KR20150130779A - The preparing method of silica-polybutadiene composite material and the silica-polybutadiene composite material thereby - Google Patents

Abstract

The present invention provides a method for preparing a silica-polybutadiene composite material which comprises the following steps: preparing polybutadiene modified with a waste vegetable oil (step 1); and adding the polybutadiene modified with the waste vegetable oil and silica to an organic solvent (step 2). The silica-polybutadiene composite material according to the present invention modifies the polybutadiene with the waste vegetable oil, and thus improves affinity with the silica. As described above, the method for preparing the silica-polybutadiene composite material of the present invention adds the polybutadiene, modified with the waste vegetable oil, and the silica to the organic solvent and stirs the same, and thus more uniformly disperses the silica. The obtained silica-polybutadiene composite material is capable of: reducing emission of carbon dioxide by using the waste vegetable oil; and improving physical properties of the composite material by the uniformly dispersed silica.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silica-polybutadiene composite material and a silica-polybutadiene composite material,

The present invention relates to a process for producing a silica-polybutadiene composite material and a silica-polybutadiene composite material produced thereby, and more particularly to a process for producing a silica-polybutadiene composite material comprising polybutadiene modified with a waste vegetable oil .

Carbon black or silica is used as a reinforcing filler in rubber composite materials used for tire manufacturing and the like. Carbon black was used as a conventional reinforcing filler. However, studies have been actively carried out to reduce the rotation resistance of a tire in order to reduce environmental pollution caused by automobile exhaust gas. One of them is silica, instead of carbon black, It is used as a filler. The silica-rubber composite material using silica as a reinforcing filler can reduce the rolling resistance and improve the braking ability as compared with the carbon black-rubber composite material.

However, since there are numerous silanol groups on the silica surface, the interaction between the silica aggregates is so strong that they are not easily dispersed in the non-polar rubber. Due to these properties, the silica-rubber composite material has a lower crosslinking reaction rate and lower crosslinking density than the carbon black-rubber composite material.

As described above, the degree of dispersion of the reinforcing filler in the rubber composite material is an important factor that affects the physical properties, and the efficient dispersion of the reinforcing filler is directly related to the productivity. In order for silica-rubber composites to exhibit excellent properties, the silica must be evenly dispersed to the aggregate level within the rubber.

Various methods have been developed, such as the use of surface treatment of silica to improve the dispersion of silica, the use of a rubber having a polar group introduced therein, or the use of a silica dispersant. Currently, the most commonly used method is a method of modifying the surface of silica using a silane coupling agent and a method of introducing 1,2-units in styrene butadiene rubber (SBR) to improve the affinity with silica. For example, bis- (3- (triethoxysilyl) -propyl) -tetrasulfide (TESPT) is the most commonly used silane coupling agent.

On the other hand, as a result of the progress of industrial technology and mass consumption of petroleum, which is a fossil resource, the limitations of global warming and dependence on fossil resources are emerging as big problems. As means for solving these problems, Technology for converting raw materials into biomass, which is a biomass resource, has been greatly demanded in the field of energy materials. However, biomass-based materials can not be applied as component materials unless they overcome various inevitable critical performances such as raw material supply and demand, physical properties and heat resistance. Therefore, it can be said that the technology for manufacturing materials with suitable physical properties applicable to parts is important.

The inventors of the present invention have been studying a silica-polybutadiene composite material in order to improve the affinity with silica by modifying polybutadiene with a waste vegetable oil and stirring it in an organic solvent to produce a silica-polybutadiene composite material The present inventors have discovered that the silica-polybutadiene composite material to be produced is eco-friendly because it uses waste vegetable oil and that the silica can be uniformly dispersed in the polybutadiene to improve the physical properties of the composite material, Thus completing the present invention.

It is an object of the present invention to provide a process for producing a silica-polybutadiene composite material and a silica-polybutadiene composite material produced thereby.

In order to achieve the above object,

Preparing a polybutadiene modified with a waste vegetable oil (step 1); And

And a step (Step 2) of adding polybutadiene modified with waste vegetable oil prepared in Step 1 and silica to an organic solvent and stirring the mixture (Step 2).

In addition,

The present invention provides a silica-polybutadiene composite material comprising the polybutadiene prepared by the above-described method and modified with a waste vegetable oil.

Further,

Injecting a rubber compound comprising the silica-polybutadiene composite into a mold, and vulcanizing the rubber compound in the mold.

The process for producing the silica-polybutadiene composite material according to the present invention can improve the affinity with silica by modifying the polybutadiene with a waste vegetable oil. In this way, the polybutadiene modified with the waste vegetable oil is reacted with silica in an organic solvent And stirred to disperse silica more uniformly. The silica-polybutadiene composite material thus produced can reduce the carbon dioxide emission because of the use of the waste vegetable oil, and the physical properties of the composite material are improved by the uniformly dispersed silica.

1 is a graph of infrared spectroscopy (FT-IR) analysis of polybutadiene and polybutadiene modified with waste vegetable oil prepared in Production Example 1 and Production Example 2 according to the present invention;
FIG. 2 is a graph showing nuclear magnetic resonance spectroscopy (H-NMR) analysis of polybutadiene and polybutadiene modified with waste vegetable oil prepared in Production Example 1 and Production Example 2 according to the present invention;
3 is a scanning electron microscope (SEM) photograph of the silica-polybutadiene composite material prepared in Example 1 and Comparative Example 1 according to the present invention;
4 is a graph showing mechanical properties of the rubber compound prepared in Example 2, Example 3, Comparative Example 2 and Comparative Example 3 according to the present invention.

The present invention

Preparing a polybutadiene modified with a waste vegetable oil (step 1); And

And a step (Step 2) of adding polybutadiene modified with waste vegetable oil prepared in Step 1 and silica to an organic solvent and stirring the mixture (Step 2).

Hereinafter, the method for producing the silica-polybutadiene composite material according to the present invention will be described in detail for each step.

First, in the method for producing a silica-polybutadiene composite material according to the present invention, step 1 is a step of preparing polybutadiene modified with a waste vegetable oil.

In the above step 1, the polybutadiene may be modified into a waste vegetable oil to improve the affinity of the polybutadiene with silica, and the carbon dioxide generated when the waste rubber is treated can be reduced. When applied to a tire, the rolling resistance ) And the like are improved.

Specifically, Step 1 of preparing the polybutadiene modified with the waste vegetable oil is, for example,

Adding a butadiene monomer and an initiator to an organic solvent, and performing a polymerization reaction to prepare a reaction product comprising polybutadiene (step a); And

(B) adding a waste vegetable oil to the reactant prepared in step (a) and performing a coupling reaction (step (b)).

The anionic polymerization method can easily control the molecular weight and control the microstructure of the polymer, so that the polybutadiene, which is a polymer, and the waste vegetable oil can be efficiently synthesized.

First, step (a) is a step of adding a butadiene monomer and an initiator to an organic solvent, and performing a polymerization reaction to prepare a reactant containing polybutadiene.

The initiator of step a may be n-butyllithium, tetra-butyllithium, or the like.

The organic solvent used in step (a) is not limited as long as it is a solvent capable of dissolving the butadiene monomer and the initiator, and examples thereof include cyclohexane, heptane, hexane, and tetrahydrofuran ) Can be used.

At this time, the polar additive may be further added in step a. As an example, when THF is added as a polar additive, it acts as a Lewis base (a-Ligand) in anionic polymerization and interacts with lithium ions, which are counter ions, in the form of a chelate to form aggregated anions It serves to disperse. As a result, it plays a role of increasing the polymerization rate in the nonpolar solvent and can act as a large variable in the anionic polymerization.

In addition, it is preferable that the polymerization reaction of step (a) is carried out at a temperature of 50 to 130 DEG C for 20 to 60 minutes. When the polymerization reaction of step (a) is carried out at a temperature lower than 50 ° C., there is a problem that the butadiene monomer and the initiator react with each other and the polymerization reaction is difficult to start. When the polymerization is carried out at a temperature exceeding 130 ° C., There is a problem with safety.

Further, when the polymerization reaction of step (a) is carried out for less than 20 minutes, an unreacted material is excessively formed and a desired molecular weight can not be obtained. When the polymerization reaction is carried out for more than 60 minutes, Can not do it.

Next, step (b) is a step of adding a waste vegetable oil to the reactant prepared in step (a) to perform a coupling reaction.

Specifically, since anionic polymerization does not have a stopping reaction and a chain transfer reaction, a carbon anion (Carbanion) is present at the growing chain terminal even after the monomer is completely consumed. At this time, a coupling reaction can be performed using a waste vegetable oil.

For example, when an epoxidized soybean oil is used as a waste vegetable oil, the carbon anion at the end of the polybutadiene is added to a nucleophilic additive that attacks the a-carbon of the ester group of the triglyceride The polybutadiene can bind to triglycerides by a nucleophilic addition reaction.

At this time, the content of the waste vegetable oil added in the step b is preferably 0.1 to 10.0 parts by weight based on 100 parts by weight of the polybutadiene. If the content of the waste vegetable oil added in the step b is less than 0.1 part by weight with respect to 100 parts by weight of the polybutadiene, it is difficult to modify the polybutadiene with the waste vegetable oil. When the amount exceeds 10.0 parts by weight, There is a problem that the waste vegetable oil remains unreacted material.

As described above, polybutadiene modified with a waste vegetable oil can be prepared,

The vegetable oil of step 1 may be epoxidized soybean oil, sunflower oil, and palm oil, but is not limited thereto.

The molecular weight of the polybutadiene modified with the waste vegetable oil in step 1 is preferably 50,000 to 100,000 g / mol. If the molecular weight of the polybutadiene modified with the waste vegetable oil in the step 1 is less than 50,000 g / mol, the coupling reaction of the waste vegetable oil and the polybutadiene is not performed. If the molecular weight exceeds 100,000 g / mol There is a problem that the processability is insufficient when the rubber molded product is manufactured later.

Further, the polybutadiene modified with the waste vegetable oil of step 1 above may be polybutadiene modified with an epoxidized soybean oil as a specific example.

Next, in the method for producing a silica-polybutadiene composite material according to the present invention, Step 2 is a step of adding polybutadiene modified with waste vegetable oil prepared in Step 1 and silica to an organic solvent and stirring.

The method for producing a silica-polybutadiene composite material according to the present invention is characterized in that, as in step 2, solution mixing is performed by adding polybutadiene modified with waste vegetable oil prepared in step 1 and silica to an organic solvent and stirring It is possible to uniformly disperse silica.

Specifically, the polybutadiene modified with the waste vegetable oil in step 2 may be added to the organic solvent in a liquid phase. In preparing the polybutadiene modified with the waste vegetable oil in the step 1, the polybutadiene modified with the waste vegetable oil prepared by the anionic polymerization method may exist in the form of a liquid. The polybutadiene modified with the liquid vegetable oil Butadiene is easily mixed with silica in an organic solvent.

The organic solvent of step 2 may be cyclohexane, hepthane, hexane, tetrahydrofuran, or the like, but is not limited thereto. For example, cyclohexane, heptane, 9: 1 by volume.

The amount of silica added in step 2 is preferably 15 to 50 parts by weight based on 100 parts by weight of polybutadiene modified with waste vegetable oil. If the amount of silica added in step 2 is less than 15 parts by weight based on 100 parts by weight of the polybutadiene modified with the waste vegetable oil, there is a problem that the physical properties of the silica-polybutadiene composite material decrease, There is a problem that the physical properties of the silica-polybutadiene composite material are also reduced.

Further,

The present invention provides a silica-polybutadiene composite material comprising the polybutadiene prepared by the above-described method and modified with a waste vegetable oil.

The silica-polybutadiene composite material containing the polybutadiene modified with the waste vegetable oil according to the present invention contains polybutadiene improved in affinity with silica by modifying the polybutadiene with a waste vegetable oil so that the silica is uniformly dispersed . In addition, since the silica-polybutadiene composite material according to the present invention uses waste vegetable oil, the carbon dioxide emission can be reduced, and the physical properties of the composite material can be improved by the uniformly dispersed silica.

In the silica-polybutadiene composite material containing the polybutadiene modified with the waste vegetable oil according to the present invention, the waste vegetable oil may be, but is not limited to, epoxidized soybean oil, sunflower oil and palm oil .

In the silica-polybutadiene composite material comprising the polybutadiene modified with the waste vegetable oil according to the present invention, the molecular weight of the modified polybutadiene modified with the waste vegetable oil is preferably 50,000 to 100,000 g / mol. If the molecular weight of the polybutadiene modified with the waste vegetable oil is less than 50,000 g / mol, the coupling reaction between the waste vegetable oil and the polybutadiene will not be performed. If the molecular weight exceeds 100,000 g / mol, There is a problem that workability is insufficient when a molded article is produced.

In the silica-polybutadiene composite material comprising the polybutadiene modified with the waste vegetable oil according to the present invention, the content of silica in the silica-polybutadiene composite material is preferably 15 to 15 parts by weight based on 100 parts by weight of the polybutadiene modified with the waste vegetable oil. To 50 parts by weight. If the content of silica in the silica-polybutadiene composite material is less than 15 parts by weight based on 100 parts by weight of the polybutadiene modified with the waste vegetable oil, there is a problem that the physical properties of the silica-polybutadiene composite material are reduced. There is a problem that the physical properties of the silica-polybutadiene composite material are reduced.

In addition,

And a rubber blend comprising the silica-polybutadiene composite material.

The rubber compound according to the present invention may further comprise a raw rubber which is generally used as a raw material rubber and which contains silica-polybutadiene composite material prepared by the production method according to the present invention, And may contain a compounding agent such as a softening agent and a plasticizer. Also, it may include a vulcanization accelerator such as dibenzothiazyl disulfide (DM), tetrabenzylthiuram disulfide (TBzTD), and sulfur (IS).

The rubber compound according to the present invention may further comprise a waste vegetable oil. By way of example, tensile strength or elongation can be improved if the oil further comprises epoxidized soybean oil.

The rubber compound containing the silica-polybutadiene composite material according to the present invention includes the silica-polybutadiene composite material in which silica is uniformly dispersed, so that the rubber molded article produced using the rubber compound according to the present invention has excellent physical properties .

Further,

Injecting the rubber compound into the mold, and vulcanizing the rubber compound in the mold.

A rubber compound containing a silica-polybutadiene composite material according to the present invention can be injected into a mold, and the rubber compound can be vulcanized in the mold to produce a rubber molded article.

In addition,

A rubber molded article produced by the above production method is provided.

The rubber molded articles produced using the rubber blend containing the silica-polybutadiene composite material according to the present invention show excellent physical properties through the silica-polybutadiene composite material in which silica is evenly dispersed.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

It should be noted, however, that the following examples and experimental examples are illustrative of the present invention, but the scope of the invention is not limited by the examples and the experimental examples.

PREPARATION EXAMPLE 1 Preparation of polybutadiene modified with waste vegetable oil 1

Step 1: Nitrogen was injected into a 1 L high-temperature and high-pressure reactor for 1 hour to form a nitrogen atmosphere, and cyclohexane from which dissolved oxygen was removed was connected to the high-temperature and high-pressure reactor through a line. The temperature of the reactor filled with cyclohexane as a solvent was set to 40 DEG C using a bath circulator and stirred at 300 RPM.

The pressure inside the high-temperature and high-pressure reactor was removed, and a small amount of tetrahydrofuran (THF) was added as a polar additive. Next, 100 g of butadiene monomer was charged into a cylinder, the cylinder was connected to the high-temperature and high-pressure reactor upper line, and the nitrogen line was connected to the upper portion of the cylinder. Thereafter, both the line valve connected to the high-temperature and high-pressure reactor and the cylinder valve were opened to introduce the butadiene monomer into the high-temperature and high-pressure reactor.

1 ml of n-butyllithium as an initiator was charged into a high-temperature and high-pressure reactor, and polymerization was carried out for about 60 minutes.

Step 2: After completion of the polymerization reaction in Step 1, 2.3 g of epoxidized soybean oil (ESO) was put into a high-temperature and high-pressure reactor as a waste vegetable oil and the coupling reaction was carried out at a temperature of 60 ° C for 30 minutes Respectively.

Thereafter, the reaction solution was charged into a high-temperature and high-pressure reactor, stirred for a predetermined time to terminate the reaction, the residual pressure of the reactor was removed, and the reaction product was recovered and treated with methanol three times. Thus, unreacted materials and impurities were removed and polybutadiene modified with liquid epoxidized soybean oil was prepared.

At this time, the molecular weight of the prepared polybutadiene modified with epoxidized soybean oil is about 100,000 g / mol.

PREPARATION EXAMPLE 2 Preparation of Polybutadiene 1

Nitrogen was injected into a 1 L high-temperature and high-pressure reactor for 1 hour to form a nitrogen atmosphere. Cyclohexane in which dissolved oxygen was removed was connected to the high-temperature and high-pressure reactor through a line. The temperature of the reactor filled with cyclohexane as a solvent was set to 40 DEG C using a bath circulator and stirred at 300 RPM.

The pressure inside the high-temperature and high-pressure reactor was removed, and a small amount of tetrahydrofuran (THF) was added as a polar additive. Next, 100 g of butadiene monomer was charged into a cylinder, the cylinder was connected to the high-temperature and high-pressure reactor upper line, and the nitrogen line was connected to the upper portion of the cylinder. Thereafter, both the line valve connected to the high-temperature and high-pressure reactor and the cylinder valve were opened to introduce the butadiene monomer into the high-temperature and high-pressure reactor.

1 ml of n-butyllithium as an initiator was charged into a high-temperature and high-pressure reactor, and the polymerization reaction was carried out for about 180 minutes to prepare polybutadiene.

The molecular weight of the prepared polybutadiene is about 50,000 g / mol.

≪ Example 1 > Preparation of silica-polybutadiene composite material 1

Step 1: The polybutadiene modified with the liquid epoxidized soybean oil prepared in Preparation Example 1 was prepared.

Step 2: 100 g of the polybutadiene modified with the liquid epoxidized soybean oil prepared in the step 1 and 30 g of silica were added to a mixed solvent of cyclohexene and heptane in a volume ratio of 9: 1, Lt; / RTI > to produce a silica-polybutadiene composite material.

≪ Example 2 > Preparation of rubber compound containing silica-polybutadiene composite material 1

Step 1: As the first compounding step, 130 g of the silica-polybutadiene composite material prepared in Example 1 and 120 g of butadiene rubber (manufactured by Kumho Petrochemical Co., Ltd.) were added to an internal mixer set at a temperature of 70 캜 and a rotational speed of 600 RPM, Chem., KBR01) was added and blended for 180 seconds. Next, 1 g of stearic acid (St / A) was added and mixed for 60 seconds. 20 g of silica (Zeosil-175, Rhodia) was added and mixed for 120 seconds. Polyethylene glycol (PEG4000, Mw: 4000 g / mol) and 5 g of zinc oxide (ZnO) were added and mixed for 60 seconds. Finally, the first mixing was completed by further mixing for 180 seconds.

Step 2: In the second mixing step, the material having been firstly mixed in Step 1 was put into a two-roll mill set at a temperature of 50 ° C, preblended for 40 seconds 0.7 g of dibenzothiazyl disulfide (DM), 0.3 g of tetrabenzylthiuram disulfide (TBzTD) and 1.6 g of sulfur (Insoluble sulfur, IS) were added in this order. The number of times of winding the roll of the two-roll mill was performed five times to prepare a rubber compound.

≪ Example 3 > Preparation of rubber compound containing silica-polybutadiene composite material 2

A rubber compound was prepared in the same manner as in Example 2 except that 2.3 g of epoxidized soybean oil was further added in the step 1 of Example 2 above.

≪ Comparative Example 1 &

The procedure of Example 1 was repeated except that the polybutadiene prepared in Preparation Example 2 was used instead of the polybutadiene modified with the liquid epoxidized soybean oil prepared in Production Example 1 in Step 1 of Example 1 To prepare a silica-polybutadiene composite material.

≪ Comparative Example 2 &

The procedure of Example 2 was repeated except that the silica-polybutadiene composite material prepared in Comparative Example 1 was used instead of the silica-polybutadiene composite material prepared in Example 1 in Step 1 of Example 2 Rubber blends were prepared.

≪ Comparative Example 3 &

The procedure of Example 3 was repeated except that the silica-polybutadiene composite material prepared in Comparative Example 1 was used instead of the silica-polybutadiene composite material prepared in Example 1 in Step 1 of Example 3 Rubber blends were prepared.

≪ Experimental Example 1 > FT-IR and H-NMR analysis

Infrared spectroscopic analysis (FT-IR) of the polybutadiene and polybutadiene modified with the waste vegetable oil prepared in Preparation Examples 1 and 2 was carried out in order to confirm the structure of the polybutadiene modified with the waste vegetable oil according to the present invention. And nuclear magnetic resonance spectroscopy (H-NMR). The results are shown in FIGS. 1 and 2. FIG.

As shown in Fig. 1, in the case of Production Example 1, which is polybutadiene modified with a waste vegetable oil, a peak could be confirmed at a wavenumber of 1747 cm ^-1 . This is the peak that can appear in the epoxidized soybean oil used as a waste vegetable oil at the peak indicating C = 0.

Further, as shown in Fig. 2, peaks at 2.8 to 3.2 ppm could be observed in the epoxidized soybean oil. As a result, it was confirmed that polybutadiene was modified with epoxidized soybean oil which is a waste vegetable oil.

<Experimental Example 2> Scanning electron microscopic observation

In order to observe the dispersibility of silica in the silica-polybutadiene composite material prepared by the production method according to the present invention and containing polybutadiene modified with waste vegetable oil, the silica-polybutadiene composite material prepared in Example 1 and Comparative Example 1, The polybutadiene composite material was observed with a scanning electron microscope (SEM), and the results are shown in Fig.

As shown in Fig. 3, in the case of Example 1, which is a silica-polybutadiene composite material produced by the production method of the present invention and containing a polybutadiene modified with a waste vegetable oil, silica is added to the surface of the silica-polybutadiene composite material In the case of Comparative Example 1, which is a silica-polybutadiene composite material containing an unmodified polybutadiene, silica having a size of about 10 탆 is aggregated .

Thus, it was confirmed that the silica-polybutadiene composite material prepared by the production method of the present invention and containing polybutadiene modified with waste vegetable oil had excellent dispersibility.

<Experimental Example 3> Mechanical Property Analysis

In order to confirm the physical properties of the rubber compound comprising the silica-polybutadiene composite material containing the polybutadiene modified with the waste vegetable oil according to the present invention, in Example 2, Example 3, Comparative Example 2 and Comparative Example 3 The tensile strength and elongation were measured using a UTM (Bong Shin, Tensometer 2000), and the hardness was measured using a hardness meter (JIS-A) The results are shown in Fig.

As shown in Fig. 4, the tensile strength in the case of Example 2 and Example 3, which is a rubber compound comprising a silica-polybutadiene composite material containing a polybutadiene modified with a waste vegetable oil according to the present invention, Of about 6.63 and about 6.70 MPa, respectively. On the other hand, in the case of Comparative Example 2 and Comparative Example 3, which are rubber formulations comprising a silica-polybutadiene composite material containing polybutadiene not modified with a waste vegetable oil, tensile strengths of about 6.13 and about 6.05 MPa, respectively, Which is 0.5 MPa or more lower than that of Example 2 and Example 3, respectively.

On the other hand, in the case of hardness, the values of 67 to 74 (shore A hardness) in the case of Example 2, Example 3, Comparative Example 2 and Comparative Example 3 were similar.

However, elongation at break was about 633% in Example 2 and about 655% in Example 3, while elongation ratios of Comparative Example 2 and Comparative Example 3 were about 586% And 594%, respectively.

Particularly, in the case of Example 3 in which epoxidized soybean oil, which is a waste vegetable oil, was added during the production of the rubber compound, the most excellent physical properties were confirmed.

Thus, it was confirmed that the rubber compound comprising the silica-polybutadiene composite material prepared by the production method according to the present invention and containing polybutadiene modified with waste vegetable oil had excellent physical properties.

Claims (11)

Preparing a polybutadiene modified with a waste vegetable oil (step 1); And
And a step (Step 2) of adding the polybutadiene modified with the waste vegetable oil prepared in Step 1 and silica to an organic solvent and stirring the resultant mixture (Step 2).
The method according to claim 1,
The step 1 of preparing the polybutadiene modified with the waste vegetable oil comprises:
Adding a butadiene monomer and an initiator to an organic solvent, and performing a polymerization reaction to prepare a reaction product comprising polybutadiene (step a); And
(B) performing a coupling reaction by adding a waste vegetable oil to the reactant prepared in the step (a).
3. The method of claim 2,
Wherein the initiator of step (a) is n-butyllithium or tetra-butyllithium.
3. The method of claim 2,
Wherein the organic solvent of step (a) is at least one selected from the group consisting of cyclohexane, heptane, hexane and tetrahydrofuran. Way.
3. The method of claim 2,
Wherein the polymerization reaction of step (a) is carried out at a temperature of 50 to 130 DEG C for 20 to 60 minutes.
3. The method of claim 2,
Wherein the content of the waste vegetable oil added in the step (b) is 0.1 to 10.0 parts by weight based on 100 parts by weight of the polybutadiene.
The method according to claim 1,
Wherein the molecular weight of the polybutadiene modified with the waste vegetable oil in step 1 is 50,000 to 100,000 g / mol.
The method according to claim 1,
Wherein the content of silica added in step 2 is 15 to 50 parts by weight based on 100 parts by weight of the polybutadiene modified with the waste vegetable oil.
The method according to claim 1,
Wherein the organic solvent of step 2 is at least one selected from the group consisting of cyclohexane, hepthane, hexane and tetrahydrofuran. Way.
A silica-polybutadiene composite material produced by the manufacturing method of claim 1, comprising polybutadiene modified with a waste vegetable oil.
A method for manufacturing a rubber molded article, comprising injecting a rubber compound comprising the silica-polybutadiene composite material of claim 10 into a mold, and vulcanizing the rubber compound in the mold.

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