KR20110107675A - Polyurethan foam composition using nano compound material and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a cold-curable polyurethane foam composition using a nano composite material and a method for manufacturing the same, by adding and dispersing carbon nanotubes or carbon nanotubes and carbon nanoplates in a polyurethane stock solution to form a polyurethane foam by foaming When using a polyurethane foam as a heat insulating material, even if the thickness is reduced, durability, heat insulation and thermal stability is improved technology that can show excellent heat insulation efficiency.

Description

Polyurethane foam composition using nano compound material and manufacturing method

The present invention relates to a polyurethane foam composition, and more particularly, to a manufacturing method capable of increasing the thermal insulation and thermal stability of a rigid polyurethane foam used as a cold insulation material and a polyurethane foam composition produced thereby.

Polyurethane foams are usually obtained by reacting polyols, isocyanates, water, reaction catalysts, crosslinking agents and other additives with foaming agents to foam.

These polyurethane foams have excellent heat insulation characteristics due to the fine and independently formed honeycomb cell structure and low thermal conductivity gas present inside the cell, and are light and strong against impacts, resulting in construction, water tanks, district heating, pipelines, etc. It is widely used as a heat insulator and is also used as a product packaging material.

Polyurethane foam is divided into soft, semi-rigid and hard according to its rigidity.Double soft foam is used for quilts, mattresses and automobile seats due to its flexibility, and rigid foam is used as a heat insulating material due to its rigidity, excellent thermal insulation and low temperature properties. .

In addition to rigid polyurethane foams, plywood, fiberglass, and styrofoam are also used as insulation materials, but the insulation material that can be used in a wide range of temperatures from 150 ° C to cryogenic areas such as fuel tanks of satellite launch rockets is made of rigid polyurethane foams. Unique. In addition, as shown in FIG. 1, the rigid urethane foam has the lowest thermal conductivity compared to other thermal insulators even at a thin thickness, and also has excellent waterproofing effect, excellent adhesion to a face plate, and magnetic buoyancy. It is easy to occupy more than 80% of the insulation market.

In addition, polyurethane foam is very excellent in cold storage effect, it is used as a cold storage material in refrigerators and freezers, such as refrigerators and freezers. In such a refrigeration / freezing facility, polyurethane must be used for a certain thickness or more in order to exhibit sufficient cold storage performance, but there is also a need to reduce the size of the refrigeration / freezing facility by reducing the thickness.

The present invention has been made to solve the problems of the prior art as described above, by adding and dispersing the nano-composite material in the polyurethane stock solution and foamed by further insulating cold insulation using a nano-composite material further increased thermal insulation and thermal stability It is an object to provide a foam composition and a method for producing the same.

In addition, by providing polyurethane foam with increased insulation and thermal stability, it is possible to ensure cold performance even if the thickness is reduced, thereby maximizing the internal volume when applied to various refrigeration / freezing equipment, Another object of the present invention is to provide a cold-curable polyurethane foam composition and a method of manufacturing the same using a nano-composite material capable of securing economic efficiency through cost reduction.

Method for producing a cold-resistant polyurethane foam composition using a nano-composite material according to the present invention for achieving the above object, preparing a polyurethane stock solution; Producing a composite solution by adding and dispersing a nanocomposite material to the polyurethane stock solution; And foaming the composite solution, wherein the nanocomposite material includes carbon nanotubes.

Here, the nanocomposite material may further include carbon nanoplates.

The polyurethane stock solution is produced by reacting water, a catalyst, and an additive with a polyol component and an isocyanate component.

In addition, the nanocomposite material is added to the polyurethane stock solution in an amount of 0.1 wt% to 10 wt% based on 100 wt% of the total composite solution.

On the other hand, the present invention includes a cold-curable polyurethane foam composition using a nano composite material produced by the above production method.

Since the cold-curable polyurethane foam composition using the nanocomposite material according to the present invention includes a nanocomposite material composed of carbon nanotubes or carbon nanotubes and carbon nanoplates, the following effects can be expected when used as a heat insulating material.

First, in the case of including carbon nanotubes, the carbon nanotubes can increase the thermal insulation performance by maximizing the porosity of the polyurethane foam due to the large voids that can absorb air (air), and also well dispersed carbon nanotubes The penetration of heat due to the formation of the network of is dispersed by the carbon nanotubes, thereby minimizing the penetration of heat. In addition, the strength of the polyurethane foam is also increased by the characteristics of the carbon nanotubes. Therefore, the thickness of the insulation may be reduced.

Second, in the case of including both carbon nanotubes and carbon nanoplates, in addition to the effects of the carbon nanotubes, due to the plate-like structural properties of the carbon nanoplates, the heat reflectivity is increased to further improve thermal insulation performance. In addition, thermal stability may be improved than that of a conventional polyurethane foam by lowering heat transfer due to the characteristics of carbon nanoplates having high heat reflectance and relatively large heat capacity of carbon nanoplates when high-temperature radiant heat penetrates.

In addition, when the cold insulating polyurethane foam composition using the nanocomposite material according to the present invention is used as a heat insulator of a refrigeration / refrigeration equipment, an excellent heat insulation and thermal stability effect can be obtained even if the thickness is reduced, thereby reducing the size of the device. Therefore, it is possible to maximize the internal volume of the refrigerating and freezing equipment, and to secure economic feasibility by reducing the weight and cost of the equipment. In addition, the use of polyurethane can be reduced to reduce the emission of environmental pollutants.

1 is a view for comparing the thermal conductivity of materials used as a heat insulating material.
Figure 2 is a view for explaining a method for producing a cold-curable polyurethane foam composition using a nano composite material according to a first embodiment of the present invention.
3 and 4 are views for explaining a cold-resistant polyurethane foam composition using a nano composite material according to a first embodiment of the present invention.
5 is a view for explaining a method of manufacturing a cold-curable polyurethane foam composition using a nano composite material according to a second embodiment of the present invention.
6 and 7 are views for explaining a cold-resistant polyurethane foam composition using a nano composite material according to a second embodiment of the present invention.

Hereinafter, a method for preparing a cold-curable polyurethane foam composition using a nanocomposite material according to a preferred embodiment of the present invention and a polyurethane foam composition prepared thereby will be described.

2 is a view for explaining a method of manufacturing a cold-curable polyurethane foam composition using a nano composite material according to a first embodiment of the present invention, Figures 3 and 4 is a poly produced by the manufacturing method shown in FIG. It is a figure for demonstrating a urethane foam composition.

First, to prepare a cold-resistant polyurethane foam composition (hereinafter referred to as 'polyurethane foam') using the nano-composite material provided by the present invention, a polyol component and an isocyanate component is included. Prepare a polyurethane stock solution <S110>.

It is preferable to use polyester polyol as the polyol component, for example, those prepared by reacting a carboxylic acid and / or a derivative thereof or a polycarboxylic anhydride with a polyhydric alcohol. The polycarboxylic acid may be any of known aliphatic, cycloaliphatic, aromatic and / or heterocyclic polycarboxylic acids and may be substituted and / or unsaturated. Examples of suitable carboxylic acids and anhydrides are oxalic acid, malonic acid, glutaric acid, pimelic acid, succinic acid, adipic acid, suveric acid, azeraic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Trimellitic anhydride, pyromellitic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, and monomeric fatty acids Dimeric and trimeric fatty acids, such as oleic acid, which can form mixtures are included. Simple esters of polycarboxylic acids can be used, such as terephthalic acid dimethyl ester, terephthalic acid bisglycol and extracts thereof. Although aromatic polyester polyols can be prepared from substantially pure reactants as listed above, more complex components such as side streams, waste or scrap residues from the preparation of phthalic acid, phthalic anhydride, terephthalic acid, dimethyl terephthalate, polyethylene terephthalate, etc. Can be advantageously used.

Diphenylmethane-4,4'-diisocyanate (MDI) can also be used as an isocyanate component. Diphenylmethane diisocyanate (MDI) is a substance obtained by treating phosgene to diphenylmethane diamine (MDA), which is generally produced by condensation of aniline and formaldehyde. Diphenylmethane diisocyanate (MDI) can be classified into monomeric MDI and polymeric MDI. The latter is mainly used in the production of foamed polyurethane foam. The diphenylmethane diisocyanate (MDI) is mixed with other materials of the polyurethane stock in a weight ratio of 1 to 0.6 to 1.4.

Meanwhile, the polyurethane stock solution may be mixed with water, a silicon foam stabilizer, a catalyst, a flame retardant, a crosslinking agent, and other functional additives in addition to the polyol component and the isocyanate component. At this time, the viscosity of the rising polyurethane stock solution can be adjusted with tricresyl phosphate (T.C.P.P).

When the polyurethane stock solution is prepared, carbon nanotubes (CNTs) are added to the polyurethane stock solution as a nanocomposite material and dispersed to produce a composite solution <S120>.

In this case, carbon nanotubes, which are nanocomposites, are added to the polyurethane stock solution prepared to be 0.1 wt% to 10 wt% with respect to 100 wt% of the total composite solution.

As the content of carbon nanotubes, which are nanocomposites, increases, the density of polyurethane decreases as the volume decreases. Therefore, the content of the carbon nanotubes may be selectively adjusted according to the use requirements of the polyurethane foam, but the carbon nanotubes are preferably not more than 10% by weight in the total composite solution.

Then, a polyurethane foam is formed by adding a blowing agent to the composite solution containing carbon nanotubes and foaming <S130>.

As the blowing agent, an inorganic blowing agent, an organic blowing agent and / or a chemical blowing agent can be used.

The inorganic blowing agent can be carbon dioxide, nitrogen, argon, water, air, nitrogen or helium and the like.

The organic blowing agent may be an aliphatic hydrocarbon having 1 to 9 carbon atoms, an aliphatic alcohol having 1 to 3 carbon atoms, a fully or partially halogenated aliphatic hydrocarbon having 1 to 4 carbon atoms, and the like. The aliphatic hydrocarbon may also be methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, or neopentane, and the aliphatic alcohol may be methanol, ethanol, n-propanol, and isopropanol. Fully or partially halogenated aliphatic hydrocarbons can be fluorocarbons, chlorocarbons, chlorofluorocarbons and cyclopentane. Examples of fluorocarbons are methyl fluoride, perfluoromethane, ethyl fluoride (HFC-161), ethyl fluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoro Ethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), pentafluoroethane (HFC- 125), difluoromethane (HFC-32), perfluoroethane, 2,2-difluoropropane (HFC-272fb), 1,1,1-trifluoropropane (HFC-263fb), perfluoro Lopropan, 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,3,3-pentafluoropropane (HFC 245fa), 1,1,1,2, 3,3,3-heptafluoropropane (HFC-227ea), dichloropropane, difluoropropane, perfluorobutane, or perfluorocyclobutane. Wherein the partially halogenated chlorocarbons and chlorofluorocarbons are methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane (HCFC-141b), 1 -Chloro-1,1-difluoroethane (HCFC-142b), 1,2-difluoroethane (HFC-142), chlorodifluoromethane (HCFC-22), 1,1-dichloro-2, 2,2-trifluoroethane (HCFC-123), or 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124) and the like. And fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-tri Fluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, or dichlorohexafluoropropane.

Chemical blowing agents include azodicarbonamide, azodiisobutyro-nitrile, benzenesulfonhydrazide, 4,4-oxybenzene sulfonylsemicarbazide, p-toluene sulfide Polyvinyl semi-carbazide, barium azodicarboxylate, and N, N'-dimethyl-N, N'-dinitrosoterephthalamide, or trihydrazino triazine. Mixtures containing approximately the same amount of 1,1,2,2-tetrafluoroethane (HFC-134a) as 1,1-difluoroethane (HFC-152a) can also be used as blowing agents.

By adding such a foaming agent, a composite solution including a polyurethane stock solution and carbon nanotubes is foamed to form a polyurethane foam. As illustrated in FIGS. 3 to 4, carbon nanotubes form a network in a cell of polyurethane foam. When the polyurethane foam manufactured by forming and positioning is used as a heat insulating material, the following characteristics appear.

First, carbon nanotubes can increase air insulation efficiency when mounted as a heat insulator in a refrigeration / refrigeration system by increasing the heat insulation performance by maximizing the porosity of polyurethane foam due to the large voids that can accommodate gas. That is, although there are no voids in the diaphragm constituting the cell in pure polyurethane foam, in the polyurethane foam according to the first embodiment of the present invention, since the carbon nanotubes are disposed in the diaphragm constituting the cell, the porosity of the polyurethane foam is reduced. It can be maximized.

In addition, when high-temperature radiant heat penetrates, the heat transfer is reduced due to the net structure of the carbon nanotubes and the relatively large heat capacity, thereby providing excellent thermal stability.

In addition, since the carbon nanotubes are well dispersed in the polyurethane resin and form a network, the radiant heat penetrates from one side of the polyurethane foam through the network of carbon nanotubes, so radiant heat is transmitted in the thickness direction of the polyurethane foam. Minimize your work. Therefore, it can effectively protect the inside by minimizing the transmission of external heat when used as a thermal insulation for cold insulation.

In addition, the strength of the polyurethane foam is also improved due to the characteristics of the strong carbon nanotubes.

That is, even if the thickness is reduced by improving the durability, thermal insulation, and thermal stability of the polyurethane foam, it can be confirmed that the excellent performance as a cold insulation and insulation. Therefore, it is possible to reduce the size of the device by reducing the thickness of the coolant mounted on the refrigerating / freezing equipment, to maximize the internal volume, it is possible to reduce the weight and cost of the equipment. In addition, the use of polyurethane can be reduced to reduce the emission of environmental pollutants.

5 is a view for explaining a method of manufacturing a cold-curable polyurethane foam composition using a nano composite material according to a second embodiment of the present invention, Figure 6 and Figure 7 is a poly produced by the manufacturing method shown in FIG. It is a figure for demonstrating a urethane foam composition.

First, to prepare a polyurethane foam, a polyurethane stock solution containing a polyol component and an isocyanate component is prepared <S210>.

Since the description of the polyurethane stock solution is detailed in the description of the first embodiment, overlapping descriptions are avoided.

When the polyurethane stock solution is prepared, carbon nanotubes and carbon nanoplate powders are added to the polyurethane stock solution as a nanocomposite material and dispersed to produce a composite solution. Here, carbon nanoplate means graphite having a plate-like structure.

In this case, carbon nanotubes and carbon nanoplates, which are nanocomposite materials, are added to the polyurethane stock solution prepared to be 0.1 wt% to 10 wt% based on 100 wt% of the total composite solution.

As the content of carbon nanotubes and carbon nanoplates, which are nanocomposites, increases, the density of polyurethane decreases as the volume decreases. Therefore, the content of the carbon nanotubes and the carbon nanoplates may be selectively controlled according to the use requirements of the polyurethane foam, but the carbon nanotubes and the carbon nanoplates are preferably not more than 10% by weight in the total composite solution.

Then, a polyurethane foam is formed by adding a blowing agent to the composite liquid containing carbon nanotubes and carbon nanoplates and foaming <S230>.

Since the description of the blowing agent is also detailed in the first embodiment, overlapping descriptions are to be avoided.

As shown in FIGS. 6 to 7, the carbon nanotubes and the carbon nanoplates are formed by being positioned in the cell of the polyurethane foam, and thus, when the polyurethane foam prepared as a heat insulating material is used, the carbon nanotubes described above are included. In addition, the following characteristics by carbon nanoplates are also shown.

That is, because of the plate-like structural properties of the carbon nanoplates, the reflectance of the heat is high, the porosity of the polyurethane foam is high by the carbon nanotubes, and heat can be dispersed by forming the network, so even if radiant heat penetrates, It can minimize the transmission of heat. Therefore, when mounted as a coolant in the refrigerating / freezing equipment, it is possible to effectively block the external radiant heat from penetrating the inside.

In addition, when the high-temperature radiant heat penetrates, the heat transfer is lowered due to the mesh structure of the carbon nanotubes, the characteristics of the carbon nanoplates having high heat reflectance, and the relatively large heat capacity of the carbon nanotubes and the carbon nanoplates, thereby providing excellent thermal stability.

In addition, due to the high strength of the carbon nanotubes and carbon nanoplates, the strength of the polyurethane foam is also improved, and even if the thickness is reduced, it is possible to confirm the superior performance as the insulator and insulation. Therefore, it is possible to reduce the size of the device by reducing the thickness of the coolant mounted in the refrigeration / freezing equipment, to maximize the internal volume, it is possible to reduce the weight and cost of the equipment. In addition, the use of polyurethane can be reduced to reduce the emission of environmental pollutants.

On the other hand, the present invention is to improve the thermal insulation and thermal stability of the polyurethane foam through the characteristics of the nano composite material consisting of carbon nanotubes or carbon nanotubes and carbon nanoplates. Therefore, the polyurethane foam is not necessarily manufactured by the above-described process, and further includes a process of adding a nano composite material including carbon nanotubes or carbon nanotubes and carbon nanoplates in a conventional polyurethane foam manufacturing process. The object of the present invention may also be achieved. Therefore, such a manufacturing method should also be considered to be included in the present invention.

Preferred embodiments of the present invention described above are disclosed for the purpose of illustration, and those skilled in the art will be able to make various modifications, changes and additions within the spirit and scope of the present invention. And additions should be considered to be within the scope of the claims of the present invention.

Claims (5)

Preparing a polyurethane stock solution;
Producing a composite solution by adding and dispersing a nanocomposite material to the polyurethane stock solution; And
Foaming the complex solution; including;
The nanocomposite material is a method for producing a cold-curable polyurethane foam composition using a nanocomposite material, characterized in that containing carbon nanotubes.
The method of claim 1,
The nanocomposite material is a method for producing a cold-curable polyurethane foam composition using a nanocomposite material characterized in that it further comprises a carbon nanoplate.
The method according to claim 1 or 2,
The polyurethane stock solution is produced by reacting a polyol component and an isocyanate component with water, a catalyst, and an additive.
The method according to claim 1 or 2,
The nanocomposite material is a method for producing a cold-curable polyurethane foam composition using a nanocomposite material, characterized in that added to the polyurethane stock solution at 0.1% to 10% by weight relative to 100% by weight of the total composite solution.
A cold-retaining polyurethane foam composition using the nanocomposite material produced by the method of any one of claims 1 or 2.

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