Composition for preparing remodelable styrene-butadiene rubber material, remodelable styrene-butadiene rubber material and preparation method of remodelable styrene-butadiene rubber material

Abstract

The invention relates to the field of high polymer materials, and discloses a composition for preparing a remodelable styrene butadiene rubber material, the remodelable styrene butadiene rubber material and a preparation method of the remodelable styrene butadiene rubber material. The composition for preparing the remoldable styrene-butadiene rubber material contains solution polymerized styrene-butadiene rubber, a sulfydryl reagent, an initiator and a coordination metal compound, wherein relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber, the content of the sulfydryl reagent is 13 to 35 parts by weight, the content of the initiator is 0.01 to 0.05 part by weight, and the content of the coordination metal compound is 2 to 20 parts by weight. The mechanical property of the remoldable styrene-butadiene rubber material disclosed by the invention is remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a composition for preparing remodelable styrene-butadiene rubber (SBR) materials, the remodelable SBR materials, and a method for preparing the same. Background Technology

[0002] Rubber is an indispensable material in daily life and a polymer of significant strategic importance. Its excellent flexibility, extensibility, resilience, and unique entropic elasticity make it widely used in many fields. Rubber's high elasticity and stability are attributed to its permanently cross-linked network structure. Raw rubber typically requires chemical cross-linking for application; the sulfur vulcanization and peroxide vulcanization methods commonly used in rubber production form covalent cross-links. However, due to the irreversible nature of traditional vulcanization cross-linking networks, these vulcanized rubbers are difficult to recycle or reconstitute. To date, the main methods for treating waste rubber have been incineration for energy recovery, landfilling, and desulfurization for rubber regeneration. These methods consume energy and cause further environmental pollution, placing a significant burden on the environment.

[0003] Therefore, to address the aforementioned issues, many studies have introduced dynamic interactions into the rubber crosslinking network, enabling the material to undergo reversible "fracture" and "reorganization" under external stimuli (light, heat, pH, and catalysts, etc.). Through thermodynamic equilibrium reactions between molecules, the polymer network structure is rearranged, thereby endowing the rubber material with remodeling properties. The literature (Hou Xiaoyu et al., Preparation and Properties of Carboxylated Styrene-Butadiene Rubber / Carboxylated Cellulose Nanocrystal Self-Healing Composites; Acta Polymerica Sinica, 2023, Vol. 54, No. 07: 1074-1083) utilizes the ZnO of zinc oxide (ZnO) 2+ Ionic bonds can be formed between the carboxyl groups of carboxylated styrene-butadiene rubber (XSBR) and carboxylated cellulose nanocrystals (CCA), while hydrogen bonds can be formed between the carboxyl groups of CCA and XSBR. This led to the preparation of a carboxylated styrene-butadiene rubber (X / C / Z) composite material with a dual dynamic crosslinking network of hydrogen and ionic bonds. The results showed that the dual dynamic crosslinking network with coexisting ionic and hydrogen bonds, along with the synergistic reinforcement of CCA and ZnO, endowed the X / C / Z composite material with superior physical and mechanical properties and self-healing ability. However, its elongation at break was low, and its self-repair effect was unsatisfactory. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of poor mechanical strength and repair effect of existing remodelable styrene-butadiene rubber (SBR), and to provide a composition for preparing remodelable SBR materials, remodelable SBR materials and their preparation methods. The remodelable SBR materials of this invention have significantly improved mechanical properties.

[0005] To achieve the above objectives, a first aspect of the present invention provides a composition for preparing remodelable styrene-butadiene rubber materials, wherein the composition comprises solution-polymerized styrene-butadiene rubber, a mercapto reagent, an initiator, and a coordination metal compound; wherein, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber, the content of the mercapto reagent is 13-35 parts by weight, the content of the initiator is 0.01-0.05 parts by weight, and the content of the coordination metal compound is 2-20 parts by weight.

[0006] Preferably, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber, the content of the mercapto reagent is 16-32 parts by weight, the content of the initiator is 0.01-0.03 parts by weight, and the content of the coordination metal compound is 4-18 parts by weight; more preferably, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber, the content of the mercapto reagent is 24-32 parts by weight, the content of the initiator is 0.02-0.03 parts by weight, and the content of the coordination metal compound is 6-14 parts by weight.

[0007] Preferably, the styrene content in the solution-polymerized styrene-butadiene rubber is 20-22% by weight, and the 1,2-vinyl content is 50-60% by weight.

[0008] Preferably, the solution-polymerized styrene-butadiene rubber has a Mooney viscosity of 70-80.

[0009] Preferably, the thiol reagent is one or more of mercaptopropionic acid, mercaptoethylamine, and N-acetyl-L-cysteine, with N-acetyl-L-cysteine ​​being the most preferred.

[0010] Preferably, the initiator is one of azobisisobutyronitrile, benzoyl peroxide, persulfate, and ferrous peroxide, and more preferably azobisisobutyronitrile.

[0011] Preferably, the coordination metal compound is one or more of copper chloride, ferric chloride, cobalt chloride, and zinc chloride, with ferric chloride being the most preferred.

[0012] According to a second aspect of the present invention, a remodelable styrene-butadiene rubber material is provided, wherein it is prepared by using the composition for preparing a remodelable styrene-butadiene rubber material as described in the first aspect of the present invention.

[0013] According to a third aspect of the present invention, a method for preparing a remodelable styrene-butadiene rubber material is provided, wherein the material is prepared by using the composition for preparing a remodelable styrene-butadiene rubber material as described in the first aspect of the present invention as a raw material.

[0014] Preferably, the method includes:

[0015] 1) Steps for preparing the solution for solution-polymerized styrene-butadiene rubber;

[0016] 2) The step of reacting the solution of the solution-polymerized styrene-butadiene rubber with a mercapto reagent and an initiator to obtain the reaction product;

[0017] 3) The step of co-precipitating the contact reaction product with a poor solvent for rubber to obtain mercapto-modified styrene-butadiene rubber;

[0018] 4) Steps for preparing the adhesive solution of mercapto-modified styrene-butadiene rubber;

[0019] 5) The step of coordinating the thiol-modified styrene-butadiene rubber solution with the coordination metal compound.

[0020] Preferably, in step 1), the solution-polymerized styrene-butadiene rubber is mixed with a first good rubber solvent to obtain a solution of the solution-polymerized styrene-butadiene rubber.

[0021] Preferably, in step 1), the weight ratio of the solution-polymerized styrene-butadiene rubber to the first rubber solvent is 1:5-15, more preferably 1:8-12.

[0022] Preferably, the first good solvent for the rubber is one or more of tetrahydrofuran, cyclohexane, and toluene, with tetrahydrofuran being the most preferred.

[0023] Preferably, in step 2), the solution of the solution-polymerized styrene-butadiene rubber is reacted with a solution containing a mercapto reagent and an initiator to obtain a reaction product.

[0024] Preferably, in the solution containing the thiol reagent and the initiator, the total weight ratio of the thiol reagent and the initiator to the solvent is 1:5-15, more preferably 1:8-12.

[0025] Preferably, in step 2), the conditions for the contact reaction include: the contact reaction temperature is 50-80℃, and the contact reaction time is 2-8h.

[0026] Preferably, the contact reaction is carried out under an inert atmosphere.

[0027] Preferably, in step 3), the poor solvent for rubber is one or more of methanol, ethanol, and ethylene glycol, with methanol being the most preferred.

[0028] Preferably, in step 4), the mercapto-modified styrene-butadiene rubber is mixed with a second good rubber solvent to obtain a solution of the mercapto-modified styrene-butadiene rubber.

[0029] Preferably, in step 4), the weight ratio of the mercapto-modified styrene-butadiene rubber to the second rubber solvent is 1:5-15, more preferably 1:8-12.

[0030] Preferably, the second good solvent for the rubber is one or more of tetrahydrofuran, cyclohexane, and toluene, with tetrahydrofuran being the most preferred.

[0031] Preferably, in step 5), the thiol-modified styrene-butadiene rubber solution is coordinated with a solution containing a coordination metal compound.

[0032] Preferably, in step 5), the weight ratio of the coordination metal compound to the solvent in the solution containing the coordination metal compound is 1:5-15, more preferably 1:8-12.

[0033] Preferably, in step 5), the solution containing the coordination metal compound is added dropwise to the thiol-modified styrene-butadiene rubber solution to perform the coordination.

[0034] Preferably, the method further includes the step of removing the solvent after coordination.

[0035] According to a fourth aspect of the present invention, a remodelable styrene-butadiene rubber material is provided, wherein it is prepared by the method for preparing remodelable styrene-butadiene rubber material described in the third aspect of the present invention.

[0036] According to a fifth aspect of the present invention, a remodelable styrene-butadiene rubber material is provided, wherein the remodelable styrene-butadiene rubber material contains thiol groups and a coordinating metal, and the grafting rate of thiol groups on the styrene-butadiene rubber material is 5-20%, and the content of the coordinating metal is 0.5-6% by weight.

[0037] Through the above technical solutions, the present invention can provide a composition for preparing a remodelable styrene-butadiene rubber material based on a dual dynamic crosslinking network of thiol hydrogen bonds and coordination bonds, a remodelable styrene-butadiene rubber material based on a dual dynamic crosslinking network of thiol hydrogen bonds and coordination bonds, and a method for preparing the same. The remodelable styrene-butadiene rubber material of the present invention has significantly improved mechanical properties, and the mechanical strength can be adjusted within a wide range by adjusting the amount of grafted thiol groups and the amount of added crosslinking metal ions. Attached Figure Description

[0038] Figure 1 This is a photograph of the remodelable styrene-butadiene rubber sample from Example 3, showing that it can be remelted (remodeled) after molding.

[0039] Figure 2 The images show the NMR spectra of the styrene-butadiene rubber before and after modification in Example 3.

[0040] Figure 3 This is a mechanical comparison diagram of the remodelable styrene-butadiene rubber in Example 3. Detailed Implementation

[0041] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0042] In a first aspect, the present invention provides a composition for preparing a remodelable styrene-butadiene rubber material, wherein the composition comprises solution-polymerized styrene-butadiene rubber, a mercapto reagent, an initiator, and a coordination metal compound; wherein, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber, the content of the mercapto reagent is 13-35 parts by weight, the content of the initiator is 0.01-0.05 parts by weight, and the content of the coordination metal compound is 2-20 parts by weight.

[0043] According to the present invention, from the viewpoint of further improving mechanical properties, preferably, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber, the content of the mercapto reagent is 16-32 parts by weight, the content of the initiator is 0.01-0.03 parts by weight, and the content of the coordination metal compound is 4-18 parts by weight; more preferably, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber, the content of the mercapto reagent is 24-32 parts by weight, the content of the initiator is 0.02-0.03 parts by weight, and the content of the coordination metal compound is 6-14 parts by weight.

[0044] Specific examples of the content of the mercapto reagent relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber include, for example, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, etc., as well as any range of the above and all values ​​within that range.

[0045] Specific examples of the initiator content relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber include, for example, 0.01 parts by weight, 0.012 parts by weight, 0.015 parts by weight, 0.018 parts by weight, 0.02 parts by weight, 0.022 parts by weight, 0.025 parts by weight, 0.028 parts by weight, 0.03 parts by weight, 0.032 parts by weight, 0.035 parts by weight, 0.038 parts by weight, 0.04 parts by weight, 0.042 parts by weight, 0.045 parts by weight, 0.048 parts by weight, 0.05 parts by weight, etc., as well as any range formed by any two of the above and all values ​​within that range.

[0046] Specific examples of the content of the coordination metal compound relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber include, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, etc., as well as any range formed by any two of the above and all values ​​within that range.

[0047] According to the present invention, preferably, the styrene structural unit content in the solution-polymerized styrene-butadiene rubber is 20-22% by weight, and the 1,2-vinyl content is 50-60% by weight.

[0048] In a preferred embodiment of the present invention, the styrene structural unit content in the solution-polymerized styrene-butadiene rubber is 20-22% by weight, and the 1,2-vinyl content is 54% by weight.

[0049] According to the present invention, preferably, the Mooney viscosity of the solution-polymerized styrene-butadiene rubber is 70-80.

[0050] In a preferred embodiment of the present invention, the styrene structural unit content in the solution-polymerized styrene-butadiene rubber is 20-22% by weight, the 1,2-vinyl content is 54% by weight, and the Mooney viscosity is 70-80.

[0051] According to the present invention, the thiol reagent is used to thiolize solution-polymerized styrene-butadiene rubber; any thiol reagent capable of achieving this purpose may be used. Preferably, the thiol reagent is one or more selected from mercaptopropionic acid, mercaptoethylamine, and N-acetyl-L-cysteine; more preferably, the thiol reagent is N-acetyl-L-cysteine.

[0052] According to the present invention, the initiator and the thiol reagent work together to mercaptify solution-polymerized styrene-butadiene rubber. The initiator need only be able to achieve the above-mentioned objective. Preferably, the initiator is one of azobisisobutyronitrile, benzoyl peroxide, persulfate, and ferrous hydrogen peroxide; more preferably, the initiator is azobisisobutyronitrile.

[0053] According to the present invention, preferably, the coordination metal compound is one or more of copper chloride, ferric chloride, cobalt chloride and zinc chloride; more preferably, the coordination metal compound is ferric chloride.

[0054] Specifically, copper chloride dihydrate can be used as copper chloride; ferric chloride hexahydrate can be used as ferric chloride; and cobalt chloride hexahydrate can be used as cobalt chloride.

[0055] In this invention, the mechanical properties can be significantly improved through a dual dynamic crosslinking network of hydrogen bonds and coordination bonds. Furthermore, the mechanical strength can be adjusted within a wide range by regulating the amount of grafted thiol groups and the amount of crosslinked metal ions added.

[0056] According to a second aspect of the present invention, a remodelable styrene-butadiene rubber material is provided, wherein it is prepared by using the composition for preparing a remodelable styrene-butadiene rubber material as described in the first aspect of the present invention.

[0057] According to a third aspect of the present invention, a method for preparing a remodelable styrene-butadiene rubber material is provided, wherein the material is prepared by using the composition for preparing a remodelable styrene-butadiene rubber material as described in the first aspect of the present invention as a raw material.

[0058] Preferably, the method includes:

[0059] 1) Steps for preparing the solution for solution-polymerized styrene-butadiene rubber;

[0060] 2) The step of reacting the solution of the solution-polymerized styrene-butadiene rubber with a mercapto reagent and an initiator to obtain the reaction product;

[0061] 3) The step of co-precipitating the contact reaction product with a poor solvent for rubber to obtain mercapto-modified styrene-butadiene rubber;

[0062] 4) Steps for preparing the adhesive solution of mercapto-modified styrene-butadiene rubber;

[0063] 5) The step of coordinating the thiol-modified styrene-butadiene rubber solution with the coordination metal compound.

[0064] According to the present invention, the solution-polymerized styrene-butadiene rubber (SBR) adhesive solution can be obtained using conventional methods in the art. Preferably, in step 1), the solution-polymerized SBR is mixed with a first good rubber solvent to obtain the solution-polymerized SBR adhesive solution.

[0065] Preferably, in step 1), the weight ratio of the solution-polymerized styrene-butadiene rubber to the first good rubber solvent is 1:5-15; more preferably, in step 1), the weight ratio of the solution-polymerized styrene-butadiene rubber to the first good rubber solvent is 1:8-12.

[0066] In step 1), by mixing the solution-polymerized styrene-butadiene rubber with the first good rubber solvent at the above ratio, a solution solution in which the solution-polymerized styrene-butadiene rubber is fully dissolved can be obtained.

[0067] There are no particular restrictions on the temperature of the above mixing, but it is preferred to be carried out at room temperature, for example, at 5-45°C.

[0068] There is no particular time limit for the above mixing, as long as the solution-polymerized styrene-butadiene rubber is fully dissolved.

[0069] In this invention, the first good solvent for rubber is a solvent that has good solubility for the solution-polymerized styrene-butadiene rubber. Preferably, the first good solvent for rubber is one or more of tetrahydrofuran, cyclohexane, and toluene; more preferably, the first good solvent for rubber is tetrahydrofuran.

[0070] According to the present invention, in step 2), a contact reaction product is obtained by reacting the solution of the solution-polymerized styrene-butadiene rubber with a mercapto reagent and an initiator.

[0071] Preferably, in step 2), the solution-polymerized styrene-butadiene rubber (SBR) solution is reacted with a solution containing a thiol reagent and an initiator to obtain a contact reaction product. By reacting the solution-polymerized SBR solution with a solution containing a thiol reagent and an initiator, the contact reaction between the solution-polymerized SBR solution and the thiol reagent and initiator can be carried out more easily.

[0072] Preferably, in the solution containing the thiol reagent and the initiator, the total weight ratio of the thiol reagent and the initiator to the solvent is 1:5-15; more preferably, in the solution containing the thiol reagent and the initiator, the total weight ratio of the thiol reagent and the initiator to the solvent is 1:8-12.

[0073] The first good rubber solvent described above can be used as a solvent in the solution containing the thiol reagent and the initiator. Preferably, the same solvent as the first good rubber solvent is used.

[0074] By obtaining the solution containing the thiol reagent and the initiator at the above ratio, a solution in which the thiol reagent and the initiator are fully dissolved can be obtained.

[0075] Preferably, in step 2), the conditions for the contact reaction include: a contact reaction temperature of 50-80°C and a contact reaction time of 2-8 hours; more preferably, in step 2), the conditions for the contact reaction include: a contact reaction temperature of 60-70°C and a contact reaction time of 4-6 hours.

[0076] Preferably, the contact reaction is carried out under an inert atmosphere. For example, a nitrogen atmosphere or an argon atmosphere may be used as the inert atmosphere.

[0077] According to the present invention, in step 3), mercapto-modified styrene-butadiene rubber is obtained by co-precipitating the contact reaction product with a poor rubber solvent.

[0078] The term "unsuitable solvent for rubber" refers to a solvent that has poor solubility in rubber (solution-polymerized styrene-butadiene rubber). Preferably, in step 3), the unsuitable solvent for rubber is one or more of methanol, ethanol, and ethylene glycol; more preferably, in step 3), the unsuitable solvent for rubber is methanol.

[0079] In this invention, the rubber-poor solvent is used in excess. For example, the weight ratio of the contact reaction product to the rubber-poor solvent can be 1:3-15; preferably, the weight ratio of the contact reaction product to the rubber-poor solvent is 1:3-12; more preferably, the weight ratio of the contact reaction product to the rubber-poor solvent is 1:3-8.

[0080] Preferably, in step 3), the method further includes: drying the precipitate obtained by co-precipitation to obtain the mercapto-modified styrene-butadiene rubber.

[0081] The drying process is preferably vacuum drying, for example, drying at a temperature of 30-40℃ and a vacuum degree of -0.01 to -0.09 MPa for 10-40 hours; preferably, drying at a temperature of 30-40℃ and a vacuum degree of -0.01 to -0.09 MPa for 20-30 hours.

[0082] According to the present invention, in step 4), a solution of mercapto-modified styrene-butadiene rubber is prepared.

[0083] In this invention, the adhesive solution can be obtained using methods commonly used in the art. Preferably, in step 4), the mercapto-modified styrene-butadiene rubber is mixed with a second good rubber solvent to obtain the adhesive solution of the mercapto-modified styrene-butadiene rubber.

[0084] Preferably, in step 4), the weight ratio of the mercapto-modified styrene-butadiene rubber to the second good rubber solvent is 1:5-15; more preferably, in step 4), the weight ratio of the mercapto-modified styrene-butadiene rubber to the second good rubber solvent is 1:8-12.

[0085] In step 4), by mixing the mercapto-modified styrene-butadiene rubber with the second good rubber solvent at the above ratio, a glue solution in which the mercapto-modified styrene-butadiene rubber is fully dissolved can be obtained.

[0086] There are no particular restrictions on the temperature of the above mixing, but it is preferred to be carried out at room temperature, for example, at 5-45°C.

[0087] There is no particular time limit for the above mixing, as long as the solution-polymerized styrene-butadiene rubber is fully dissolved.

[0088] In this invention, the second good solvent for rubber is a solvent that has good solubility in the solution-polymerized styrene-butadiene rubber. Preferably, the second good solvent for rubber is one or more of tetrahydrofuran, cyclohexane, and toluene; more preferably, the second good solvent for rubber is tetrahydrofuran.

[0089] In a preferred embodiment of the present invention, the first good rubber solvent and the second good rubber solvent are the same. This reduces impurities and improves operational convenience.

[0090] In another preferred embodiment of the invention, the solvent in the first good rubber solvent, the solution containing the thiol reagent and the initiator, and the second good rubber solvent are all the same. This further reduces impurities and improves operational convenience.

[0091] According to the present invention, in step 5), the thiol-modified styrene-butadiene rubber solution is coordinated with the coordination metal compound.

[0092] In order to enable the coordination metal to be distributed more uniformly in the remodelable styrene-butadiene rubber material and further improve the mechanical properties of the remodelable styrene-butadiene rubber material, preferably, in step 5), the thiol-modified styrene-butadiene rubber adhesive solution is coordinated with the solution containing the coordination metal compound; more preferably, in step 5), the solution containing the coordination metal compound is added dropwise to the thiol-modified styrene-butadiene rubber adhesive solution to carry out the coordination.

[0093] Preferably, in step 5), the weight ratio of the coordination metal compound to the solvent in the solution containing the coordination metal compound is 1:5-15; more preferably, in step 5), the weight ratio of the coordination metal compound to the solvent in the solution containing the coordination metal compound is 1:8-12.

[0094] The first good rubber solvent described above can be used as a solvent in the solution containing the coordination metal compound. It is preferable to use the same solvent as the first good rubber solvent.

[0095] In a preferred embodiment of the present invention, the first good rubber solvent, the solvent in the solution containing the thiol reagent and the initiator, the second good rubber solvent, and the solvent in the solution containing the coordination metal compound are all the same. This further reduces impurities and improves operational convenience.

[0096] Preferably, in step 5), the coordination conditions include: a coordination temperature of 5-45°C and a coordination time of 30-120 min.

[0097] Preferably, in step 5), the method further includes the step of removing the solvent after coordination.

[0098] The above-described method for removing solvent is not particularly limited and can be any of the various methods in the art for evaporating solvent, such as natural evaporation to remove solvent.

[0099] According to a fourth aspect of the present invention, a remodelable styrene-butadiene rubber material is provided, wherein it is prepared by the method for preparing remodelable styrene-butadiene rubber material described in the third aspect of the present invention.

[0100] According to a fifth aspect of the present invention, a remodelable styrene-butadiene rubber material is provided, wherein the remodelable styrene-butadiene rubber material contains thiol groups and a coordinating metal, and the grafting rate of thiol groups on the styrene-butadiene rubber material is 5-20%, and the content of the coordinating metal is 0.5-6% by weight.

[0101] Preferably, the grafting rate of mercapto groups onto the styrene-butadiene rubber material is 5-15%.

[0102] Specific examples of the grafting rate of mercapto groups on styrene-butadiene rubber materials include, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc., as well as any range of the above and all values ​​within that range.

[0103] Preferably, the content of the coordination metal is 0.8-5% by weight.

[0104] Specific examples of the content of coordination metals include: 0.5 wt%, 0.8 wt%, 1 wt%, 1.3 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.3 wt%, 2.6 wt%, 2.8 wt%, 3 wt%, 3.3 wt%, 3.6 wt%, 3.8 wt%, 4 wt%, 4.3 wt%, 4.6 wt%, 4.8 wt%, 5 wt%, 5.3 wt%, 5.6 wt%, 5.8 wt%, 6 wt%, etc., as well as any range formed by any two of the above and all values ​​within that range.

[0105] Through the above technical solutions, the present invention can provide a composition for preparing a remodelable styrene-butadiene rubber material based on a dual dynamic crosslinking network of thiol hydrogen bonds and coordination bonds, a remodelable styrene-butadiene rubber material based on a dual dynamic crosslinking network of thiol hydrogen bonds and coordination bonds, and a method for preparing the same. The remodelable styrene-butadiene rubber material of the present invention has significantly improved mechanical properties, and the mechanical strength can be adjusted within a wide range by adjusting the amount of grafted thiol groups and the amount of added crosslinking ions.

[0106] The present invention will be described in detail below through embodiments, but the present invention is not limited to the following embodiments.

[0107] The raw materials and equipment used in the following examples and comparative examples are all known products, obtained by purchasing commercially available products.

[0108] In the following examples and comparative examples, "parts" means "parts by weight".

[0109] Example 1

[0110] The composition of the composition for preparing a remodelable styrene-butadiene rubber material based on a dual dynamic crosslinked network of hydrogen bonds and coordination bonds in this embodiment is as follows:

[0111]

[0112]

[0113] The mercapto reagent is N-acetyl-L-cysteine, the initiator is azobisisobutyronitrile, the coordination metal compound is ferric chloride hexahydrate, and the good and bad solvents for the rubber are tetrahydrofuran and methanol, respectively.

[0114] The method for preparing the remodelable styrene-butadiene rubber is as follows.

[0115] (1) At 25°C, solution-polymerized styrene-butadiene rubber is fully dissolved in tetrahydrofuran (the weight ratio of solution-polymerized styrene-butadiene rubber to tetrahydrofuran is 1:10) to obtain a solution of solution-polymerized styrene-butadiene rubber, which is used as a rubber solution for later use.

[0116] (2) At 25°C, the mercapto reagent and the initiator are fully dissolved in tetrahydrofuran (the weight ratio of mercapto reagent and initiator to tetrahydrofuran is 1:10) and prepared as solutions for later use.

[0117] (3) After thoroughly mixing the solution obtained in step (2) into the rubber solution obtained in step (1), react at 66°C under an Ar atmosphere for 5 hours.

[0118] (4) Pour the adhesive solution obtained in step (3) into excess methanol for co-precipitation and purification (the weight ratio of the adhesive solution obtained in step (3) to methanol is 1:3), filter, obtain the precipitate, and vacuum dry the precipitate at 35°C and vacuum degree -0.03MPa for 24h to obtain mercapto-modified styrene-butadiene rubber.

[0119] (5) At 25°C, the mercapto-modified styrene-butadiene rubber obtained in step (4) is fully dissolved in tetrahydrofuran (the weight ratio of the mercapto-modified styrene-butadiene rubber obtained in step (4) to tetrahydrofuran is 1:10) and used as a rubber solution for later use.

[0120] (6) At 25°C, the coordination metal compound is fully dissolved in tetrahydrofuran (the weight ratio of the coordination metal compound to tetrahydrofuran is 1:10) and used as a solution for later use;

[0121] (7) At 25°C, the solution obtained in step (6) is added dropwise to the solution obtained in step (5) and stirred thoroughly for 60 minutes. After mixing, the uniformly mixed adhesive is poured into a PTFE mold and the solvent is allowed to evaporate naturally to form the material, thus obtaining the remodelable styrene-butadiene rubber material S1.

[0122] Example 2

[0123] The composition of the composition for preparing a remodelable styrene-butadiene rubber material based on a dual dynamic crosslinked network of hydrogen bonds and coordination bonds in this embodiment is as follows:

[0124]

[0125] The mercapto reagent is N-acetyl-L-cysteine, the initiator is azobisisobutyronitrile, the coordination metal compound is ferric chloride hexahydrate, and the good and bad solvents for the rubber are tetrahydrofuran and methanol, respectively.

[0126] The method for preparing the remodelable styrene-butadiene rubber is as follows.

[0127] (1) At 25°C, solution-polymerized styrene-butadiene rubber is fully dissolved in tetrahydrofuran (the weight ratio of solution-polymerized styrene-butadiene rubber to tetrahydrofuran is 1:10) to obtain a solution of solution-polymerized styrene-butadiene rubber, which is used as a rubber solution for later use.

[0128] (2) At 25°C, the mercapto reagent and the initiator are fully dissolved in tetrahydrofuran (the weight ratio of mercapto reagent and initiator to tetrahydrofuran is 1:10) and prepared as solutions for later use.

[0129] (3) After thoroughly mixing the solution obtained in step (2) into the rubber solution obtained in step (1), react at 66°C under an Ar atmosphere for 5 hours.

[0130] (4) Pour the adhesive solution obtained in step (3) into excess methanol for co-precipitation and purification (the weight ratio of the adhesive solution obtained in step (3) to methanol is 1:3), filter, obtain the precipitate, and vacuum dry the precipitate at 35°C and vacuum degree -0.03MPa for 24h to obtain mercapto-modified styrene-butadiene rubber.

[0131] (5) At 25°C, the mercapto-modified styrene-butadiene rubber obtained in step (4) is fully dissolved in tetrahydrofuran (the weight ratio of the mercapto-modified styrene-butadiene rubber obtained in step (4) to tetrahydrofuran is 1:10) and used as a rubber solution for later use.

[0132] (6) At 25°C, the coordination metal compound is fully dissolved in tetrahydrofuran (the weight ratio of the coordination metal compound to tetrahydrofuran is 1:10) and used as a solution for later use;

[0133] (7) At 25°C, the solution obtained in step (6) is added dropwise to the solution obtained in step (5) and stirred thoroughly for 60 minutes. After mixing, the uniformly mixed adhesive is poured into a PTFE mold and the solvent is allowed to evaporate naturally to form the material, thus obtaining the remodelable styrene-butadiene rubber material S2.

[0134] Example 3

[0135] The composition of the composition for preparing a remodelable styrene-butadiene rubber material based on a dual dynamic crosslinked network of hydrogen bonds and coordination bonds in this embodiment is as follows:

[0136]

[0137] The mercapto reagent is N-acetyl-L-cysteine, the initiator is azobisisobutyronitrile, the coordination metal compound is ferric chloride hexahydrate, and the good and bad solvents for the rubber are tetrahydrofuran and methanol, respectively.

[0138] The method for preparing the remodelable styrene-butadiene rubber is as follows.

[0139] (1) At 25°C, solution-polymerized styrene-butadiene rubber is fully dissolved in tetrahydrofuran (the weight ratio of solution-polymerized styrene-butadiene rubber to tetrahydrofuran is 1:10) to obtain a solution of solution-polymerized styrene-butadiene rubber, which is used as a rubber solution for later use.

[0140] (2) At 25°C, the mercapto reagent and the initiator are fully dissolved in tetrahydrofuran (the weight ratio of mercapto reagent and initiator to tetrahydrofuran is 1:10) and prepared as solutions for later use.

[0141] (3) After thoroughly mixing the solution obtained in step (2) into the rubber solution obtained in step (1), react at 66°C under an Ar atmosphere for 5 hours.

[0142] (4) Pour the adhesive solution obtained in step (3) into excess methanol for co-precipitation and purification (the weight ratio of the adhesive solution obtained in step (3) to methanol is 1:3), filter, obtain the precipitate, and vacuum dry the precipitate at 35°C and vacuum degree -0.03MPa for 24h to obtain mercapto-modified styrene-butadiene rubber.

[0143] (5) At 25°C, the mercapto-modified styrene-butadiene rubber obtained in step (4) is fully dissolved in tetrahydrofuran (the weight ratio of the mercapto-modified styrene-butadiene rubber obtained in step (4) to tetrahydrofuran is 1:10) and used as a rubber solution for later use.

[0144] (6) At 25°C, the coordination metal compound is fully dissolved in tetrahydrofuran (the weight ratio of the coordination metal compound to tetrahydrofuran is 1:10) and used as a solution for later use;

[0145] (7) At 25°C, the solution obtained in step (6) is added dropwise to the solution obtained in step (5) and stirred thoroughly for 60 minutes. After mixing, the uniformly mixed adhesive is poured into a PTFE mold and the solvent is allowed to evaporate naturally to form the material, thus obtaining the remodelable styrene-butadiene rubber material S3.

[0146] Figure 1 The images show the remodelable styrene-butadiene rubber material samples (sample 1, sample 3 and sample 5) in Example 3, which can be remelted (remodeled) after molding. Figure 2 The images show the NMR spectra of the styrene-butadiene rubber (SSBRC) before and after modification in Example 3. The 1H NMR spectrum shows that the styrene-butadiene rubber modified with mercapto grafting (SSBRC) has an additional peak at around 2.9 ppm compared to the pure styrene-butadiene rubber. This peak can be attributed to the H atom in the -CH2- group connected to the sulfur atom. Figure 3 The mechanical comparison diagram of the remodelable styrene-butadiene rubber in Example 3 shows that the styrene-butadiene rubber (SSBR-C) modified with mercapto reagent has a large number of hydrogen bonds, and its modulus, strength and elongation at break are better than those of pure rubber. The strength of the styrene-butadiene rubber (SSBR-CF) after the introduction of metal atoms for coordination is greatly improved.

[0147] Example 4

[0148] The method of Example 3 was followed, except that the composition of the composition for preparing the remodelable styrene-butadiene rubber material based on a dual dynamic crosslinking network of hydrogen bonds and coordination bonds in this example is as follows, resulting in remodelable styrene-butadiene rubber material S4.

[0149]

[0150] Example 5

[0151] The method of Example 3 was followed, except that the composition of the composition for preparing the remodelable styrene-butadiene rubber material based on a dual dynamic crosslinking network of hydrogen bonds and coordination bonds in this example is as follows, resulting in remodelable styrene-butadiene rubber material S5.

[0152]

[0153] Example 6

[0154] The method of Example 3 was followed, except that the composition of the composition for preparing the remodelable styrene-butadiene rubber material based on a dual dynamic crosslinking network of hydrogen bonds and coordination bonds in this example is as follows, resulting in remodelable styrene-butadiene rubber material S6.

[0155]

[0156] Example 7

[0157] The method of Example 3 was followed, except that the coordination metal compound was cobalt chloride hexahydrate, to obtain remodelable styrene-butadiene rubber material S7.

[0158] Example 8

[0159] The method of Example 3 was followed, except that the coordination metal compound was copper chloride dihydrate, to obtain remodelable styrene-butadiene rubber material S8.

[0160] Example 9

[0161] The method of Example 3 was followed, except that the coordination metal compound was zinc chloride, to obtain remodelable styrene-butadiene rubber material S9.

[0162] Comparative Example 1

[0163] The method of Example 6 is followed, except that the composition of the composition for preparing styrene-butadiene rubber material in this example is as follows, and steps (2) to (5) are not performed. Instead, the solution obtained in step (6) is directly added dropwise to the solution obtained in step (1) and stirred thoroughly for 60 minutes. The uniformly mixed rubber solution is then poured into a PTFE mold, the solvent is evaporated, and the molding process is completed to obtain the remodelable styrene-butadiene rubber material DS1.

[0164] Comparative Example 2

[0165] The mercapto-modified styrene-butadiene rubber DS2 was obtained according to steps (1) to (4) of Example 6.

[0166] Comparative Example 3

[0167] This comparative example is used to prepare existing vulcanized rubber.

[0168] 100 parts of solution-polymerized styrene-butadiene rubber, 5 parts of zinc oxide, 1 part of stearic acid, 2 parts of sulfur, 1 part of N-cyclohexyl-2-benzothiazole sulfenamide and 1 part of antioxidant 4010 were mixed evenly on a two-roll mill and then hot-pressed at 143°C for 20 minutes to obtain vulcanized rubber DS3.

[0169] Test case

[0170] The rubbers obtained in Examples 1-9 and Comparative Examples 1-3 were tested as follows.

[0171] (1) Fracture strength

[0172] According to ASTM D412 testing, the tensile rate is 100 mm / min.

[0173] (2) Young's modulus

[0174] The test was conducted using a universal testing machine, and the stress-strain curves were used for calculation.

[0175] (3) Grafting rate

[0176] The grafting rate was calculated based on the NMR results and the following formula.

[0177]

[0178] (4) Coordination metal content

[0179] It is calculated based on the raw material input ratio.

[0180] Table 1

[0181]

[0182] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition for preparing a remoldable styrene-butadiene rubber material, characterized in that, The composition contains solution-polymerized styrene-butadiene rubber, a mercapto reagent, an initiator, and a coordination metal compound; wherein, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber, the content of the mercapto reagent is 13-35 parts by weight, the content of the initiator is 0.01-0.05 parts by weight, and the content of the coordination metal compound is 2-20 parts by weight.

2. The composition of claim 1, wherein, The content of the mercapto reagent is 16-32 parts by weight, the content of the initiator is 0.01-0.03 parts by weight, and the content of the coordination metal compound is 4-18 parts by weight, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber; The content of the mercapto reagent is 24-32 parts by weight, the content of the initiator is 0.02-0.03 parts by weight, and the content of the coordination metal compound is 6-14 parts by weight, relative to 100 parts by weight of the solution-polymerized styrene-butadiene rubber.

3. The composition of claim 1, wherein, The content of styrene structural units in the solution-polymerized styrene-butadiene rubber is 20-22% by weight, and the content of 1,2-vinyl groups is 50-60% by weight. Preferably, the solution-polymerized styrene-butadiene rubber has a Mooney viscosity of 70-80.

4. The composition according to any one of claims 1-3, wherein, The mercapto reagent is one or more of mercaptopropionic acid, mercaptoethylamine, and N-acetyl-L-cysteine, and is preferably N-acetyl-L-cysteine.

5. The composition according to any one of claims 1-3, wherein, The initiator is one of azobisisobutyronitrile, dibenzoyl peroxide, persulfate, and hydrogen peroxide-ferrous salt, and is preferably azobisisobutyronitrile.

6. The composition according to any one of claims 1-3, wherein, The coordination metal compound is one or more of copper chloride, iron chloride, cobalt chloride, and zinc chloride, and is preferably iron chloride.

7. A recyclable styrene-butadiene rubber material, characterized by, It is prepared by using the composition for preparing a remoldable styrene-butadiene rubber material according to any one of claims 1-6 as a raw material.

8. A method of preparing a recyclable styrene-butadiene rubber material, characterized by, It is prepared by using the composition for preparing a remoldable styrene-butadiene rubber material according to any one of claims 1-6 as a raw material.

9. The method of claim 8, wherein, The method comprises: 1) a step of preparing a gum solution of solution-polymerized styrene-butadiene rubber; 2) a step of allowing the gum solution of solution-polymerized styrene-butadiene rubber to contact with a mercapto reagent and an initiator to obtain a contact reaction product; 3) a step of allowing the contact reaction product to co-precipitate with a rubber poor solvent to obtain a mercapto-modified styrene-butadiene rubber; 4) a step of preparing a gum solution of mercapto-modified styrene-butadiene rubber; 5) a step of allowing the gum solution of mercapto-modified styrene-butadiene rubber to coordinate with a coordination metal compound.

10. The method of claim 9, wherein, In step 1), the solution-polymerized styrene-butadiene rubber is mixed with a first rubber good solvent to obtain the gum solution of solution-polymerized styrene-butadiene rubber; Preferably, in step 1), the weight ratio of the solution-polymerized styrene-butadiene rubber to the first rubber good solvent is 1:5-15, preferably 1:8-12; Preferably, the first rubber good solvent is one or more of tetrahydrofuran, cyclohexane, and toluene, and is preferably tetrahydrofuran.

11. The method of claim 9, wherein, In step 2), the gum solution of solution-polymerized styrene-butadiene rubber is allowed to contact with a solution containing a mercapto reagent and an initiator to obtain a contact reaction product; Preferably, in the solution containing a mercapto reagent and an initiator, the weight ratio of the total weight of mercapto reagent and initiator to the weight of solvent is 1:5-15, preferably 1:8-12.

12. The method of any of claims 9-11, wherein, In step 2), the conditions of the contact reaction include: the temperature of the contact reaction is 50-80℃, and the time of the contact reaction is 2-8h. Preferably, the contact reaction is carried out under inert atmosphere.

13. The method of any of claims 9-11, wherein, In step 3), the rubber poor solvent is one or more of methanol, ethanol and ethylene glycol, preferably methanol.

14. The method of any one of claims 9-11, wherein, In step 4), the thiol-modified styrene-butadiene rubber is mixed with a second rubber good solvent to obtain a rubber solution of the thiol-modified styrene-butadiene rubber. Preferably, in step 4), the weight ratio of the thiol-modified styrene-butadiene rubber to the second rubber good solvent is 1:5-15, preferably 1:8-12. Preferably, the second rubber good solvent is one or more of tetrahydrofuran, cyclohexane and toluene, preferably tetrahydrofuran.

15. The method of any of claims 9-11, wherein, In step 5), the rubber solution of the thiol-modified styrene-butadiene rubber is coordinated with a solution containing a coordination metal compound. Preferably, in step 5), the weight ratio of the coordination metal compound to the solvent in the solution containing the coordination metal compound is 1:5-15, preferably 1:8-12. Preferably, in step 5), the solution containing the coordination metal compound is added dropwise to the rubber solution of the thiol-modified styrene-butadiene rubber to carry out the coordination.

16. The method of any one of claims 9-11, wherein, The method further comprises a step of removing the solvent after the coordination.

17. A recyclable styrene butadiene rubber material, characterized by, The remoldable styrene-butadiene rubber material is prepared by the preparation method of any one of claims 8-16.

18. A recyclable styrene butadiene rubber material, characterized by, The remoldable styrene-butadiene rubber material contains thiol and coordination metal, and the grafting rate of the thiol on the styrene-butadiene rubber material is 5-20%, and the content of the coordination metal is 0.5-6% by weight. The remoldable styrene-butadiene rubber material contains thiol and coordination metal, and the grafting rate of the thiol on the styrene-butadiene rubber material is 5-20%, and the content of the coordination metal is 0.5-6% by weight.

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