Formula and preparation method of bio-based rubber

Abstract

A formula and a preparation method of bio-based rubber belong to the technical field of high-molecular compounds. The bio-based rubber material produced by the formula and the preparation method disclosed by the invention is obtained by matching different types of rubber according to a specific proportion. The bio-based raw material is creatively used for replacing a traditional petroleum-based raw material, the requirement for the petroleum-based raw material is effectively reduced, and the prepared rubber material can meet all use requirements of the cooling pipeline. The preparation method disclosed by the invention is low in production cost, efficient in process and suitable for industrialized production. The bio-based rubber prepared according to the formula and the preparation method is used for producing a cooling pipeline of a bio-based rubber sizing material. The cooling pipeline is good in high and low temperature resistance, low in cost and excellent in cooling liquid resistance, on the premise that vehicle cooling is met, the requirement for petroleum-based raw materials in a rubber formula is greatly reduced through use of bio-based materials, and the requirements for sustainable development, reduction of carbon dioxide emission and the like are met.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer compounds, and in particular relates to a formula and a preparation method of bio-based rubber. Background Art

[0002] Automobile cooling hoses are an important component of the automobile cooling system. They are the medium for transmitting coolant and are distributed in the automobile engine compartment and around the battery.

[0003] Currently, automotive cooling system hoses are typically made from traditional ethylene propylene diene monomer (EPDM), and the raw materials in traditional rubber formulations are all petroleum-based. With the global demand for sustainable development, rubber formulations are increasingly requiring the use of bio-based or recyclable materials to mitigate environmental impact. Due to the specific requirements for high and low temperature resistance, mechanical strength, compressive strain resistance, and electrical resistance of automotive cooling system hoses, there is currently no bio-based rubber hose preparation method that can meet these parameter requirements.

[0004] Therefore, a new technical solution is urgently needed in the existing technology to solve this problem. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a formula and preparation method of bio-based rubber to solve the technical problem that there is currently no preparation method for bio-based rubber hoses that can meet the various parameter requirements of automobile cooling system hoses.

[0006] A bio-based rubber formula is used to prepare a bio-based rubber compound. The bio-based rubber comprises the following components, calculated by weight: 100 parts of a rubber raw material, 0 to 50 parts of a filler, 70 to 125 parts of a reinforcing agent, and 30 to 50 parts of a plasticizer. At least one of the rubber raw material, filler, reinforcing agent, and plasticizer is mixed with a bio-based material or at least one is a bio-based material.

[0007] The rubber raw material includes common rubber raw materials and / or bio-based rubber raw materials.

[0008] The ordinary rubber raw material includes at least one of EPDM 2650C, EPDM 5470C, EPDM 6470C and EPDM 4045M; the bio-based rubber raw material includes at least one of bio-based EPDM 5470, bio-based EPDM 8550 and bio-based EPDM 6950.

[0009] The bio-based rubber raw material includes bio-based rubber, wherein the ethylene content is 45 wt.% to 70 wt.%, and the Mooney viscosity of the bio-based rubber is 25 to 80 under the condition of ML125°C (1+4).

[0010] The filler includes at least one of bio-based silicon carbon black and white carbon black.

[0011] The reinforcing agent is carbon black, which includes at least one of carbon black N550, DUREX O carbon black, N774 and N990 with different particle sizes. The carbon black is ordinary carbon black or bio-based carbon black.

[0012] The plasticizer includes at least one of paraffin oil 2280, bio-based paraffin oil RECOR-T4867, and paraffin oil 2286T.

[0013] A formula of bio-based rubber also includes rubber additives; the rubber additives include an activator, an anti-aging agent, a vulcanizing agent and a vulcanizing accelerator.

[0014] A method for preparing bio-based rubber, using the above-mentioned bio-based rubber formula, comprises the following steps:

[0015] (a) mixing 0 to 50 parts of a filler, 70 to 125 parts of a reinforcing agent, and 30 to 50 parts of a plasticizer to obtain a mixture A;

[0016] (b) mixing 100 parts of the rubber raw material with the anti-aging agent to obtain a mixture B;

[0017] (c) mixing the filler, reinforcing agent, plasticizer, rubber raw material and the remaining raw materials except the anti-aging agent to obtain a mixture C;

[0018] (d) Mixture B and mixture C are kneaded until the kneading temperature reaches 100°C to 125°C, and mixture A is added and the kneading is continued until the temperature reaches 160°C to 180°C to obtain rubber.

[0019] The remaining raw materials include active agents, vulcanizing agents and vulcanization aids.

[0020] Through the above design scheme, the present invention can bring the following beneficial effects:

[0021] One objective of the present invention is to provide a bio-based rubber formulation. This formulation produces a bio-based rubber compound composed of different rubber types in specific proportions. The formulation innovatively uses bio-based raw materials in place of traditional petroleum-based raw materials, effectively reducing the demand for these raw materials. The bio-based components, including but not limited to rubber, plasticizers, reinforcing agents, fillers, and other additives, result in a rubber compound exhibiting excellent high- and low-temperature resistance, mechanical strength, compression deformation resistance, and electrical resistance. Furthermore, the compound exhibits excellent mixing and extrusion processability, meeting all cooling pipe application requirements.

[0022] A second object of the present invention is to provide a method for preparing bio-based rubber, which has low production cost, high process efficiency, and is suitable for factory production.

[0023] The cooling pipes for producing bio-based rubber compounds using the bio-based rubber prepared using the formula and preparation method of the present invention not only have excellent high and low temperature resistance and low cost, but also have excellent coolant resistance. Under the premise of meeting vehicle cooling requirements, the use of bio-based materials greatly reduces the demand for petroleum-based raw materials in the rubber formula, meeting the requirements of sustainable development and reducing carbon dioxide emissions. DETAILED DESCRIPTION

[0024] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0025] A bio-based rubber formula for preparing a bio-based rubber compound comprises the following components, calculated by weight: 100 parts of a rubber raw material, 0 to 50 parts of a filler, 70 to 125 parts of a reinforcing agent, and 30 to 50 parts of a plasticizer.

[0026] Preferably, the rubber compound comprises the following components in parts by mass: 100 parts of rubber raw material, 45 parts of filler, 80 parts of reinforcing agent and 40 parts of plasticizer.

[0027] In the present invention, the technical effect of the rubber compound of the present invention is further optimized by further adjusting and optimizing the usage ratio of each component raw material.

[0028] The rubber compound provided by the present invention is primarily prepared from a rubber raw material, a reinforcing agent, a filler, and a plasticizer in specific component proportions. At least one of the rubber raw material, filler, reinforcing agent, and plasticizer is mixed with a bio-based material, or at least one is a bio-based material. By combining bio-based and petroleum-based raw materials in specific ratios, the rubber compound produced by the present invention achieves sustainable development and reduces carbon dioxide emissions.

[0029] Among them, the rubber raw material is typically but not limited to a preferred embodiment: 100 parts, and in the rubber raw material, the ratio of medium Mooney high ethylene content to high Mooney low ethylene content can be 40:60, 45:55, 50:50, 55:45 or 60:40. The filler is typically but not limited to a preferred embodiment: 0 parts, 10 parts, 20 parts, 30 parts, 40 parts or 50 parts. The reinforcing agent is typically but not limited to a preferred embodiment: 70 parts, 80 parts, 90 parts, 110 parts or 125 parts. The plasticizer is typically but not limited to a preferred embodiment: 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.

[0030] The rubber raw material is a rubber having an ethylene content of 60-65 wt% and a Mooney viscosity of 25-80 at ML125°C (1+4); the rubber is preferably a bio-based rubber, and the bio-based rubber raw material is preferably bio-based EPDM rubber 5470 and / or bio-based EPDM rubber 8550 / or bio-based EPDM rubber 6950;

[0031] The filler comprises at least one of bio-based silicon carbon black and white carbon black. Preferably, the filler is bio-based silicon carbon black. Bio-based silicon carbon black is refined from rice crops and undergoes multiple layers of deep processing to form a spherical nanostructured silicon carbon black. It is primarily composed of nano-silicon dioxide and micron carbon black. After organic modification, it has excellent reinforcing properties and can be widely used in industries such as rubber, plastics, and inks. In the rubber industry, silicon bio-carbon black is currently the most cost-effective bio-based material with the best overall process performance and reinforcing properties, replacing or partially replacing carbon black.

[0032] The reinforcing agent is carbon black of different particle sizes, including N550, DUREX O carbon black, N774, and N990; preferably, the reinforcing agent is bio-based carbon black.

[0033] The plasticizer includes at least one of paraffin oil 2280, bio-based paraffin oil RECOR-T4867 and paraffin oil 2286T; preferably, the plasticizer is a bio-based plasticizer.

[0034] The rubber compound further comprises a rubber additive; the rubber additive comprises at least one of an active agent, an anti-aging agent, a vulcanizing agent and a vulcanizing accelerator. Preferably, the rubber additive comprises an active agent, an anti-aging agent, a vulcanizing agent and a vulcanizing accelerator at the same time.

[0035] The active agent includes at least one of zinc oxide, magnesium oxide and titanium dioxide. The active agent can act as an acid absorber and stabilizer to increase the vulcanization speed, and can also act as a cross-linking agent to improve the cross-linking strength and tensile properties.

[0036] The mass proportion of the active agent in the rubber compound is 5 to 10 parts by mass, with typical but non-limiting preferred embodiments being 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.

[0037] The anti-aging agent includes at least one of anti-aging agent RD, anti-aging agent MB, and anti-aging agent 445. The anti-aging agent is present in the rubber compound in an amount of 1.5 to 5 parts by mass, with typical but non-limiting preferred embodiments being 1.5 parts, 2.5 parts, 3.5 parts, or 4.5 parts.

[0038] The vulcanizing agent includes at least one of peroxide 14-40B, peroxide 101-45D, peroxide BIPB-40, and peroxide DBPH-45. The vulcanizing agent can crosslink rubber molecules to form a three-dimensional network structure, thereby improving rubber properties. The vulcanizing agent is present in the rubber compound in an amount of 3 to 15 parts by weight, with typical but non-limiting preferred embodiments being 6, 7, 8, 9, 10, 11, 12, or 13 parts.

[0039] The vulcanization accelerator includes at least one of sulfur, TAIC, and TAC. The amount of the vulcanization accelerator in the rubber compound is 0.5 to 3 parts by weight. The vulcanization accelerator can shorten vulcanization time, lower vulcanization temperature, reduce the amount of vulcanizing agent used, and improve the physical and mechanical properties of the rubber.

[0040] Typical but non-limiting preferred embodiments of the above-mentioned vulcanization auxiliary are: 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, and 3 parts.

[0041] A method for preparing bio-based rubber comprises mixing the raw materials in the bio-based rubber formula to obtain a rubber compound. The method comprises the following steps:

[0042] (a) mixing 0 to 50 parts of a filler, 60 to 125 parts of a reinforcing agent, and 25 to 50 parts of a plasticizer to obtain a mixture A;

[0043] (b) mixing 100 parts of the rubber raw material with the anti-aging agent to obtain a mixture B;

[0044] (c) mixing the filler, reinforcing agent, plasticizer, rubber raw material and the remaining raw materials except the anti-aging agent to obtain a mixture C;

[0045] (d) Mixture B and mixture C are kneaded until the kneading temperature reaches 100°C to 125°C, and mixture A is added and the kneading is continued until the temperature reaches 160°C to 180°C to obtain rubber.

[0046] The order of steps (a), (b) and (c) can be changed, which has the advantage of easy operation.

[0047] The remaining raw materials include active agents, vulcanizing agents and vulcanization aids.

[0048] The bio-based rubber compound prepared by the method of the present invention can be used to prepare cooling hoses used in automobile cooling systems. The cooling hoses include full-rubber cooling hoses or three-layer cooling hoses.

[0049] The bio-based rubber compound prepared by the present invention is extruded and then vulcanized to obtain a cooling hose. Preferably, the extrusion temperature of the bio-based rubber compound is: 70°C to 100°C for the die head, 70°C to 100°C for the extrusion section, 60°C to 90°C for the feeding section, and 50°C to 80°C for the screw.

[0050] Preferably, the vulcanization temperature is 170° C. to 190° C., and the vulcanization time is 15 min to 45 min.

[0051] The technical solution of the present invention will be further described below with reference to embodiments and comparative examples.

[0052] Weigh the raw materials according to the weight ratio of the raw materials in the following table:

[0053]

[0054]

[0055]

[0056]

[0057] Table 2 Comparison of carbon dioxide emissions in the above examples

[0058] Example 1 Example 2 Example 3 Example 4 Example 5 <![CDATA[Carbon emission kgCO2 / kg]]> 2.43 2.26 2.20 2.37 2.13 Carbon emissions reduction ratio (%) 12.6 18.2 20.2 15.4 20.7 Example 6 Example 7 Example 8 Example 9 Example 10 Carbon emissions kgCO2 / kg 2.43 2.26 2.20 2.37 2.13 Carbon emissions reduction ratio (%) 12.6 18.2 20.2 15.4 20.7

[0059] Table 3 Test results of rubber compounds obtained in various embodiments

[0060]

[0061]

[0062] The carbon emissions of the various raw materials listed in Table 1 were calculated. These raw materials include collagen, fillers, reinforcing agents, and plasticizers. Table 2 shows that the use of bio-based raw materials can significantly reduce CO2 emissions. Further adjustment and optimization of the bio-based raw material ratios in each component can further reduce CO2 emissions while maintaining product performance. Table 3 shows that the 10 examples meet the requirements for cooling hose use in terms of thermal aging performance, mechanical strength, coolant performance, compression set, and electrochemical resistance.

Claims

1. A bio-based rubber formula for preparing a bio-based rubber compound, characterized by: The bio-based rubber comprises the following components in parts by mass: 100 parts of rubber raw material, 0 to 50 parts of filler, 70 to 125 parts of reinforcing agent, and 30 to 50 parts of plasticizer; at least one of the rubber raw material, filler, reinforcing agent, and plasticizer is mixed with bio-based material or at least one is made of bio-based material.

2. The bio-based rubber formulation according to claim 1, characterized in that: The rubber raw material includes common rubber raw materials and / or bio-based rubber raw materials.

3. The bio-based rubber formulation according to claim 2, characterized in that: The ordinary rubber raw material includes at least one of EPDM 2650C, EPDM 5470C, EPDM 6470C and EPDM 4045M; the bio-based rubber raw material includes at least one of bio-based EPDM 5470, bio-based EPDM 8550 and bio-based EPDM 6950.

4. The bio-based rubber formulation according to claim 2, characterized in that: The bio-based rubber raw material includes bio-based rubber, wherein the ethylene content is 45 wt.% to 70 wt.%, and the Mooney viscosity of the bio-based rubber is 25 to 80 under the condition of ML125°C (1+4).

5. The bio-based rubber formulation according to claim 1, characterized in that: The filler includes at least one of bio-based silicon carbon black and white carbon black.

6. The bio-based rubber formulation according to claim 1, characterized in that: The reinforcing agent is carbon black, which includes at least one of carbon black N550, DUREX O carbon black, N774 and N990 with different particle sizes. The carbon black is ordinary carbon black or bio-based carbon black.

7. The bio-based rubber formulation according to claim 1, characterized in that: The plasticizer includes at least one of paraffin oil 2280, bio-based paraffin oil RECOR-T4867, and paraffin oil 2286T.

8. The bio-based rubber formulation according to claim 1, characterized in that: It also includes rubber additives; the rubber additives include activators, anti-aging agents, vulcanizers and vulcanizing additives.

9. A method for preparing a bio-based rubber, using the bio-based rubber formula of claim 1, characterized by: The following steps are involved: (a) mixing 0 to 50 parts of a filler, 60 to 125 parts of a reinforcing agent, and 25 to 50 parts of a plasticizer to obtain a mixture A; (b) mixing 100 parts of the rubber raw material with the anti-aging agent to obtain a mixture B; (c) mixing the filler, reinforcing agent, plasticizer, rubber raw material and the remaining raw materials except the anti-aging agent to obtain a mixture C; (d) Mixture B and mixture C are kneaded until the kneading temperature reaches 100°C to 125°C, and mixture A is added and the kneading is continued until the temperature reaches 160°C to 180°C to obtain rubber.

10. The method for preparing a bio-based rubber according to claim 9, characterized in that: The remaining raw materials include active agents, vulcanizing agents and vulcanization aids.

Images