desulfurizer is a combination of dibenzothiazole disulfide and a thiol compound; preferably, the thiol compound includes a mixture of one or more of thioglycolic acid, dipropionic acid disulfide, 2-mercaptoethanol, mercaptoethylamine, thioacetamide and mercaptobenzothiazole.

4. The hose rubber composition according to claim 1, characterized in that: The plasticizer is epoxidized vegetable oil or a citrate plasticizer; preferably, the citrate plasticizer is selected from one or a mixture of triethyl citrate, triethyl acetyl citrate, tributyl citrate, acetyl tributyl citrate, triisononyl citrate, tri(2-ethylhexyl) citrate, and triisooctyl citrate.

5. The hose rubber composition according to claim 1, characterized in that: The compatibilizer is one or more of a silane coupling agent, a titanate coupling agent, and a zirconate coupling agent; preferably, the compatibilizer is a silane coupling agent Si69.

6. The hose rubber composition according to claim 1, characterized in that: The plasticizer is selected from aromatic oil, terpene resin, epoxidized soybean oil or a combination thereof.

7. The hose rubber composition according to claim 1, characterized in that: The vulcanization accelerator is selected from one or more of accelerator CZ, accelerator DM and accelerator TMTD; the antioxidant is selected from one or two of antioxidant 4010 and antioxidant RD.

8. The hose rubber composition according to claim 1, characterized in that: The carbon black is of N330 type, and the white carbon black is fumed white carbon black.

9. The method for mixing a hose rubber composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: a) Adding waste rubber and compound chemical desulfurization aid into high shear mechanical desulfurization equipment for mechanical desulfurization treatment, the desulfurization conditions are temperature 140-180°C, shear rate 500-1500 rpm, pressure 2-5 MPa, and time 15-30 minutes; b) Recycled rubber and natural rubber are mixed in proportion, and carbon black, white carbon black, softener and ingredients other than vulcanizer and vulcanization accelerator are added; the mixture is kneaded in an internal mixer at 140-160°C for 5-10 minutes to ensure that all ingredients are fully mixed and uniformly formed into a homogeneous rubber compound; c) The vulcanizing agent and the vulcanization accelerator are continuously mixed in the internal mixer to form a homogeneous rubber compound; d) Extruding and tableting to obtain the triangle tape rubber composition.

10. A hose, characterized in that: The rubber hose is prepared by vulcanizing the rubber hose composition described in any one of claims 1 to 8.