Formulation and preparation method for BIO-based rubber

Abstract

A formulation and a preparation method for bio-based rubber. The bio-based rubber is obtained by blending different types of rubber at specific proportions. Bio-based raw materials are creatively used to replace conventional petroleum-based raw materials, which effectively reduces the demand for petroleum-based raw materials, and the prepared rubber compound can meet all usage requirements for cooling pipelines. The preparation method has low production cost and high process efficiency, and is suitable for industrialized production. The bio-based rubber is used for manufacturing cooling pipelines with bio-based rubber compounds. The cooling pipelines not only have excellent resistance to both high and low temperatures and offer low cost, but also have outstanding resistance to cooling fluids. While satisfying vehicle cooling requirements, the use of bio-based materials significantly reduces the demand for petroleum-based raw materials in the rubber formulation and meets requirements for sustainable development and reducing carbon dioxide emission.

Description

Attorney Docket No. 91601-01145Client Ref. No. P24031WOFORMULATION AND PREPARATION METHOD FOR BIO-BASED RUBBERRELATED APPLICATIONS

[0001] The present disclosure claims priority to and the benefit of Chinese Application 202411429378.3, filed on October 14, 2024, the entire contents of each of which are incorporated herein by reference.FIELD

[0002] The present disclosure belongs to the technical field of polymer compounds, and in particular relates to a formulation and a preparation method for bio-based rubber.BACKGROUND

[0003] Automotive cooling rubber hoses are important components of an automotive cooling system, serve as a medium for transporting a cooling fluid, and are distributed in the automotive engine compartment and around the battery.

[0004] At present, rubber hoses in automotive cooling systems are typically made of conventional ethylene propylene diene monomer (EPDM), and all raw materials used in conventional rubber formulations are petroleum based. With the growing global demand for sustainable development, more and more raw materials in rubber formulations are required to be bio-based or recyclable so as to reduce environmental impact. Due to the special requirements of rubber hoses in automotive cooling systems in terms of resistance to high and low temperatures, mechanical strength, compression set resistance, and electrical resistance, there is currently no preparation method for bio-based rubber hoses capable of meeting these parameter requirements thereof.

[0005] Therefore, there is an urgent need in the prior art for a novel technical solution to address this problem.Attorney Docket No. 91601-01145Client Ref. No. P24031WOBRIEF SUMMARY

[0006] The technical problem to be solved by the present disclosure is to provide a formulation and a preparation method for bio-based rubber to address the technical problem that there is currently no preparation method for biobased rubber hoses capable of meeting various parameter requirements of automotive cooling system hoses.

[0007] A formulation for bio-based rubber used for preparing a bio-based rubber compound, wherein the bio-based rubber comprises, based on parts by mass, the following components: 100 parts of a rubber raw material, 0 part to 50 parts of a filler, 70 parts to 125 parts of a reinforcing agent, and 30 parts to 50 parts of a plasticizer; at least one of the rubber raw material, the filler, the reinforcing agent, and the plasticizer is mixed with a bio-based material, or at least one thereof uses a bio-based material.

[0008] The rubber raw material comprises conventional rubber raw materials and / or bio-based rubber raw materials.

[0009] The conventional rubber raw materials comprise at least one of EPDM 2650C, EPDM 5470C, EPDM 6470C, and EPDM 4045M; and the biobased rubber raw materials comprise at least one of bio-based EPDM 5470, bio-based EPDM 8550, and bio-based EPDM 6950.

[0010] The bio-based rubber raw materials comprise bio-based rubber, wherein the ethylene content is 45 wt.% to 70 wt.%, and the bio-based rubber has a Mooney viscosity of 25 to 80 under conditions of ML 125°C (1+4).

[0011] The filler comprises at least one of bio-based silicon-carbon black and silica.

[0012] The reinforcing agent is carbon black, the carbon black comprises at least one of carbon black N550, DU REX O carbon black, N774, and N990 having different particle sizes, and the carbon black is of conventional carbon black or bio-based carbon black.

[0013] The plasticizer comprises at least one of paraffinic oil 2280, biobased paraffinic oil RECOR-T4867, and paraffinic oil 2286T.

[0014] A formulation for bio-based rubber, further comprising rubberAttorney Docket No. 91601-01145Client Ref. No. P24031WO additives; and the rubber additives comprise activators, anti-aging agents, vulcanizing agents, and vulcanization accelerators.

[0015] A preparation method for bio-based rubber that uses the formulation for bio-based rubber, comprising the following steps:

[0016] (a) mixing 0 part to 50 parts of the filler, 70 parts to 125 parts of the reinforcing agent, and 30 parts to 50 parts of the plasticizer to obtain mixture A;

[0017] (b) mixing 100 parts of the rubber raw material with the anti-aging agent to obtain mixture B;

[0018] (c) mixing the remaining raw materials other than the filler, the reinforcing agent, the plasticizer, the rubb w material, and the anti-aging agent to obtain mixture C;

[0019] (d) mixing mixture B with mixture C and a mixing temperature is raised to 100°C to 125°C, adding mixture A thereto, continuing the mixing, and discharging the compound at 160°C to 180°C to obtain rubber.

[0020] The remaining raw materials comprise activators, vulcanizing agents, and vulcanization accelerators.

[0021] Through the above design solutions, the present disclosure can achieve the following beneficial effects:

[0022] The present disclosure provides a formulation for bio-based rubber, wherein the bio-based rubber compound produced using this formulation is obtained by blending different types of rubber at specific proportions, and biobased raw materials are innovatively used in the formulation to replace conventional petroleum-based raw materials, thereby effectively reducing the demand for petroleum-based raw materials. The bio-based components thereof include, but are not limited to, rubber, plasticizers, reinforcing agents, fillers, and other additives, so that the prepared rubber compound exhibits good performance in resistance to high and low temperatures, mechanical strength, compression set resistance, and electrical resistance; at the same time, it also provides excellent mixing and extrusion processability, thereby meeting all performance requirements of cooling pipelines.

[0023] The present disclosure also provides a preparation method for bio-Attorney Docket No. 91601-01145Client Ref. No. P24031WO based rubber, and the method has low production cost and high process efficiency, and is suitable for industrialized production.

[0024] Cooling pipelines made of the bio-based rubber compound prepared using the formulation and preparation method of the present disclosure not only have excellent resistance to both high and low temperatures and offer low cost, but also have outstanding resistance to cooling fluids. While satisfying vehicle cooling requirements, the use of bio-based materials significantly reduces the demand for petroleum-based raw materials in the rubber formulation and meets requirements for sustainable development and reducing carbon dioxide emission.DETAILED DESCRIPTION

[0025] The technical solutions of the present disclosure will be described clearly and completely below in conjunction with embodiments. Obviously, the described embodiments are only part of the embodiments of the present disclosure, rather than all embodiments thereof. Based on the embodiments of the present disclosure, all other embodiments obtained by a person skilled in the art without creative effort shall fall within the scope of protection of the present disclosure.

[0026] A formulation for bio-based rubber used for preparing a bio-based rubber compound, wherein the bio-based rubber comprises, based on parts by mass, the following components: 100 parts of a rubber raw material, 0 part to 50 parts of a filler, 70 parts to 125 parts of a reinforcing agent, and 30 parts to 50 parts of a plasticizer; at least one of the rubber raw material, the filler, the reinforcing agent, and the plasticizer is mixed with a bio-based material, or at least one thereof uses a bio-based material.

[0027] Preferably, based on parts by mass, the bio-based rubber comprises the following components: 100 parts of a rubber raw material, 45 parts of a filler, 80 parts of a reinforcing agent, and 40 parts of a plasticizer.

[0028] In the present disclosure, the technical effects of the rubber compound according to the present disclosure are further optimized by furtherAttorney Docket No. 91601-01145Client Ref. No. P24031WO adjusting and optimizing the proportions of the respective component raw materials.

[0029] The bio-based rubber compound provided by the present disclosure is obtained mainly by the rubber raw material, the reinforcing agent, the filler, and the plasticizer at specific proportions. At least one of the rubber raw material, the filler, the reinforcing agent, and the plasticizer is mixed with a biobased material, or at least one of them uses a bio-based material. According to the present disclosure, bio-based raw materials and petroleum-based raw materials are used in combination at specific proportions, enabling the prepared rubber compound to meet sustainable development objectives and reduce carbon dioxide emission.

[0030] Herein, a typical but non-limiting preferred embodiment of the rubber raw materials is: 100 parts. Of the rubber raw materials, the ratio of rubber raw materials with medium Mooney and a high ethylene content to rubber raw materials with high Mooney and a low ethylene content may be 40:60, 45:55, 50:50, 55:45, or 60:40.

[0031] A typical but non-limiting preferred embodiment of the filler is: 0 part, 10 parts, 20 parts, 30 parts, 40 parts, or 50 parts. A typical but non-limiting preferred embodiment of the reinforcing agent is: 70 parts, 80 parts, 90 parts, 110 parts, or 125 parts. A typical but non-limiting preferred embodiment of the plasticizer is: 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts.

[0032] The rubber raw material is rubber with an ethylene content of 60 wt.% to 65 wt.%, and a Mooney viscosity of 25 to 80 under conditions of ML 125°C (1+4); the rubber is preferably bio-based rubber, and the bio-based rubber raw materials are preferably bio-based EPDM 5470 and / or bio-based EPDM 8550 and / or bio-based EPDM 6950.

[0033] The filler comprises at least one of bio-based silicon-carbon black and silica. Preferably, the filler is bio-based silicon-carbon black. The bio-based silicon-carbon black is obtained from refined rice crops through multi-stage deep processing, forming a quasi-spherical nano-microstructured silica carbon black, which mainly comprises nano-silica and micro-scale carbon black. AfterAttorney Docket No. 91601-01145Client Ref. No. P24031WO organic modification, it exhibits good reinforcing capabilities and can be widely used in industries such as rubber, plastics, inks, and the like. In the rubber industry, bio-based silica carbon black is currently the most cost-effective biobased material with comprehensive processing and reinforcing performance, capable of replacing or partially replacing conventional carbon black.

[0034] The reinforcing agent is carbon blacks having different particle sizes, including N550, DLIREX O carbon black, N774, and / or N990; and preferably, the reinforcing agent is bio-based carbon black.

[0035] The plasticizer comprises at least one of paraffinic oil 2280, biobased paraffinic oil RECOR-T4867, and / or paraffinic oil 2286T; and preferably, the plasticizer is a bio-based plasticizer.

[0036] The rubber compound further comprises rubber additives; and the rubber additives comprise at least one of activators, anti-aging agents, vulcanizing agents, and / or vulcanization accelerators. Preferably, the rubber additives comprise activators, anti-aging agents, vulcanizing agents, and / or vulcanization accelerators at the same time.

[0037] The activators comprise at least one of zinc oxide, magnesium oxide, and / or titanium dioxide. The activators may serve as an acid scavenger or stabilizer to increase the vulcanization speed, and may also serve as a cocrosslinking agent to improve crosslinking strength and tensile properties.

[0038] Based on parts by mass, the activators account for 5 to 10 parts by mass in the rubber compound, and a typical but non-limiting preferred embodiment thereof is 5, 6, 7, 8, 9, or 10 parts.

[0039] The anti-aging agents comprise at least one of anti-aging agent RD, anti-aging agent MB, and anti-aging agent 445. Based on parts by mass, the anti-aging agents account for 1.5 to 5 parts by mass in the rubber compound, and a typical but non-limiting preferred embodiment thereof is 1.5, 2.5, 3.5, or 4.5 parts.

[0040] The vulcanizing agents comprise at least one of peroxide 14-40B, peroxide 101-45D, peroxide BIPB-40, and / or peroxide DBPH-45. The vulcanizing agents can produce crosslinks between rubber molecules to form aAttorney Docket No. 91601-01145Client Ref. No. P24031WO three-dimensional network structure, thereby improving the rubber’s properties. Based on parts by mass, the vulcanizing agents account for 3 to 15 parts by mass in the rubber compound, and a typical but non-limiting preferred embodiment thereof is 6, 7, 8, 9, 10, 11 , 12, or 13 parts.

[0041] The vulcanization accelerators comprise at least one of sulfur, vulcanization accelerator TAIC, and vulcanization accelerator TAC. Based on parts by mass, the vulcanization accelerators account for 0.5 to 3 parts by mass in the rubber compound. The vulcanization accelerators may shorten the vulcanization time, reduce the vulcanization temperature, decrease the amount of vulcanizing agents used, and improve the rubber’s physical and mechanical properties.

[0042] A typical but non-limiting preferred embodiment of the above vulcanization accelerators is 0.5, 1 , 1.5, 2, 2.5, or 3 parts.

[0043] A preparation method for bio-based rubber that uses the formulation for bio-based rubber in which the raw materials in the formulation are mixed to obtain a rubber compound. The preparation method comprises the following steps:

[0044] (a) mixing 0 part to 50 parts of the filler, 60 parts to 125 parts of the reinforcing agent, and 25 parts to 50 parts of the plasticizer to obtain mixture A;

[0045] (b) mixing 100 parts of the rubber raw material with the anti-aging agent to obtain mixture B;

[0046] (c) mixing the remaining raw materials other than the filler, the reinforcing agent, the plasticizer, the rubber raw material, and the anti-aging agent to obtain mixture C;

[0047] (d) mixing mixture B with mixture C and the mixing temperature is raised to 100°C to 125°C, adding mixture A thereinto, continuing the mixing, and discharging the compound at 160°C to 180°C to obtain rubber.

[0048] The sequence of steps (a), (b), and (c) may be interchanged, which also has the advantage of ease operation.

[0049] The remaining raw materials comprise activators, vulcanizing agents, and vulcanization accelerators.Attorney Docket No. 91601-01145Client Ref. No. P24031WO

[0050] The bio-based rubber compound prepared using the method of the present disclosure may be used to make cooling hoses used in automotive cooling systems. The cooling hoses may be all-rubber cooling hoses or three- layer cooling hoses.

[0051] A cooling hose can be obtained by extruding and then vulcanizing the bio-based rubber compound prepared according to the present disclosure. Preferably, the extrusion temperature for the bio-based rubber compound is as follows: die head 70°C to 100°C, extrusion section 70°C to 100°C, feed section 60°C to 90°C, and screw 50°C to 80°C.

[0052] Preferably, the vulcanization temperature is 170°C to 190°C, and the vulcanization time is 15 min to 45 min.

[0053] The technical solutions of the present disclosure will be further described below with reference to embodiments and comparative examples.

[0054] Weigh respective raw materials according to the parts by weight of the raw materials listed in the table below:Attorney Docket No. 91601-01145Client Ref. No. P24031WOTable 2 Comparison of carbon dioxide emission of the above embodimentsAttorney Docket No. 91601-01145Client Ref. No. P24031WOTable 3 Test results of the rubber compounds prepared in various embodimentsAttorney Docket No. 91601-01145Client Ref. No. P24031WOCarbon emission is calculated for various raw materials in Table 1 , and the raw materials comprise rubber raw materials, fillers, reinforcing agents, and plasticizers. It can be seen from Table 2 that the use of the bio-based raw materials can significantly reduce the carbon dioxide emission, and while ensuring the product performance, the carbon dioxide emission can be further reduced by further adjusting and optimizing the proportions of the bio-based raw materials in respective component. It can be seen from Table 3 that the data for thermal aging performance, mechanical strength, cooling fluid performance, compression set performance, and electrochemical resistance all meet the performance requirements of cooling hoses in the ten embodiments.

Claims

Attorney Docket No. 91601-01145Client Ref. No. P24031WOCLAIMS1 . A formulation for bio-based rubber used for preparing a bio-based rubber compound, wherein the bio-based rubber comprises, based on parts by mass, the following components: 100 parts of a rubber raw material, 0 part to 50 parts of a filler, 70 parts to 125 parts of a reinforcing agent, and 30 parts to 50 parts of a plasticizer; wherein at least one of the rubber raw material, the filler, the reinforcing agent, and / or the plasticizer is mixed with a bio-based material, or at least one thereof uses a bio-based material.

2. The formulation for bio-based rubber according to claim 1 , wherein the rubber raw material comprises conventional rubber raw materials and / or bio-based rubber raw materials.

3. The formulation for bio-based rubber according to claim 2, wherein the conventional rubber raw materials comprise at least one of Ethylene Propylene Diene Monomer (EPDM) 2650C, EPDM 5470C, EPDM 6470C, and EPDM 4045M; and the bio-based rubber raw materials comprise at least one of bio-based EPDM 5470, biobased EPDM 8550, and / or bio-based EPDM 6950.

4. The formulation for bio-based rubber according to claim 2, wherein the biobased rubber raw materials comprise bio-based rubber having an ethylene content is 45 wt.% to 70 wt.%, and the bio-based rubber has a Mooney viscosity of 25 to 80 under conditions of ML 125°C (1 +4).

5. The formulation for bio-based rubber according to claim 1 , wherein the filler comprises at least one of bio-based silicon-carbon black and / or silica.

6. The formulation for bio-based rubber according to claim 1 , wherein the reinforcing agent is carbon black, the carbon black comprises at least one of carbon black N550, DUREX O carbon black, N774, and / or N990 having different particle sizes, and the carbon black is of conventional carbon black or bio-based carbonAttorney Docket No. 91601-01145Client Ref. No. P24031WO black.

7. The formulation for bio-based rubber according to claim 1 , wherein the plasticizer comprises at least one of paraffinic oil 2280, bio-based paraffinic oil RECOR-T4867, and / or paraffinic oil 2286T.

8. The formulation for bio-based rubber according to claim 1 , wherein the formulation further comprises rubber additives, and the rubber additives comprise activators, anti-aging agents, vulcanizing agents, and / or vulcanization accelerators.

9. A preparation method for bio-based rubber that uses the formulation for biobased rubber according to claim 1 , wherein the method comprises the following steps:(a) mixing 0 part to 50 parts of the filler, 60 parts to 125 parts of the reinforcing agent, and 25 parts to 50 parts of the plasticizer to obtain mixture A;(b) mixing 100 parts of the rubber raw material with the anti-aging agent to obtain mixture B;(c) mixing the remaining raw materials other than the filler, the reinforcing agent, the plasticizer, the rubber raw material, and the anti-aging agent to obtain mixture C;(d) mixing mixture B with mixture C and a mixing temperature is raised to 100°C to 125°C, adding mixture A thereinto, continuing the mixing, and discharging the compound at 160°C to 180°C to obtain rubber.

10. The preparation method for bio-based rubber according to claim 9, wherein the remaining raw materials comprise activators, vulcanizing agents, and vulcanization accelerators.

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