KR101818749B1 - Carbon nanotube complex coated with dicyclopentadiene polymer and method for preparation of polydicyclopentadiene using the same as an additive - Google Patents

Abstract

The present invention relates to a method for manufacturing a carbon nanotube complex coated with a dicyclopentadiene (DCPD) polymer on the surface, polydicyclopentadiene comprising a carbon nanotube complex coated with a DCPD complex as an additive and a method for manufacturing a molded article thereof. A carbon nanotube complex coated with DCPD on the surface according to the present invention has improved miscibility, thereby being uniformly distributed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a carbon nanotube composite coated with a dicyclopentadiene polymer and a method for producing a polydicyclopentadiene using the same as an additive.

The present invention relates to a method for producing a carbon nanotube composite having a surface coated with dicyclopentadiene (DCPD) polymer; To a polydicyclopentadiene comprising a carbon nanotube composite in which a dicyclopentadiene polymer is coated as an additive, and a process for producing a molded product thereof.

C5, a compound with five carbon atoms, is the last by-product that can be used in the petrochemical process. C5 inducing products are the next generation growth engine for domestic petrochemical companies, which are struggling with low costs in the Middle East and high- .

According to NexantThinking's 2013 data, the production of dicyclopentadiene (DCPD) has steadily increased from about 500,000 tons in 2000 to about 800,000 tons in 2012, and demand is also increasing. Of these, low purity dicyclopentadiene used as UPCR (unsaturated polyester) and HCR (hydrocarbon resin) accounts for more than 70%, and the remaining 20 to 30% is used as EPDM, ENB, COC, COP, p- And ultra-high-purity dicyclopentadiene, the use of ultra-high-purity dicyclopentadiene has recently been increasing.

Polydicyclopentadiene (polyDCPD) is a thermosetting resin with high cross-link density and is formed through ring opening metathesis polymerization (ROMP). It has high rigidity and corrosion resistance, excellent surface appearance, low cost and easy processability. And has been widely applied to high performance polymer composite materials.

In particular, dicyclopentadiene reactive injection molding materials have been steadily increasing in demand since they were commercialized in Paramont's truck hoods and agricultural tractor parts in 1995, replacing existing FP and metal materials, due to their lightweight and excellent properties .

In addition, the polymerization of dicyclopentadiene using a metathesis catalyst can be applied to reactive injection molding and can be used to manufacture snowmobiles, boat housings, chlorine cell covers, wastewater treatment equipment, and the like.

Dicyclopentadiene is easier to use because it has a fast cycle time in which it is crosslinked in a few minutes and is removed from the mold in 10 minutes.

On the other hand, in order to enhance the physical properties of the polydicyclopentadiene, a dicyclopentadiene may be used as a matrix to be made into a fiber reinforced and rubber reinforced composite material, and further, an additive may be prepared to further improve heat resistance and glass transition temperature (Tg) .

Also, polymer based composites reinforced with carbon nanotubes (CNT) having excellent mechanical properties and electric and thermal conductivity are being studied. In carrying out such a study, there is a problem that the added carbon nanotubes have poor dispersibility with respect to dicyclopentadiene, and therefore, it is very important to solve this problem. For example, when the carbon nanotube is not well dispersed in the dicyclopentadiene, a polydicyclopentadiene having a remarkably low uniformity is produced. In this case, the added carbon nanotube acts as a foreign substance rather than the generated polydicyclone The physical properties of the pentadiene become poor, and it is difficult to store for a long time because the carbon nanotubes precipitate over time.

In this context, Chinese Patent No. 102675802 discloses a method for producing a polydicyclopentadiene complex by reacting dicyclopentadiene with carbon nanotubes modified with acrylic acid under a tungsten catalyst. In addition, there has been reported a method of synthesizing a silane coupling agent and a norbornene-based monomer after forming a carboxyl group by acid-treating the carbon nanotube, and attaching a functional group to the carbon nanotube by bonding them. However, the manufacturing process is difficult, .

However, it is still difficult to produce polydicyclopentadiene having improved uniformity and improved strength by improving the dispersibility of carbon nanotubes.

The inventors of the present invention have conducted intensive researches to find out a method for producing a polydicyclopentadiene and a molded article thereof having improved physical properties by using a carbon nanotube-based additive and the additive. As a result, they have found that when dicyclopentadiene is added to a carbon nanotube, , The dispersibility of the carbon nanotube-based additive in the dicyclopentadiene is remarkably improved when the carbon nanotubes coated with the dicyclopentadiene polymer are added to the surface of the carbon nanotube-based additive, Can be improved and can be stored for a long time. The present invention has been completed based on this finding.

A first aspect of the present invention is a method for producing a polymer electrolyte fuel cell comprising the steps of charging carbon nanotubes (CNT) and dicyclopentadiene (DCPD) into a reaction vessel and polymerizing at 100 to 200 ° C, The present invention provides a method for producing a carbon nanotube composite coated with a polymer.

The second aspect of the present invention provides a carbon nanotube composite having a surface coated with a dicyclopentadiene polymer as an additive for the decomposition reaction of dicyclopentadiene to produce polydicyclopentadiene.

In a third aspect of the present invention, there is provided a carbon nanotube composite comprising a carbon nanotube composite having a surface coated with a dicyclopentadiene polymer as an additive, and performing ring opening metathesis polymerization (ROMP) of dicyclopentadiene (Polydicyclopentadiene) (polyDCPD), comprising the steps of:

In a fourth aspect of the present invention, there is provided a process for preparing a carbon nanotube composite, comprising dissolving a carbon nanotube complex having a surface coated with a dicyclopentadiene polymer in dicyclopentadiene, adding a solution prepared by dissolving a catalyst for decomposition reaction in an organic solvent, A first step of preparing a first step; A second step of preparing a second solution by dissolving a carbon nanotube complex having a surface coated with a dicyclopentadiene polymer in dicyclopentadiene and then adding a co-catalyst for the decomposition of the carbon nanotubes; And a third step of mixing the first solution and the second solution and injecting the mixed solution into a mold to perform a single decomposition decomposition reaction. The carbon nanotube composite according to claim 1, A process for producing a molded article of dicyclopentadiene is provided.

Hereinafter, the present invention will be described in more detail.

Conventionally, carbon nanotubes having excellent strength and electrochemical properties have been used as additives in order to improve physical properties of polydicyclopentadiene. However, since carbon nanotubes have poor dispersibility in dicyclopentadiene as a raw material, There is a problem that a polydicyclopentadiene can not be produced. In addition, there is a problem that the effect of improving the physical properties is not high even though the carbon nanotubes are added, and carbon nanotubes are deposited when stored for a long period of time. To improve this, the surface of the carbon nanotubes was modified by various materials and / or methods, but this required complicated and / or difficult experimental conditions. DISCLOSURE OF THE INVENTION The present invention was devised to solve such a problem, and the dicyclopentadiene itself was thermally polymerized with carbon nanotubes so that the dicyclopentadiene polymer was coated on the surface of the carbon nanotubes. When it is used in the polymerization of polydicyclopentadiene, the miscibility with dicyclopentadiene is remarkably improved and can be dispersed evenly, and the effect of improving the physical properties is more excellent, and the problem can be solved without adding another substance It is based on being able to solve.

More specifically, the present invention relates to a method for producing a dicyclopentadiene polymer (hereinafter referred to as " dicyclopentadiene polymer ") comprising the step of charging carbon nanotubes (CNT) and dicyclopentadiene Coated carbon nanotube composite can be provided.

For example, the polymerization may be carried out at 100 to 200 ° C. Specifically, it may be carried out at 130 to 170 ° C, more specifically at 140 to 160 ° C, but is not limited thereto. If the polymerization temperature is lower than 100 ° C, there may be a problem that DCPD may be mixed with CNT without becoming a polymer, and when the temperature exceeds 200 ° C, the DCPD polymer produced may be discolored due to heat.

For example, the reaction may be carried out with stirring for 6 to 24 hours. Specifically, it may be carried out for 9 to 15 hours, more specifically for 11 to 13 hours, but is not limited thereto. If it is less than 6 hours, there may be a problem that all of the added DCPD remain unreacted, and if it exceeds 24 hours, more energy than necessary may be consumed.

The pressure, temperature, and / or time of the reaction of polymerizing dicyclopentadiene to coat the surface of the carbon nanotube with the dicyclopentadiene polymer may be appropriately selected .

The dicyclopentadiene polymer may have a weight average molecular weight (Mw) of 100 to 1000.

The weight average molecular weight (Mw) of the carbon nanotube composite coated with the dicyclopentadiene polymer on the surface may be 100 to 1500, specifically 500 to 1400, more specifically 1000 to 1380, more specifically 1200 to 1370.

The number average molecular weight (Mn) of the carbon nanotube complex coated with the dicyclopentadiene polymer on the surface may be 100 to 1000, specifically 200 to 800, more specifically 300 to 700, and more specifically 400 to 600.

The polydispersity index (PDI) of the carbon nanotube composite having the surface coated with the dicyclopentadiene polymer may be 1 to 5, specifically 2 to 4, more specifically 2.3 to 2.7.

The carbon nanotubes may be added in an amount of 50 to 200 vol%, specifically 80 to 150 vol%, more specifically 100 to 120 vol%, based on the volume of the dicyclopentadiene. If it is less than 50% by volume, there may be a problem that the added carbon nanotube remains in an undispersed state, and when it exceeds 200% by volume, there is a problem that the carbon nanotube is not well dispersed in the dicyclopentadiene polymer have.

As a result of scanning electron microscope (SEM) measurement of a carbon nanotube composite having a surface coated with a dicyclopentadiene polymer according to an embodiment of the present invention, the result was as shown in FIG. 2, and dicyclopentadiene It was observed that the carbon nanotubes were uniformly dispersed by thermal polymerization.

The present invention can provide a carbon nanotube composite in which a dicyclopentadiene polymer is coated on the surface thus prepared. Specifically, the carbon nanotubes may be dispersed in the dicyclopentadiene polymer. The carbon nanotubes can be surface-modified with a dicyclopentadiene polymer and used as an additive for the decomposition reaction of dicyclopentadiene in order to prepare polydicyclopentadiene. Specifically, the carbon nanotube composite prepared by the method of the present invention can be prepared by using dicyclopentadiene, which is one of the raw materials of polydicyclopentadiene, in a single step reaction, When used as an additive in the production process of dicyclopentadiene, the dispersibility is excellent, and a better physical property improvement effect can be obtained as compared with the case of simply adding carbon nanotubes.

Meanwhile, the carbon nanotube composite according to the present invention is different from the polydicyclopentadiene in which carbon nanotubes are dispersed. The carbon nanotube composite is a dicyclopentadiene polymer having a weight average molecular weight of about 100 to 1,000, Lt; / RTI > In addition, the carbon nanotube composite of the present invention is thermoplastic while the polydicyclopentadiene is a thermosetting resin. The result of thermogravimetric analysis (TGA) of the carbon nanotube composite according to one embodiment of the present invention is shown in FIG.

In another aspect, the present invention provides a method for producing a carbon nanotube composite material, which comprises a carbon nanotube composite having a surface coated with a dicyclopentadiene polymer as an additive, wherein the ring opening metathesis polymerization (ROMP) of dicyclopentadiene is carried out in the presence of a catalyst, (Polydicyclopentadiene) (polyDCPD), which comprises the steps of:

At this time, the catalyst used may be a catalyst for a single-ring degradation reaction, or a combination of a catalyst for a single-ring degradation reaction and a cocatalyst. The specific types of catalysts are described in detail below.

The above-mentioned "dicyclopentadiene" can be obtained by polymerizing norbornene cycloolefins. The dicyclopentadiene is a yellow liquid at room temperature and can be used as the main raw material for the resin. In the case of dicyclopentadiene, the unit cost is low, and the polymerization and the high-speed compression molding process can be performed in an oxygen atmosphere, so that the overall process cost can be lowered and the time can also be shortened.

The polydicyclopentadiene is excellent in impact strength and flexural strength, and is a material having high impact resistance at low temperatures unlike other polymer materials. In addition, it has excellent chemical resistance against acid and alkali, and has excellent cold resistance. Therefore, it shows superior mechanical properties to glass fiber reinforced plastics even at minus 40 ℃, so it can be applied to materials used in low temperature environment. It is also a friendly material that is easy to polish after coating, harmless when it is incinerated, and does not leave residues because it has excellent adhesion with paints and can be applied as material coating material.

The dicyclopentadiene polymer may have a weight average molecular weight of 100 to 1,000.

The single decomposition decomposition reaction of the dicyclopentadiene may be carried out with polybutadiene. When polybutadiene is included, physical properties such as impact strength can be further improved. The polybutadiene may be contained in an amount of 0.01 to 10 parts by weight, 1 to 5 parts by weight, and 1.5 to 3 parts by weight based on 100 parts by weight of the dicyclopentadiene according to the present invention. The polybutadiene may be added as an elastomer and other elastomers known in the art may be used instead.

According to another aspect of the present invention, there is provided a method for producing a carbon nanotube composite material, which comprises dissolving a carbon nanotube composite and a polybutadiene having a surface coated with a dicyclopentadiene polymer in a dicyclopentadiene, adding a solution prepared by dissolving a catalyst for decomposition reaction in an organic solvent A first step of preparing a first solution; A second step of preparing a second solution by dissolving a carbon nanotube composite and a polybutadiene having a surface coated with a dicyclopentadiene polymer on dicyclopentadiene, And a third step of mixing the first solution and the second solution and injecting the mixed solution into a mold to perform a single decomposition decomposition reaction. The carbon nanotube composite according to claim 1, A process for producing a molded article of dicyclopentadiene is provided.

The dicyclopentadiene and polydicyclopentadiene are as defined above.

The dicyclopentadiene polymer coated on the surface of the carbon nanotubes may have a weight average molecular weight of 100-1000.

The one-fold degradation reaction may be carried out with polybutadiene. When polybutadiene is included, physical properties such as impact strength can be further improved. The polybutadiene may be contained in an amount of 0.01 to 10 parts by weight, 1 to 5 parts by weight, and 1.5 to 3 parts by weight based on 100 parts by weight of the dicyclopentadiene according to the present invention. The polybutadiene may be added as an elastomer and other elastomers known in the art may be used instead.

The production of the polydicyclopentadiene molded article to which the carbon nanotube composite with the dicyclopentadiene polymer coated on the surface of the present invention is added can be carried out by reaction injection molding (RIM). Since the thermosetting resin is not melted again once the resin is made, the product is molded while performing the synthesis reaction in the mold. The chemicals that react as a polymer are supplied separately. Mix them in the mixing head just before entering the mold, and push the mixed material through the plunger to enter the mold. By doing so, the liquid with a very low viscosity is filled with the low pressure in the cavity of the mold, and the reaction is completed in the mold to obtain the product of the thermosetting resin. The solidification of the polymer resin is achieved by lowering the temperature in general injection molding, but by completing the reaction in the reaction injection molding. In the case of reactive injection, the temperature of the mold is higher than that of the conventional injection molding, which improves the reaction.

Reactive injection molding can be performed by mixing different components in a mixing head at a high pressure through a compression press, mixing them uniformly, injecting them into a mold, and hardening them in a mold.

The RIM forming process according to the present invention can be performed in the following order. From each raw material tank containing two types of liquid resin, each resin is uniformly mixed in a mixing head at a pressure of 1,500 to 3,000 psi and then injected into a mold. The mixed solution injected into the mold is cured within a few minutes and commercialized. RIM molding can be very important in the reactivity of the two components injected into the mixing head. If the amount of the catalyst and the promoter is large, the product can not be obtained because the solution is hardened before uniformly mixing the liquid. On the contrary, if the amount of the catalyst and the promoter is small, the two solutions are mixed, The product may not be obtained. Therefore, it is important to control the curing time and cross-linking density by controlling the reactivity of the two liquids in RIM molding.

The term "catalyst" of the present invention means a substance which is added to a chemical reaction in addition to a reactant to increase the rate of a chemical reaction by participating in a specific reaction. Specifically, the catalyst for the decomposition reaction of the present invention may be a substance which is added to the decomposition reaction for decomposition and promotes the reaction.

The term "co-catalyst or cocatalyst " of the present invention means a substance added to the reaction together with the catalyst to promote the activity of the catalyst.

For example, the catalyst for decomposition decomposition reaction may be one selected from the group consisting of tungsten (W), molybdenum (Mo), ruthenium, titanium (Ti) Or more.

Specifically, the catalyst may further include a cocatalyst in the case where the catalyst for decomposing and decomposing the catalyst is a tungsten (W), molybdenum (Mo) or ruthenium (Ru) system.

Specifically, the cocatalyst for the single-drop decomposition reaction may be at least one substance selected from the group consisting of HCl, CuCl, AlCl ₃ , HSiCl ₃ , trialkylaluminum, alkylaluminum dihalide, dialkylaluminum halide, However, the present invention is not limited thereto, and a person skilled in the art can appropriately select it depending on the kind of catalyst used together.

For example, the ruthenium-based catalyst may be a Grubbs first-generation, second-generation, or third-generation catalyst, and may be a Hoveyda type catalyst. A latent ruthenium catalyst is a combination of a ruthenium catalyst with a schiff base and can be used together with a cocatalyst. At this time, as a co-catalyst of the potential ruthenium catalyst, HCl, CuCl, AlCl ₃ , HSiCl ₃ and the like can be used, but it is not limited thereto.

For example, the tungsten-based catalyst may be WCl ₆ or WOCl ₄ . The cocatalyst that can be used with the tungsten-based catalyst may be trialkylaluminum, alkylaluminum dihalide or dialkylaluminum halide. Specifically, diethylaluminum chloride may be used in combination as a cocatalyst with a WCl6 catalyst, but the present invention is not limited thereto.

For example, the molybdenum-based catalyst may be Mo (CO) ₅ PPh ₃ , and the co-catalyst that can be used with it may be alkylaluminum, but is not limited thereto.

The dicyclopentadiene polymer coated on the surface of the carbon nanotubes may have a weight average molecular weight of 100-1000.

On the other hand, when the catalyst is a tungsten-based catalyst or a molybdenum-based catalyst, it may further contain a stabilizer.

For example, the stabilizer may be acetylacetone, alkyl acetoacetate, benzonitrile, or tetrahydrofuran. At this time, the stabilizer may be used in a proportion of 1 to 5 moles per mole of the catalyst for the decomposition reaction for decomposition.

The organic solvent in the first step may be toluene, as long as it can dissolve the catalyst for decomposing the single decomposition reaction.

Specifically, the mixing of the third step may be performed for 10 seconds to 1 minute. For example, if the mixing is shortened to 10 seconds or less, the reactants may not be mixed uniformly. If the mixing is performed for more than 1 minute, the reaction may start before the mixture is injected into the mold,

As described above, when the first solution contains a tungsten-based or molybdenum-based catalyst as a catalyst, it may further include a stabilizer. The types of stabilizers usable are the same as those exemplified above.

The second solution may further include a reaction modifier to adjust the reaction induction time. For example, the reaction modifier may be ethyl benzoate, dibutyl ether, or bis (2-methoxyethyl) ether. Specifically, the reaction modifier may be dibutyl ether, but is not limited thereto. At this time, the reaction modifier may be used in a proportion of 1 to 3 moles per mole of the cocatalyst to be used.

Specifically, the single decomposition decomposition reaction may be carried out at 40 to 100 ° C. More specifically, the reaction can be carried out at 50 to 80 占 폚, but is not limited thereto. If the temperature of decomposition at the single decomposition is less than 40 ° C, all the dicyclopentadienes may not react completely, resulting in poor physical properties and unreacted dicyclopentadienes may remain. If the temperature is more than 100 ° C, The dicyclopentadienes remain in the unreacted form in the dicyclopentadiene, which may be problematic.

In addition, the above-mentioned one-step decomposition reaction can be carried out for 1 to 30 minutes, but is not limited thereto. If the reaction time is shorter than 1 minute, sufficient crosslinking may not occur. On the other hand, if the reaction time is longer than 30 minutes, productivity may be lowered.

The temperature and / or the time of the single decomposition reaction may be appropriately selected by a person skilled in the art in a mutually complementary manner.

Other factors of the single decomposition decomposition reaction are preferably a pressure, and the reaction is performed at 1 to 3 bar, but the present invention is not limited thereto. The pressure may be adjusted by varying the viscosity of the first solution and the second solution and / And can be appropriately adjusted by those skilled in the art.

The polydicyclopentadiene molded article produced by the method of the present invention can be used in a snowmobile, a boat housing, a chlorine cell cover, or a wastewater treatment apparatus, but is not limited thereto.

The carbon nanotube composite coated with the dicyclopentadiene polymer on the surface of the present invention has significantly improved compatibility with dicyclopentadiene and can be uniformly dispersed in comparison with uncoated carbon nanotubes. Therefore, when used as an additive in the process for producing polydicyclopentadiene, the physical properties of the product are remarkably increased, and no problem arises because the carbon nanotube additive coated with a component other than the raw material is not used. In addition, since carbon nanotubes are surface-modified with dicyclopentadiene polymers, when they are used as additives in the process for manufacturing polydicyclopentadiene, they are strongly bonded to each other and can be maintained in a uniformly dispersed form for a long time, It is excellent.

1 is a view showing a scanning electron microscope (SEM) measurement result of a carbon nanotube itself.
2 is a view showing a scanning electron microscope (SEM) measurement result of a carbon nanotube composite having a surface coated with a dicyclopentadiene polymer.
3 is a graph showing the result of thermogravimetric analysis of a carbon nanotube composite having a surface coated with a dicyclopentadiene polymer.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited by the following examples.

Manufacturing example  One: Dicyclopentadiene  Polymer coated Carbon nano  Tube composite manufacturing

60 ml of CNT (Carbon Nano-material Technology Co., Ltd., Type: multiwall, diameter: 15 nm, length: 5 μm) was placed in a high-pressure reactor and 50 ml of DCPD was completely impregnated. The mixture was stirred at 150 ° C for 12 hours to prepare a CNT thermopolymer coated with a dicyclopentadiene polymer, that is, a carbon nanotube composite. The prepared CNT thermal polymer was measured as Mn of 550, Mw of 1350 and PDI of 2.45.

Example  One: Dicyclopentadiene  Polymer coated Carbon nano  Preparation of polyDCPD with Tube Complex 1

2.5 g of the carbon nanotube composite of Preparation Example 1, 2 g of polybutadiene having a molecular weight of 200,000 and 98 g of DCPD were thoroughly stirred and dissolved, then 1.1174 g of 26% WCl ₆ / toluene and 0.0825 g of benzonitrile were added and thoroughly stirred A first solution was prepared.

2.5 g of the carbon nanotube composite of Production Example 1, 2 g of polybutadiene having a molecular weight of 200,000, 98 g of DCPD, 1.325 g of 1M diethylaluminum chloride (Et ₂ AlCl) and 0.492 g of dibutyl ether were added and thoroughly stirred A second solution was prepared.

The first solution and the second solution were thoroughly stirred for 30 seconds and then put into a mold to prepare a specimen at 60 ° C for 10 minutes.

Example  2: Dicyclopentadiene  Polymer coated Carbon nano  Manufacture of polyDCPD with tube composite 2

A first solution was prepared in the same manner as in Example 1 except that 5 g of the carbon nanotube composite of Preparation Example 1 was used.

A second solution was prepared in the same manner as the second solution of Example 1, except that 5 g of the carbon nanotube composite of Preparation Example 1 was used.

The first solution and the second solution were thoroughly stirred for 30 seconds and then put into a mold to prepare a specimen at 60 ° C for 10 minutes.

Example  3: Dicyclopentadiene  Polymer coated Carbon nano  Manufacture of polyDCPD with tube composite 3

A first solution was prepared in the same manner as in the first solution of Example 1, except that 7.5 g of the carbon nanotube composite of Production Example 1 was used.

A second solution was prepared in the same manner as the second solution of Example 1, except that 7.5 g of the carbon nanotube composite of Production Example 1 was used.

The first solution and the second solution were thoroughly stirred for 30 seconds and then put into a mold to prepare a specimen at 60 ° C for 10 minutes.

Comparative Example 1: Production of polyDCPD

2 g of a polybutadiene having a molecular weight of 200,000 and 98 g of DCPD were completely stirred and dissolved. Then, 1.1174 g of 26% WCl ₆ / toluene and 0.0825 g of benzonitrile were added and thoroughly stirred to prepare a first solution.

100 g of DCPD, 1.325 g of 1M diethylaluminum chloride (Et ₂ AlCl) and 0.492 g of dibutyl ether were added and thoroughly stirred to prepare a second solution.

The first solution and the second solution were thoroughly stirred for 30 seconds and then put into a mold to prepare a specimen at 60 ° C for 10 minutes.

Comparative Example 2: Production of polyDCPD with CNT added

2 g of polybutadiene having a molecular weight of 200,000, 1 g of CNT and 98 g of DCPD were thoroughly stirred and dissolved. Then, 1.1174 g of 26% WCl ₆ / toluene and 0.0825 g of benzonitrile were added and thoroughly stirred to prepare a first solution.

2 g of polybutadiene having a molecular weight of 200,000, 1 g of CNT, 98 g of DCPD, 1.325 g of diethylaluminum chloride (Et ₂ AlCl) and 0.492 g of dibutyl ether were placed and thoroughly stirred to prepare a second solution.

The first solution and the second solution were thoroughly stirred for 30 seconds and then put into a mold to prepare a specimen at 60 ° C for 10 minutes.

Experimental Example 1: Analysis of prepared polyDCPD

The thermal and viscoelastic properties of the polyDCPD specimens prepared in the size of 35 mm × 5 mm × 1 mm according to Examples 1 to 3 and Comparative Examples 1 and 2 were measured by dynamic mechanical analysis (DMA) The results are summarized in Table 1 below.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Tensile toughness (MPa) 5.0 3.4 9.2 12.3 12.8 Storage modulus @ Tg + 30 DEG C (MPa) 15.3 14.4 17.6 19.8 20.2 Glass temperature (Tg, 캜) 151.1 152.1 153.5 154.7 154.6

As shown in Table 1, the polyDCPD prepared by using the carbon nanotube composite coated with the DCPD polymer of Preparation Example 1 as an additive according to Examples 1 to 3 according to the present invention was comparable to polyDCPD prepared without additives 1, and the tensile strength and storage modulus were significantly improved as compared with Comparative Example 2, which was polyDCPD prepared by using unmodified CNT as an additive. In addition, it was confirmed that the polyDCPD of Examples 1 to 3 of the present invention had a higher vitrification temperature than the polyDCPD of Comparative Examples 1 and 2. This indicates that the polyDCPD of Examples 1 to 3 has an excellent mechanical strength as compared with the polyDCPD of Comparative Examples 1 and 2 and can be used at a high temperature. That is, it is possible to use CNT coated with DCPD polymer as an additive according to the present invention PolyDCPD with improved mechanical strength and heat resistance can be used as a vehicle exterior material.

Experimental Example  2: Dicyclopentadiene  Polymer coated Carbon nano  Tube composite Ten Weight analysis

Thermogravimetric analysis (TGA) was performed with TA Instruments Q500.

20 mg of the carbon nanotube composite coated with the dicyclopentadiene polymer of Preparation Example 1 was mounted on a TGA pan, and the weight of the carbon nanotube composite was measured while heating at a heating rate of 10 ° C / min. At 450 ℃, all of the thermally polymerized DCPD except CNT was decomposed and it was found that it was a DCPD thermal polymer containing 15% of CNT.

From the above description, it will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. In this regard, it should be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention without departing from the scope of the present invention as defined by the appended claims.

Claims (12)

A method for producing a carbon nanotube having a surface coated with a dicyclopentadiene polymer, the method comprising the steps of charging a carbon nanotube (CNT) and dicyclopentadiene (DCPD) ≪ / RTI >
The method according to claim 1,
Wherein the dicyclopentadiene polymer has a weight average molecular weight of 100 to 1,000.
A carbon nanotube composite having a surface coated with a dicyclopentadiene polymer as an additive for the decomposition reaction of dicyclopentadiene to produce a polydicyclopentadiene.
A process for preparing a poly (cyclopentadiene) polymer, comprising the step of carrying out ring opening metathesis polymerization (ROMP) of a dicyclopentadiene in the presence of a catalyst, the carbon nanotube composite having a surface coated with a dicyclopentadiene polymer as an additive. A process for preparing polydicyclopentadiene (polyDCPD).
5. The method of claim 4,
Wherein the catalyst is a combination of a catalyst for decomposition of a single decomposition reaction or a catalyst for decomposition of a single decomposition reaction and a cocatalyst.
A first step of preparing a first solution by dissolving a carbon nanotube complex having a surface coated with a dicyclopentadiene polymer in dicyclopentadiene and then adding a solution prepared by dissolving a catalyst for decomposing decomposition in an organic solvent;
A second step of preparing a second solution by dissolving a carbon nanotube composite having a surface coated with a dicyclopentadiene polymer and then adding a cocatalyst for decomposing the carbon nanotubes; And
And a third step of mixing the first solution and the second solution and injecting the mixed solution into a mold to perform a single decomposition decomposition reaction. The method according to claim 1, wherein the carbon nanotube composite is coated on the surface with a dicyclopentadiene polymer- A process for producing a molded article of cyclopentadiene.
The method according to claim 5 or 6,
Wherein the catalyst for decomposing and decomposing the at least one catalyst is one or more catalysts selected from the group consisting of tungsten (W), molybdenum (Mo), ruthenium, titanium (Ti) ≪ / RTI >
The method according to claim 5 or 6,
Wherein the cocatalyst for the single reduction reaction is one or more substances selected from the group consisting of HCl, CuCl, AlCl ₃ , HSiCl ₃ , trialkylaluminum, alkylaluminum dihalide, dialkylaluminum halide, and alkylaluminum. Way.
The method according to claim 6,
And the mixing in the third step is performed for 10 seconds to 1 minute.
The method according to claim 6,
Wherein the first solution further comprises a stabilizer.
The method according to claim 6,
Wherein the second solution further comprises a reaction modifier.
The method according to claim 4 or 6,
Wherein said one-fold degradation decomposition reaction is carried out further comprising polybutadiene.

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