WO2011081485A2

WO2011081485A2 - Polyurethane foam-carbon nanotube composite, and preparation method thereof

Info

Publication number: WO2011081485A2
Application number: PCT/KR2010/009585
Authority: WO
Inventors: 김우년; 김지문; 이윤균
Original assignee: 고려대학교 산학협력단
Priority date: 2009-12-31
Filing date: 2010-12-30
Publication date: 2011-07-07
Also published as: WO2011081485A3

Abstract

The present invention relates to a polyurethane foam-carbon nanotube composite. The polyurethane foam-carbon nanotube composite according to the present invention comprises polyurethane and a carbon nanotube, and the content of the carbon nanotube is 0.01-7 parts by weight on the basis of 100 parts by weight of a polyol. The carbon nanotube contained in the polyurethane foam-carbon nanotube composite of the present invention can reduce the size of foamed cells by acting as a nucleating agent of foamed cell formation and can reduce thermal conductivity of the composite. Therefore, the polyurethane foam-carbon nanotube composite of the present invention additionally provides electrical characteristics while maintaining the mechanical characteristics of known polyurethane foams and remarkably improves thermal insulation characteristics.

Description

【Specification】

[Name of invention]

Polyurethane Product-Carbon Nano-Rube Composite and Method for Producing the Same

Technical Field

The present invention relates to a polyurethane article-carbon nanotube composite, and more particularly, to a polyurethane article-carbon nanotube composite having a reduced size of the foam cell and improved thermal insulation performance.

Background Art

Insulation is used in various fields such as agricultural and marine product packaging boxes, building panels, and consumer electronics packaging materials. Polyurethane foam (PUF) insulation provides superior insulation and processability compared to other synthetic resins. In addition, the thermal conductivity is extremely low, it can reduce the thickness of the insulation when molding the product, it can reduce the price and weight of the product. Polyurethane products are soft or hard porous urethane in which isomer isocyanate and poly, which are urethane raw materials, are mixed with a foaming agent, a catalyst, a surfactant, and the like, and the foam is vaporized by the reaction heat generated during reaction. Polyurethane products have high mechanical strength and economical efficiency, and are widely used in buildings, refrigerators, low temperature containers and cryogenic LNG storage tanks.

The composite is a composite material in which two or more materials are physically or chemically bonded to each other, and thus the physical properties of the composite are improved by bonding the materials. Composites can improve various physical properties such as mechanical, thermal or numerical stability and abrasion resistance of existing materials, and new physical properties that do not exist in each material are expressed. It is being magnified. In particular, composites based on polymer resins can significantly improve strength, flame resistance, abrasion resistance, or high temperature stability without damaging conventional physical properties such as layer resistance, toughness and transparency. Research is ongoing.

Conventional studies on polyurethane foam composites include dispersing solid additives such as clay, aerosil, cellulose, etc. in polyols having long molecular chains, and then allowing a portion of the poly with hydroxy functional groups to be intercalated between the solid additive layers. Attempts have been made to react with isocyanates to form polyurethane, thereby inserting polyurethane chains between layers or thereby stripping off solid additive layers. In addition, there has been a previous study in which the addition of glass fiber, asbestos, rock wool, chemical fiber or vegetable fiber to the polyurethane improves the durability of the insulation and at the same time increases the durability. Since carbon nanotubes were discovered in 1991, carbon nanotubes have excellent characteristics in various fields of use due to physical and chemical properties not found in conventional materials. In particular, carbon nanotubes show excellent mechanical and electrical properties compared to conventional conductive materials, and research on this is being actively conducted. In addition, carbon nanotubes are used in various technical fields because of their excellent physical properties, but many researches are being conducted as composite materials in combination with other materials. However, there have been no reports of improving the thermal insulation performance of insulating materials by combining carbon nanotubes with polyurethane.

[Detailed Description of the Invention]

[Technical problem]

Therefore, the first problem to be solved by the present invention is to provide a polyurethane foam-carbon nanotube composites that impart electrical conductivity and at the same time improve the thermal insulation performance.

The second problem to be solved by the present invention is to provide a method for producing the polyurethane foam-carbon nanotube composite.

The third problem to be solved by the present invention is to provide a polyurethane-carbon composite that provides electrical conductivity and at the same time improved heat insulation performance.

The fourth problem to be solved by the present invention is to provide a method for producing the polyurethane-carbon composite.

Technical Solution

The present invention to achieve the first object,

Polyurethane and carbon nanotubes dispersed in a polyol, the carbon nanotubes provide a polyurethane-tansonanotube composite, characterized in that 0.01-7 parts by weight based on 100 weight of the polyol.

According to one embodiment of the present invention, the carbon nanotubes may be any one of single-walled carbon nano-leave, double-walled carbon nanotubes, or a combination thereof, and may be distributed on the foam cell boundary of the polyurethane foam.

According to another embodiment of the present invention, the polyurethane is synthesized by reacting a diisocyanate compound with a polyol, and the diisocyanate compound is a polymeric methylene diphenyl isocyanate or a monomeric methylene diphenyl isocyanate, and poly is poly Ether polyols.

According to another embodiment of the present invention, the polyurethane foam-carbon nanotube composite The sieve may further comprise a flame retardant or cell stabilizer.

The present invention to achieve the second object,

(al) crushing the carbon nanotubes using a ball mill; Or (a2) acid treating the carbon nanotubes, (b) dispersing the crushed carbon nanotubes or acid treated carbon nanotubes in a polyether polyol, and (c) dispersing the carbon nanotubes. A method for producing a polyurethane foam-carbon nanotube composite comprising the step of adding a foaming agent and a diisocyanate compound selected from polymeric polyene to fullermeric methylene diphenyl isocyanate and monomeric methylene diphenyl isocyanate To provide.

According to one embodiment of the present invention, the crushing time of the carbon nanotubes of step (al) may be performed for 0.5-100 hours.

According to another embodiment of the present invention, the carbon nanotubes are acid-treated using hydrogen peroxide in the step (a2), and may be 0.2-0.4 parts by weight relative to 100 parts by weight of hydrogen peroxide.

According to another embodiment of the present invention, step (b) may be dispersed by further adding 0.05-0.15 parts by weight of the silane coupling agent to 100 parts by weight of the polyether polyol.

According to another embodiment of the present invention, the hydroxyl group of the polyether polyol and the isocyanate group of the diisocyanate compound may have a weight ratio of 1-2: 1.

According to another embodiment of the present invention, in step (b), ultrasonic waves may be used to disperse the carbon nanotubes in the polyol.

According to another embodiment of the present invention, the blowing agent added to the polyol in which the carbon nanotubes are dispersed in the step (c) is cyclopentane, isopentane, normal pentane, chlorofluorocarbon, hydrochlorofluorocarbon, hydro Fluorocarbon, water, or a combination thereof.

According to another embodiment of the present invention, the reaction of step (c) may proceed to a temperature of 25-80 ^° C.

The present invention to achieve the third object,

Carbon nanotubes, graphite, nickel-coated carbon fiber, carbon nanotube-graphite composite and carbon nanotube-nickel-coated carbon fiber composite dispersed in a polyurethane and a poly-containing, the carbon material is Polyurethane-carbon composite material is characterized in that 0.01 to 7 parts by weight based on 100 weight of the polyol Ball.

According to one embodiment of the present invention, the carbon nano-rubber may be any one of single-walled carbon nanotubes, double-walled carbon nanotubes, or a combination thereof.

According to another embodiment of the present invention, the polyurethane is synthesized by reacting a diisocyanate compound and a polyol, the diisocyanate compound is a polymeric methylene diphenyl isocyanate or a monomeric methylene diphenyl isocyanate, and the polyol is a polyester It can be poly.

The present invention to achieve the fourth object,

(dl) crushing the carbon nanotubes using a ball mill; Or (d2) acid treating the carbon nanotubes, and (e) carbon crushed or acid treated carbon nanotubes, graphite, nickel-coated carbon fibers, the crushed or acid treated carbon nanotubes and graphite Dispersing any one carbon material selected from the composite and the crushed or acid treated carbon nanotubes and nickel-coated carbon fiber composites, and (f) polymeric methylene diphenyl in the polyether polyol in which the carbon material is dispersed. Provided is a method for preparing a polyurethane-carbon composite comprising reacting one of the diisocyanate compounds selected from isocyanate and monomeric methylene diphenyl isocyanate.

According to one embodiment of the present invention, the crushing time of the carbon nanotubes of the (dl) step may be performed for 0.5-100 hours.

According to another embodiment of the present invention, in the step (d2) using the carbon peroxide acid treatment of hydrogen peroxide, 0.2 to 0.4 parts by weight relative to 100 weight of hydrogen peroxide.

According to another embodiment of the present invention, the hydroxyl group of the polyether polyol and the isocyanate group of the diisocyanate compound may have a weight ratio of 1-2: 1. According to another embodiment of the present invention, in step (e), ultrasonic waves may be used to disperse the carbon nanotubes in the polyol.

Advantageous Effects

The carbon nanotubes included in the polyurethane foam-carbon nanotube composite of the present invention may function as a nucleating agent for foaming cell formation to reduce the foaming cell size and reduce the thermal conductivity of the composite. Therefore, the polyurethane article-carbon nanotube composite of the present invention is conventional While maintaining the mechanical properties of polyurethane products, the thermal insulation properties are significantly improved. [Brief Description of Drawings]

La and lb are electron scanning micrographs showing the position of the carbon nanotubes in the polyurethane foam-carbon nano-leube complex according to an embodiment of the present invention.

Figure 2 is a graph showing the electrical conductivity of the polyurethane foam-carbon nanotube composites prepared according to Examples 2 to 4 and Comparative Examples 1 and 2.

Figure 3 is a graph showing the thermal conductivity of the polyurethane foam-carbon nanotube composite and polyurethane foam prepared according to Examples 2 to 4 and Comparative Examples 1 and 2.

4 to 5 are electron scanning micrographs of the polyurethane product-carbon sonanotube composites prepared according to Comparative Example 1 and Example 3, respectively.

Figure 6 is a graph showing the flexural strength of the polyurethane foam-carbon nano-leube composite prepared according to Examples 1, 3, 4 and Comparative Example 1.

FIG. 7 is a graph showing the electrical conductivity of polyurethane product-carbon nanotube composites prepared according to Examples 3, 5, 6, 7, 7, 8, and Comparative Example 1. FIG.

8 is a graph showing the thermal conductivity of the polyurethane product-carbon nanotube composite prepared according to Example 3, Example 5, Example 6, Example 7, Example 8, Example 9 and Comparative Example 1 .

9 is a graph showing the thermal conductivity of the polyurethane product-carbon nanotube composites prepared according to Examples 17, 18, 19, 20, 21, 22.

10 is a graph showing the thermal conductivity of the polyurethane product-carbon nanotube composite prepared according to Examples 23, 24, 25, 26, 27, 28.

[Form for implementation of invention]

Hereinafter, the present invention will be described in detail.

The present invention relates to a polyurethane article-carbon nanotube composite, wherein the polyurethane article-carbon nanotube composite according to the present invention comprises carbon or norub dispersed in polyurethane and polyol, and the content ratio of the carbon nanotubes The poly is characterized in that 0.01-7 parts by weight with respect to 100.

The thermal insulation performance of the polyurethane foam-carbon nano-leube composite according to the present invention is carbon nano It depends greatly on the content of the tube. In the manufacturing process of the composite, carbon nanotubes are dispersed in the polyol, and carbon nanotubes and polyurene are very weakly bound by the intermolecular attraction, and when the amount of added carbon nanotubes is too large, the tendency to coagulate each other becomes stronger. It is not nano-ized and the thermal insulation performance is reduced.

Conventional techniques in which carbon nanotubes are added to polyurethane use carbon nanotubes to increase the mechanical strength of the insulation, resulting in a decrease in the thermal insulation performance of the carbon nanotubes exceeding 0.1 wt% based on the total weight. However, in the present invention, by controlling the content of the carbon nano-rubber added to the polyurethane to 0.001 to 05% by weight based on the total weight to induce the carbon nanotubes to act as a nucleating agent during the formation of the foaming cell to improve the thermal insulation Rather, it can be improved.

Polyurethane article-carbon nanotube composite according to a preferred embodiment of the present invention is characterized in that the carbon nano-rubber is distributed on the foam cell boundary of the polyurethane article. La to lb are electron scanning micrographs showing the position of the carbon nanotubes in the polyurethane nano carbon nano-bubble composite according to an embodiment of the present invention. Referring to FIG. La, a triangular foam cell boundary is shown at the point where three foam cells meet, and carbon nanotubes are located at the site. Figure lb is an enlarged picture of the foam cell boundary, it can be seen more clearly that the carbon nanotubes are located on the foam cell boundary.

A foaming agent is used to form a foaming cell in the polyurethane, and carbon nanotubes dispersed in a polyol serve as a nucleating agent for foaming cell formation. Foam cells that start to grow on the surface of the tanno-nanotubes grow to areas where carbon nanotubes do not exist, and as a result carbon nanotubes are located at the boundary of the foam cell. In this case, the content of carbon nanotubes also plays an important role. If the content of carbon nanotubes is excessively high, the carbon nanotubes may be in contact with neighboring foam cells, and the foam cells may be destroyed. The gas may leak and deteriorate the thermal insulation performance.

According to a preferred embodiment of the present invention, the blowing agent added to the polyol in which the carbon nanotubes are dispersed is cyclopentane, isopentane, normal pentane, chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, water or their It may be any one of the combinations.

According to one embodiment of the present invention, the carbon nanotubes may be single-walled carbon nanotubes, double-walled carbon nanotubes, or a mixture thereof, and may be treated with hydroxide or treated in a milling step using a ball mill. In one embodiment of the present invention, the polyurethane is synthesized by reacting a diisocyanate compound with a polyol. The diisocyanate compound may be a polymeric methylene diphenyl isocyanate or a monomeric methylene diphenyl isocyanate, and the polyol may be phthalic anhydride or It may be a polyether polyol prepared by polymerizing adipic acid with ethylene oxide, propylene oxide or a mixture thereof.

According to one embodiment of the present invention, the polyurethane foam-carbon nano-leube composite may further include a flame retardant or cell stabilizer, and it is also possible to use any flame retardant or cell stabilizer known in the art.

In addition, an embodiment of the present invention for producing a polyurethane foam-carbon nano-leube composite according to the present invention is as follows.

First, the carbon nano-leave is pulverized using a ball mill. Subsequently, carbon or a norrebe is mixed with a polyol. Subsequently, the polyol mixed with the carbon nanotubes is stirred, and the carbon nanotubes are dispersed using an ultrasonic pot. Finally, the mixture obtained above and diisocyanate are mixed and stirred to react.

In the step of pulverizing the carbon nanotubes by using a ball mill, other methods for pulverizing carbon nanobubbles besides the ball mill may be used, and any method known in the art may be used. In addition, before the step of pulverizing the carbon nanotubes using a ball mill, the carbon nanotubes may be acid treated or hydroxide ionized to improve the dispersion property in the polyol.

Stirring the polyol mixed with carbon nano-lube and dispersing the carbon nano-lube using ultrasonic waves after the initial stirring at 100 to 3000rpm for 10 to 60 minutes, further stirring for 1 to 24 hours at 1000 to 5000rpm Can be. The initial stirring is to disperse the carbon nanotubes well, and when the mixture is stirred at a high speed from the beginning, the carbon nanotubes are agglomerated with each other so that the carbon nanotubes are not dispersed well in the polyol compound so that the desired reaction does not occur sufficiently. . In addition, if the initial stirring time is less than 10 minutes is insufficient to disperse the carbon nanotubes, if more than 60 minutes there is a fear that the process efficiency is lowered. After the initial stirring, if the mixture is stirred at lOOOOrpm or less, the polyol compound does not enter the reaction between the carbon nanotubes, so it is difficult to participate in reaction. Therefore, after the initial stirring, stirring at a high speed of lOOOOrpm or more is preferable. Are aggregated and do not disperse well in the polyol compound. In addition, the intensity of the ultrasonic wave is preferably carried out at 300 kHz or less, and the ultrasonic treatment for 5 to 60 minutes at a temperature of 5 to 60 ^° C. This is more preferable.

The diisocyanate compound used in the step of reacting the polyol and the diisocyanate in which the carbon nanotubes are dispersed may be the diisocyanate compound may be polymeric methylene diphenyl isocyanate or monomeric methylene diphenyl isocyanate.

It is preferable that the reaction is carried out at a silver content of 25 to 80 ^° C. If the reaction is carried out at less than 25 ^° C, reaction of isocyanate functional groups and polyol functional groups hardly occurs, and thus the desired polyurethane bonds are not formed. to be. Reaction temperature

If it exceeds 80 ^° C, organic matter inserted inside may be decomposed, and the distance between layers of carbon nanotubes may be reduced. If the reaction property is too high, water and reaction contained in the air will rapidly occur. Viscosity of the diisocyanate compound is excessively increased, there is a problem that a large amount of C0 ₂ bubbles are generated through the chemical reaction with moisture to take a long time to remove and stabilize it.

In the step of reacting the poly-dispersed polyisocyanate with the di-isocyanate, it is preferred that the hydroxyl group and the isocyanate group of the diisocyanate compound are present in a ratio of 1: 1 to 2: 1. This is because when the ratio is less than 1: 1, the polyol component is present in excess and the polyurethane formation reaction is not completed. When the ratio exceeds 2: 1, the rigid polyurethane produced is excessively high and easily broken. .

The content of the carbon nanotubes in the step of reacting the poly-dispersed polyisocyanate with the carbon nanotubes is preferably 0.01 to 0.1 parts by weight based on the polyol. The ratio is a range for the carbon nanotubes to act as a nucleating agent for the growth of foam cells, as described above, and is determined in consideration of the content ratio of poly and diisocyanate.

In the step of reacting the carbon nanotube-dispersed polyol and diisocyanate, it is preferable to further add a surfactant or a catalyst to the carbon nanotube-dispersed polyol. As a catalyst, pentamethyl ethylene triamine, Dimethykyclohexyl amine, tris (3—dimethylamin) propyl hexahydroamine, triethylene amine or a combination thereof may be used, As the surfactant, all known materials in this field can be used.

The blowing agent used in the reaction of polyol and diisocyanate in which carbon nano dispersion is dispersed has low thermal conductivity and is stable in the atmosphere of cyclopentane, isopentane, normal pentane and chloroflu Chlorofluorocarbons, hydrochlorocarm, hydrofluorocarbons, water or combinations thereof can be used. The amount of the blowing agent can be adjusted according to the density of the product to be prepared, and the amount of blowing agent to be added increases as the product of low density is obtained.

In the present invention, foamed polyurethane product-carbon nanotube nano composite new material can be produced without using ultrasonic waves. It is preferable to perform ultrasonic treatment in parallel. The reason for this is that when foaming reaction using a blowing agent, carbon nanotubes that are not dispersed well may be agglomerated, and these properties can be prevented through sonication to improve physical properties. Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are intended to illustrate the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

Example 1

(1) Crushing and Shredding of Carbon Nano-Rubes

In order to disperse well on the polyol, the carbon nanotubes were ground into smaller particles using a ball mill. At this time, milling or crushing the carbon nanotubes using a ball mill was performed for 2 hours.

(2) Preparation of Polyols Dispersed with Carbon Nanotubes

The carbon nanotubes were added at 0. 2 parts by weight based on the weight of the polyether poly (polyether polyol, purchased from KPC Co.). In order to allow the compound to be smoothly inserted into the carbon nanotubes to be dispersed and reacted, a reaction mixture was stirred for 10 minutes at a low speed of 100 rpm and then a high speed of 5000 rpm, using a mechanical stirrer. It was stirred for 20 seconds.

(3) Preparation of Polyurethane Product-Carbon Nano-Rube Composite

Carbon nanotube-containing polyols prepared according to Examples 1-2 and polymeric methylene diphenyl isocyanates (Lupranat M20, purchased from BASF Co.), catalysts (B8462, Goldschmidt) What was purchased from Co.), surfactants and blowing agents (a mixture of water and cyclopentane), the ratio of the polymer polyol compound containing the phase flow was added in excess of 5 wt ¾ of the stoichiometric ratio. Stirred at 5000 rpm for 20 seconds using a stirrer. [Table 1] to summarize the half water.

Table 1

Example 2

A polyurethane foam-carbon nanotube composite was prepared in the same manner as in Example 1, except that the amount of carbon nanotubes added was 0.05 parts by weight based on the weight of the polyol. Example 3

A polyurethane product-carbon nanotube composite was prepared in the same manner as in Example 1, except that the amount of carbon nanotubes added was 0.1 parts by weight based on the weight of the polyol compound. Example 4

A polyurethane product-carbon nanotube composite was prepared in the same manner as in Example 1, except that the amount of carbon nanotubes added was 0.2 parts by weight based on the weight of the polyol compound. Example 5 ^''

A polyurethane product-carbon nanotube composite was prepared in the same manner as in Example 3 except that the carbon nanotubes were ground or crushed for 1 hour. Example 6

Except that carbon nanotubes were ground or crushed for 3 hours In the same manner as in Example 3, a polyurethane product-carbon nanoleube composite was prepared. Example 7

Polyurethane foam-carbon nanotube composites were prepared in the same manner as in Example 3 except that the carbon nanotubes were ground or crushed for 4 hours. Example 8

A polyurethane product-carbon nanotube composite was prepared in the same manner as in Example 3 except that the carbon nanotubes were ground or crushed for 6 hours. Example 9

Except that the carbon nanotubes were pulverized or crushed for 12 hours, a polyurethane product-carbon nano-leube composite was prepared in the same manner as in Example 3. Example 10

(1) Acid Treatment of Carbon Nano-Rubes

The carbon nanotubes were acid treated with hydrogen peroxide to ensure good dispersion on the polyols. At this time, the hydrogen peroxide was added by adding 1.5 parts by weight of carbon nano-lube to 50 (l. During the acid treatment, it proceeded for 90 minutes using a bath-type ultrasonic device.

(2) Preparation of Acid-Treated Carbon Nano-Rubber-Dispersed Polyols

0.01 parts by weight of the carbon nanolybe was added based on the weight of the polyether polyol (polyether polyol, purchased from KPC Co.). The poly was stirred for 5 minutes at a high speed of 3000 rpm at a low speed of 100 rpm using a mechanical stirrer to enable the compound to be smoothly inserted and dispersed between the carbon nano-rubbers.

(3) Preparation of polyurethane product-carbon nanotube composite

Carbon nanotube-containing polyols and polymeric methylene diphenyl isocyanates (purchased from Lupranat M20, BASF Co.), catalysts (B8462, purchased from Goldschmidt's Co.), surfactants and blowing agents prepared according to Example 10-2. A mixture of cyclopentane) The reaction was added at room temperature to prepare a polyurethane product-carbon nanotube composite. The ratio of the polymer polyol compound including the carbon nanotubes was added in excess of 5% by weight relative to the stoichiometric ratio, and stirred for 20 seconds at 3000 rpm using a mechanical stirring device. Example 11

A pulley urethane foam-carbon nanotube composite was prepared in the same manner as in Example 10, except that the amount of carbon nanoleub added was 0.05 parts by weight based on the weight of the polyol. Example 12

A polyurethane product-carbon nanotube composite was prepared in the same manner as in Example 10, except that carbon nanotubes were added in an amount of 0.3 parts by weight based on the weight of poly. Example 13

(1) Acid treatment of carbon nanotubes

The carbon nanotubes were acid treated with hydrogen peroxide to ensure good dispersion of the poly phases. At this time, 1.5 parts by weight of carbon nanotubes were added to 500 ml of hydrogen peroxide. During the acid treatment, a bath-type ultrasonic device was used for 90 minutes.

(2) Preparation of Polyol Added with Silane Coupling Agent and Carbon Nanotube

0.01 parts by weight of the carbon nanotubes were added based on the weight of the polyether polyol (polyether polyol, purchased from KPC Co.). In order to allow the polyol compound to be smoothly inserted and dispersed between the carbon nanotubes, 0.1 parts by weight of a silane coupling agent was added and a high speed of 3000 rpm at a low speed of 100 rpm using a mechanical stirrer. It was stirred for 5 minutes.

(3) Preparation of Polyurethane Foam-Carbon Nano-Rube Composite

Carbon nanotube containing poly and polymeric methylene diphenyl isocyanates (purchased from Lupranat M20, BASF Co.) prepared according to Examples 13-2, catalyst (B8462, Purchased from Goldschmidt's Co.), a surfactant and a blowing agent (a mixture of water and cyclopentane) were added at room temperature to prepare a polyurethane product-carbon nanotube composite. The ratio of the polymer type poly compound containing carbon nanotubes is 5% by weight than the stoichiometric ratio? ¾ was added in excess, and the reaction was stirred at 3000 rpm for 20 seconds using a mechanical stirring device. Example 14

Polyurethane article-carbon nanotube composites were prepared in the same manner as in Example 13, except that the amount of carbon nanoleuze was added to 0.05 part by weight based on the weight of the polyol. Example 15

Polyurethane article-carbon nano-leube composite was prepared in the same manner as in Example 13, except that the amount of carbon nanotubes added was 0.3 parts by weight based on the weight of the polyol.

Example 16

A polyurethane foam-carbon nanotube composite was prepared in the same manner as in Example 13, except that the amount of carbon nanotubes added was 0.5 parts by weight based on the weight of the polyol. Example 17

(1) Preparation of Polyol Dispersed Graphite

1.0 parts by weight of graphite was added based on the weight of polyether polyol (polyether polyol, purchased from KPC Co.). The polyol compound was stirred for 5 minutes at a high speed of 3000 rpm at a low speed of 100 rpm using a mechanical stirrer so that the polyol compound could be smoothly inserted into the graphite to be dispersed and reacted.

(2) Preparation of polyurethane-graphite composite

Graphite-containing polyols and polymeric methylene diphenyl isocyanates (purchased from Lupranat M20, BASF Co.), catalysts (B8462, purchased from Goldschraidt's Co.) and surfactants prepared according to Example 17-1. I don't add a blowing agent Polyurethane-graphite composites were prepared. The ratio of the polymer-containing polyol compound including graphite was added in an amount of 5% by weight over the stoichiometric ratio, and stirred at 5000 rpm for 20 seconds using a mechanical stirring device for reaction. Example 18

A polyurethane-graphite composite was prepared in the same manner as in Example 17, except that the addition amount of graphite was 3.0 parts by weight based on the weight of the polyol. Example 19

A polyurethane-graphite composite was prepared in the same manner as in Example 17, except that the amount of graphite added was 7.0 parts by weight based on the weight of the polyol. Example 20

(1) Preparation of Polyols Dispersed with Nickel Coated Carbon Fiber

1.0 parts by weight of the nickel-coated carbon fiber was added based on the weight of the polyether polyol (polyether polyol, purchased from KPC Co.). The polyol compound was stirred for 5 minutes at a high speed of 3000 rpm at a low speed of 100 rpm using a mechanical stirrer in order to allow the polyol compound to be smoothly inserted and dispersed between the nickel-coated carbon fibers.

(2) Preparation of polyurethane-nickel coated carbon fiber composite

Nickel-coated carbon fiber-containing polyols prepared according to Example 20-1 and polymeric methylene diphenyl isocyanates (Lupranat M20, purchased from BASF Co.), catalysts (B8462, purchased from Goldschmidt's Co.), and surfactants Afterwards, the foaming agent was reacted at room temperature without adding a polyurethane-nickel coated carbon fiber composite. The ratio of the polymer polyol compound containing the nickel-coated carbon fiber was added in excess of 5% by weight of the stoichiometric ratio, and stirred for 20 seconds at 5000 rpm using a mechanical stirring device for reaction. Example 21 A polyurethane-carbon nanotube composite was prepared in the same manner as in Example 20, except that the amount of the nickel-coated carbon fiber was added to 3.0 parts by weight based on the weight of the polyol. Example 22

A polyurethane-carbon nanotube composite f was prepared in the same manner as in Example 20, except that the amount of the nickel-coated carbon fiber was 7.0 parts by weight based on the weight of the poly. Example 23

(1) Preparation of Polyols Dispersed with Carbon Nano-Rubber and Graphite

3.0 parts by weight of carbon nanotubes prepared in Example 5 were added based on the weight of polyether polyol (polyether polyol, purchased from KPC Co.), and graphite was added in 1.0 parts by weight. In order to allow the polyol compound to be smoothly inserted and dispersed between carbon nano-leubu and graphite, the polyol compound was stirred for 5 minutes at a high speed of 3000 rpm at a low speed of 100 rpm using a mechanical stirrer.

(2) Preparation of polyurethane-carbon nanotube-graphite composite

Carbon nanotubes prepared in Example 23-1, graphite-containing polyols and polymeric methylene diphenyl isocyanates (Lupranat M20, purchased from BASF Co.), catalysts (B8462, purchased from Goldschmidt's Co.), surfactants Thereafter, the foaming agent was reacted at room temperature without adding a polyurethane-carbon nanotube-graphite composite. The ratio of the polymer polyol compound containing carbon nanonob and graphite was added in an amount of 5% by weight over the stoichiometric ratio, and the reaction was stirred for 20 seconds at 5000 rpm using a mechanical stirring device. Example 24

Polyurethane-carbon nano-leube-graphite composite was prepared in the same manner as in Example 18, except that the amount of carbon nanoleube was added by 3.0 parts by weight and the amount of graphite was added by 3.0 parts by weight based on the weight of the polyol. Example 25

The ^'addition amount of the carbon nanotubes, based on the weight of polrieul 7.0 parts by weight of polyurethane in the same manner as in Example 23 except that the graphite addition amount of the part 7.0 parts by weight, was prepared the graphite composite carbon nano ryubeu. Example 26

(1) Preparation of polyols in which carbon nanotubes and nickel-coated carbon fibers are dispersed

3.0 parts by weight of carbon nanotubes prepared in Example 5 were added based on the weight of polyether polyol (polyether polyol, purchased from KPC Co.), and nickel coated carbon fibers were added in an amount of 1.0 parts by weight. In order to allow the polyol compound to be smoothly inserted and dispersed between the carbon nanotubes and the nickel-coated carbon fiber, a mechanical stirrer was used for 5 minutes at a high speed of 3000 rpm at a low speed of 100 rpm. It stirred.

(2) Preparation of polyurethane-carbon nanotube-graphite composite

Nickel-coated carbon fiber-containing polyols and polymeric methylene diphenyl isocyanates (purchased from Lupranat M20, BASF Co.), catalysts (B8462, purchased from Goldschmidt's Co.), surfactants and blowing agents prepared according to Example 26-1. A mixture of water and cyclopentane) was added and reacted at room temperature to prepare a polyurethane-carbon nanotube-nickel coated carbon fiber composite. The ratio of the polymer polyol compound including the carbon nanotubes and the nickel-coated carbon fiber was added in an excess of 5% by weight of the stoichiometric ratio, and stirred at 5000 rpm for 20 seconds using a mechanical stirrer. Example 27

Polyurethane-carbon nanotubes-nickel-coated carbon fiber composites in the same manner as in Example 26, except that 3.0 parts by weight of carbon nanotubes and 3.0 parts by weight of nickel-coated carbon fibers were added based on the weight of the polyol. Was prepared. Example 28

Polyurethane-carbon nanotubes-nickel-coated carbon fiber composites in the same manner as in Example 26, except that 7.0 parts by weight of carbon nanotubes and 7.0 parts by weight of nickel-coated carbon fibers were added based on the weight of poly; Was prepared. Example 29

(1) Acid treatment of carbon nanotubes

The carbon nanotubes were acid treated with hydrogen peroxide to ensure good dispersion on the polyols. At this time, 1.5 parts by weight of carbon nanotubes were added to 500 ml of hydrogen peroxide. During the acid treatment, a bath-type ultrasonic device was used for 90 minutes.

(2) Preparation of Polyols Dispersed with Acid-treated Carbon Nanotubes

0.01 parts by weight of the carbon nanotubes were added based on the weight of the polyether polyol (polyether polyol, purchased from KPC Co.). The poly was stirred for 5 minutes at a high speed of 3000 rpm at a low speed of 100 rpm using a mechanical stirrer to enable the compound to be smoothly inserted and dispersed between the carbon nanotubes.

(3) Preparation of polyurethane-carbon nanotube composite

Carbon nanotube-containing poly and polymethylene diphenyl isocyanate (purchased from Lupranat M20, BASF Co.), catalyst (B8462, purchased from Goldschmidt's Co.) prepared according to Example 29-2, and the surfactant ， A polyurethane-carbon nanotube composite was prepared by reacting in phase silver without adding a blowing agent. The ratio of the polymer polyol compound including the carbon nanotubes was added in excess of 5% by weight of the stoichiometry bar, and the reaction was stirred at 3000 rpm for 20 seconds using a mechanical stirring device. Example 30

A polyurethane-tan ^' sonanoleuven composite was prepared in the same manner as in Example 29, except that 7.0 parts by weight of carbon nanotubes were used based on the weight of the polyol. Comparative Example 1

A polyurethane product was manufactured in the same manner as in Example 1, except that carbon nanotubes were not added to the polyol. Comparative Example 2

Except that the amount of carbon nanotubes added to 0.5 parts by weight based on the weight of the polyol was prepared in the same manner as in Example 1. Evaluation Example 1 Observation of Electrical Conductivity

In order to observe the electrical conductivity, each of the polyurethane product-carbon nanotube composite and the polyurethane foam specimens according to Examples 1 to 9 and Comparative Examples 1 to 2 were cut out to a width of 15 mm x 15 mm x 5 mm, The electrical conductivity of the specimen was measured.

Figure 2 is a result of the electrical conductivity of the polyurethane foam-carbon nanotube composite prepared according to Examples 2 to 4 and Comparative Examples 1 and 2.

Table 2 summarizes the results of measuring the electrical conductivity (S / cm) for the polyurethane foam ᅳ carbon nano-lube composite and polyurethane foam prepared according to the Examples and Comparative Examples.

Table 2

Referring to FIGS. 2, 7 and [Table 2], the polyurethane foam-carbon nanotube composites according to Examples 1 to 9 are higher in electrical conductivity than Comparative Example 1 without adding carbon nanotubes. It can be seen that having. This is because when the polyurethane foam-carbon nanotube composite is formed due to the addition of the carbon nanotubes, the pulverized carbon nanotube particles serve to create a path for electricity to flow in the polyurethane product. It is believed that the electrical conductivity is increased accordingly. Evaluation Example 2 Measurement of Density and Thermal Conductivity

Density and thermal conductivity were measured for the polyurethane article-carbon nanotube composite and the polyurethane article prepared according to Examples and Comparative Examples.

[Table 3] shows the density and thermal conductivity (kcal / mh ^° C) of polyurethane foamed carbon nanotubes or polyurethane foam prepared according to Examples 1 to 9 and Comparative Examples 1 to 2 .

Table 3

Referring to FIGS. 3 to 5 and Table 3 and FIG. 8, it can be seen that the polyurethane product-carbon nanotube composite prepared according to the examples has a lower thermal conductivity than the comparative examples. In addition, it can be seen that the polyurethane product-carbon nanotube composite according to the embodiment is generally smaller in size than the comparative example.

Claims

[Range of request]

[Claim 1]

Polyurethane foam carbon nanotube composite comprising a carbon nanotube dispersed in a polyurethane and a polyol, the carbon nanotube is 0.01 to 7 parts by weight based on 100 weight of the polyol.

[Claim 2]

The method of claim 1,

The carbon nanotube is any one of single-walled carbon nanotubes, double-walled carbon nanotubes or a mixture thereof, and polyurethane-carbon nanotube composites, characterized in that distributed on the foam cell boundary of the polyurethane product.

[Claim 3]

The method of claim 1, wherein the polyurethane is synthesized by reacting a diisocyanate compound with a poly, and the diisocyanate compound is a polymeric methylene diphenyl isocyanate or a monomeric methylene diphenyl isocyanate, and the poly is a polyether polyol. Polyurethane product-carbon nano-leuver composite, characterized in that

[Claim 4]

The method of claim 1,

Polyurethane article-carbon nanotube composite further comprises a flame retardant or cell stabilizer.

[Claim 5]

(al) crushing the carbon nanoleubes using a ball mill; Or (a2) acid treating the carbon nanobub;

(b) dispersing the crushed carbon nanotubes or acid treated carbon nanotubes in a polyether polyol; And

(c) adding and reacting any one of the diisocyanate compounds selected from polymeric methylene diphenyl isocyanate and monomeric methylene diphenyl isocyanate and a blowing agent to the polyether polyol in which the carbon nanotubes are dispersed. Method for producing urethane product-carbon nanotube composite.

[Claim 6]

The method of claim 5,

Method for producing a polyurethane foam-carbon nanotube composite, characterized in that the crushing time of the carbon nanotubes of the step (al) proceeds for 0.5-100 hours.

[Claim 7]

The method of claim 5,

The method of producing a polyurethane foam-carbon nanotube composite, characterized in that the acid treatment of carbon nano-lube using hydrogen peroxide in the step (a2), 0.2 to 0.4 parts by weight relative to 100 weight of hydrogen peroxide.

[Claim 8]

The method of claim 5,

The step (b) is a polyurethane product-carbon nanotube composite, characterized in that the dispersion by adding 0.05 to 0.15 parts by weight of the silane coupling agent with respect to 100 weight of the polyether polyol.

[Claim 9]

The method of claim 5,

A hydroxy group of the polyether polyol and an isocyanate group of a diisocyanate compound are present in a weight ratio of 1-2: 1.

[Claim 10]

The method of claim 5,

Polyurethane polyurethane article-a method for producing a carbon nano-lung complex, characterized in that the ultrasonic wave is used to disperse the carbon nano-lube in poly in the step (b).

[Claim 111]

The method of claim 5,

The blowing agent added to the polyol in which the carbon nanotubes are dispersed in step (c) is cyclopentane, isopentane, normal pentane, chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, water or a mixture thereof. Polyurethane article, characterized in that any one of the method of producing a carbon nanotube composite.

[Claim 12]

The method of claim 5,

Addition (c) step reaction is a method for producing a polyurethane product-carbon nanotube composite, characterized in that proceeding to a temperature of 25-80 ^° C.

[Claim 13]

Carbon nanolyuves, graphite, nickel-coated carbon dispersed in polyurethanes and polyols Samyu, carbon nanotubes-graphite composites and carbon nanotubes-nickel-coated carbon fiber composites comprising any one carbon material selected from, wherein the carbon material is polyurethane polyurethane, characterized in that 0.01-7 parts by weight based on 100 weights of polyol- Carbon material composite.

[Claim 14]

The method of claim 13,

The carbon nanotube is a polyurethane-carbon composite, characterized in that any one of single-walled carbon nanotubes, double-walled carbon nanotubes or a mixture thereof.

[Claim 15]

The method of claim 13,

The polyurethane is synthesized by reacting a diisocyanate compound with a polyol, wherein the diisocyanate compound is a polymeric methylene diphenyl isocyanate or a monomeric methylene diphenyl isocyanate, and the polyol is a polyurethane poly-carbon. Material composite.

[Claim 16]

(dl) crushing the carbon nanoleubes using a ball mill; Or (d2) acid treating the carbon nanotubes;

(e) the pulverized or acid treated carbon nanotubes, graphite, nickel coated carbon fibers, the crushed or acid treated carbon nanotubes and graphite composites, and the crushed or acid treated carbon nanotubes; Dispersing any one carbon material selected from nickel-coated carbon fiber composites; And

(f) reacting any one of the diisocyanate compounds selected from polymeric methylene diphenyl isocyanate and monomeric methylene diphenyl isocyanate on the polyether polyol in which the carbon material is dispersed; Manufacturing method.

_..

[Claim 17]

The method of claim 16,

Crushing time of the carbon nanotubes of the step (dl) is a method for producing a polyurethane-carbon composite, characterized in that for 0.5-100 hours

[Claim 18]

The method of claim 16,

Polyurethane-carbon element, characterized in that the acid treatment of carbon nano-lube using hydrogen peroxide in the step (d2), 0.2 to 0.4 parts by weight based on 100 weight of hydrogen peroxide Method for preparing ash composite.

[Claim 19]

The method of claim 16,

Method for producing a polyurethane-carbon composite according to claim 1, wherein the hydroxyl group of the polyether polyol and the isocyanate group of the diisocyanate compound are present in a weight ratio of 1-2: 1.

[Claim 20]

The method of claim 16,

Method of manufacturing a polyurethane polyurethane-carbon composites, characterized in that using the ultrasonic wave to disperse the carbon nanotubes in the polyol in the step (e). [Claim 21]

The method of claim 16,

The reaction of step (c) is a method of producing a polyurethane-carbon composite, characterized in that proceeding to a temperature of 25-80.