KR20170104108A - Method of producing Isocyanuric Polyol and Polyurethane Foam Board with the Same - Google Patents

Abstract

The present invention relates to a method of producing an isocyanuric polyol with high heat resistance and low reactivity, a method of producing an aromatic polyester polyol with high flame retardancy and low reactivity, a method of producing a urethane foam by mixing the isocyanuric polyol and the aromatic polyester polyol, and making the mixture react with isocyanate, and a method of producing a urethane foam board with excellent flame retardancy, heat resistance and dimensional stability, and good workability by attaching an aluminum sheet or a glass fabric aluminum sheet to the surface of the urethane foam board. A method of producing a rigid urethane foam board according to the present invention preferably comprises the steps of: synthesizing the isocyanuric polyol with high heat resistance and low reactivity, and synthesizing the aromatic polyester polyol with high flame retardancy and low reactivity; mixing the isocyanuric polyol and the aromatic polyester polyol with a foaming agent, a catalyst, a flame retardant, additives and the like to produce a polyol compound for urethane production; and making the polyol compound for urethane production react with an aromatic polyisocyanate to produce a rigid urethane foam board in a production line of a building interior material, or attaching an aluminum sheet to the surface of the rigid urethane foam board.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an isocyanuric polyol and a flame-retardant urethane foam board containing the same,

The present invention relates to a method for producing a urethane foam insulation material for construction using a heat-resistant polyol which is thermodynamically very stable and a non-combustible material on the surface thereof, and more specifically to a process for producing an isocyanuric polyol having high heat resistance and low reactivity And a polyol mixture obtained by mixing the isocyanuric polyol and the aromatic polyester polyol to prepare a urethane foam foam having excellent flame retardancy, heat resistance and dimensional stability by using the polyol mixture, and a method of producing a urethane foam foam Which is excellent in flame retardance, heat resistance and dimensional stability, and has good workability, by attaching an aluminum sheet or a fabric aluminum sheet to the surface of a urethane foam board.

Insulation made of rigid polyurethane foam is environmentally friendly, lightweight, and has excellent heat insulation, soundproofing and molding processability, and thus is widely used for building insulation, refrigerator, freezing container, ship, insulation material and other ornaments.

In order to produce a rigid polyurethane foam to be used as a heat insulating material, an aromatic polyisocyanate and a polyol composition liquid are used. The polyol reacts with the aromatic polyisocyanate to form a macromolecule, which is then cured. In order to control the properties after curing, various compounds are mixed and used. For example, physical and chemical blowing agents are used to control density, and amine and metal catalysts are added to control the rate of cure, whereby the structure and properties of the foamed foam are different. And they have compatibility so that the problem of separating the phases during mixing should not arise. Recent technology has greatly contributed to improving the performance of insulation by developing various manufacturing process technologies that satisfy all of these conditions.

On the other hand, the materials used as interior and exterior materials of buildings should be stable against fire as well as excellent heat insulation. Polyurethane (PUR) foam insulation is increasingly in demand as an optimal material in terms of insulation performance and environmental friendliness, but the vulnerability to fire is pointed out as a serious problem. In view of the domestic and international situation, there is a growing awareness that energy saving is an important solution as an alternative to climate change and environmental pollutant emission reduction, and it is advantageous to use urethane foam materials with good thermal insulation.

In recent years, urethane foam insulation materials have been on the rise in the interior of large-scale residential complexes and buildings, but fire and other accidents have increased the damage to property and property. In addition, the enlargement of the buildings and the increase of the size of the buildings make it difficult to suppress the fire in case of fire, and the collapse of the structure and the generation of toxic gas are required.

Today, there are two ways to flame retard the polyurethane foam products.

The first method is to add a flame retardant to the raw material. In this method, an additional flame retardant component or the like is preliminarily mixed with the polyol raw material and the mixed raw material material is brought into contact with the isocyanate component so as to impart flame retardancy to the polyol component and the isocyanate component during the urethane reaction. At this time, the flame retardant used may be classified into a flame retardant based on an organic material and a flame retardant based on an inorganic material.

The second method is a method of inducing a trimerization reaction during the urethane reaction to produce polyisocyanurate (PIR) panels. When manufacturing the polyisocyanurate (PIR) panel using this method, the flame retardancy and the heat resistance can be further improved or supplemented while maintaining the advantages of the existing polyurethane foam (PUR) It is excellent, has little change such as shrinkage expansion due to heat, and has the advantage of having self-adhesive force. However, this method has the disadvantage that the production method is too difficult and difficult to proceed with mass production.

However, the polyurethane manufacturing technology that can realize various performance and stability of reaction at the same time while improving the flame retardancy and heat resistance at the same time, has not been introduced yet.

The present invention is to provide a novel polyurethane production method capable of realizing high flame retardancy and heat resistance and capable of inducing various reactions and at the same time stabilizing the reaction.

Korean Registered Patent No. 10-939000 "Semi-incombustible polyurethane foam panel and its continuous production method" (2010. 01. 20.); Korean Patent No. 10-931094 entitled "Method for producing a light urethane-modified polyisocyanurate foam" (December 02, 2009); Korean Patent Laid-Open No. 10-2014-127856 "Process for producing rigid polyurethane-polyisocyanurate foam" (Apr.

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It is an object of the present invention to provide a method for producing an isocyanuric polyol having high heat resistance and low reactivity by using an epoxy compound which has not been conventionally used for polyurethane production.

The present invention also provides a method for producing an aromatic polyester polyol having a high reactivity and a low reactivity using a glycol compound capable of controlling a reaction speed and controlling the reaction rate and a compound capable of imparting flame retardancy, There is a purpose of.

The present invention also provides a method for producing a urethane foam foam excellent in flame retardancy, heat resistance and dimensional stability by using an isocyanuric polyol having a high heat resistance and low reactivity and an aromatic polyester polyol having a low heat resistance and low reactivity, There is a purpose.

Further, the present invention provides a urethane foam foam having excellent flame retardancy, heat resistance and dimensional stability, and an aluminum sheet or a fabric aluminum sheet attached to the surface of the board of the urethane foam foam to provide an excellent flame retardancy, heat resistance and dimensional stability, A fourth object of the present invention is to provide a method for producing a urethane foam board.

In order to achieve the first object of the present invention, the present invention provides a process for producing a glycidyl ether compound, which comprises reacting a glycol compound having one or more hydroxyl groups in an epoxy group-bonded triglycidyl isocyanurate (TGIC) And propylene oxide is added to control the reaction time of the compound to synthesize a polyol compound.

In order to achieve the second object, the present invention also provides a polyester polyol compound having excellent flame retardancy by reacting a glycol compound having a different reaction order with an aromatic organic acid by preparing a glycol compound having a different reaction order.

In order to achieve the third object of the present invention, the present invention also provides a process for producing a polyol mixture, comprising mixing the polyol compound produced by the first object with the polyester polyol compound produced by the second object in an appropriate ratio, A foaming agent, an additive and the like are added to the polyol mixture and reacted with isocyanate to prepare a polyurethane foam foam excellent in flame retardancy, heat resistance and dimensional stability.

In order to achieve the fourth object of the present invention, the present invention provides a process for producing a polyol mixture, comprising mixing the polyol compound produced by the first object with the polyester polyol compound produced by the second object in an appropriate ratio, And an aluminum sheet or a fabric aluminum sheet is adhered to the surface of the urethane foam foam board by reacting the polyol mixture with a foaming agent and an additive and reacting with an isocyanate to form a urethane foam foam. And a hard urethane foam board having good workability is manufactured.

The high heat-resistant low-reactive isocyanuric polyol according to the present invention is very good in heat resistance, and thus has a merit of providing high heat resistance to polyurethane foam board and its application products when producing polyurethane foam. Since the high heat-resistant low-reactive isocyanuric polyol was prepared using triglycidyl isocyanurate having an epoxy group, which was not conventionally used for polyurethane production, as the starting material, the epoxy-triglycidyl isocyanurate And the range of use of the device is extended.

In addition, since the low-temperature-resistant low-oleic ester polyol according to the present invention has excellent flame retardancy, it has an advantage of imparting high flame retardancy to polyurethane foam and its products. The low-temperature low-reactivity oleester polyols retard the reaction rate during the urethane reaction, so that the urethane reaction can be controlled.

Further, the polyurethane foam according to the present invention is advantageous in that it has flame retardancy and high heat resistance. Since conventional polyurethane foams do not have their own flame retardant properties, they are additionally provided with flame retardant substances, whereas in the polyurethane foam according to the present invention, the main chains of all polyols are composed of a heat-resistant and flame-retardant structure.

In addition, the polyurethane foam board product according to the present invention has such a flame retardant property that it is advantageous in that the urethane foam board product is not ignited when a fire occurs, thereby suppressing the generation of toxic gas including safety of the structure , Which can greatly contribute to the security of life and property.

Further, the present invention is advantageous in that the surface of the rigid urethane foam is made of an aluminum sheet or a fabric aluminum sheet, and is lightweight but excellent in flame retardancy.

1A to 1C are representative reaction formulas for producing the high heat-resistant low-reactive isocyanuric polyol of the present invention,
2 is a typical reaction formula for synthesizing the poorly-softated low-reactivity aromatic polyester polyol of the present invention,
Figures 3a and 3b are copies of test reports from the Korea Shipbuilding & Marine Equipment Research Institute regarding the polyurethane foam of the present invention.

Hereinafter, the present invention will be described in more detail and in detail. It is apparent that the present invention is not limited to the specific numerical values or concrete examples provided by the present invention, but is only for the purpose of illustrating the technical idea of the present invention in more detail as a preferred embodiment of the present invention. Further, in the specification of the present invention, a detailed description will be omitted of parts that are well known in the technical field and can be easily created by a person having ordinary skill in the art.

One). High heat-resistant low-reactive isocyanuric polyol Synthesis:

The present invention provides a method for producing an isocyanuric polyol having high heat resistance and low reactivity. The isocyanuric polyol can be usefully used for the production of a highly heat-resistant polyurethane foam.

The present invention reacts with an epoxy group-bonded triglycidyl isocyanurate compound and a glycol compound having a first order reaction and a second order reaction to form an isocyanuric polyol compound having a high heat resistance and low reactivity.

The present invention uses a triglycidyl isocyanurate (TGIC) compound to which an epoxy group is bonded as a starting material of a polyol compound for producing a polyurethane foam. In general, isocyanurate is a very stable chemical structure and has good resistance to heat and exhibits excellent heat resistance.

The present invention preferably uses triglycidyl isocyanurate as an isocyanurate compound which is a core of heat resistance. The above-mentioned triglycidyl isocyanurate compounds have conventionally been mainly used as a curing agent for moldings, adhesives and polyester-based powder coatings, have excellent adhesion to metals, have good heat resistance and weatherability and are used as adhesives have. It is also known to be widely used in optical and electronic fields due to its excellent transparency and conductivity. However, the fact that it has been used so far to manufacture polyurethane foams is not known.

In the present invention, a polyol compound is prepared by reacting the triglycidyl isocyanurate compound with a glycol compound. The epoxy group of the triglycidyl isocyanurate compound reacts with the hydroxyl group of the glycol compound to be ring-opened to form a polyol compound. The glycol compound preferably has a hydroxyl group at its terminal in two first-order reaction orders or a hydroxyl group at the end thereof in a first-order reaction order and a second-order reaction order.

Examples of the glycol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,4-butanediol (1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol and neopentyl glycol are preferably used.

In order to control the reactivity of the polyol compound, propylene oxide may be additionally reacted. When the hydroxyl groups of the polyol compound have the same first order reaction order, it is preferable to add the propylene oxide to the polyol compound. This is because when the hydroxyl group has a first reactor, it reacts with the isocyanate group quickly and rapidly. Therefore, the polyol compound produced by the addition reaction of propylene oxide may have a second order reaction . The resulting polyol compound is structurally disturbed by adjacent groups of hydroxyl groups, and when the hydroxyl group is reacted with the isocyanate group, the urethane reaction proceeds more slowly.

The addition reaction of propylene oxide is used to control the viscosity and the reactivity of the polyol terminal. That is, when the terminal portion of the polyol has a primary hydroxyl group, the polyurethane reacts rapidly with the polyisocyanate in the urethane foam board production process. Therefore, the propylene oxide is added to give a different degree of reaction. In this case, the first order reaction group of the hydroxyl group means a state in which the hydroxyl group (-OH) reacts without hindrance, such as a -CH-OH bond to the periphery of the hydroxyl group, and the second reaction group of the hydroxyl group Refers to a state in which the hydroxyl group (-OH) reacts while receiving a structural disorder by an adjacent group such as a -C (CH ₃ ) -OH bond to the periphery of the hydroxyl group. The propylene oxide is used for controlling the urethane reaction. However, if the amount of the propylene oxide used is excessive, the flame retardancy may be lowered.

In the present invention, the triglycidyl isocyanurate compound is reacted with a glycol compound to form a polyol compound. In this case, since the epoxy group and the hydroxyl group can react with each other to form functionalities of 3 to 9 in the polyol compound, it is possible to improve the dimensional stability of the urethane foam by appropriately adjusting these functional groups .

1A through 1C show typical reaction schemes for preparing a high heat-resistant low-reactive isocyanuric polyol according to the present invention.

Referring to FIG. 1A, a case is shown in which a polyol compound is prepared by reacting triglycidyl isocyanurate with ethylene glycol. According to FIG. 1A, it can be seen that in the polyol compound, all the hydroxyl groups have a first-order reaction degree which does not have a structural disorder in the periphery.

FIG. 1B shows a case where a polyol compound is prepared by reacting propylene glycol with triglycidyl isocyanurate. Referring to FIG. 1B, it can be seen that the hydroxyl groups in the polyol compound have a first-order reaction sequence which does not have a structural disorder in the periphery, and a second-order reaction sequence which has a structural disorder in the periphery. In this case, the hydroxyl groups of the first order reaction order cause a urethane reaction very rapidly, whereas the hydroxyl groups of the second order order form a urethane reaction slowly.

FIG. 1C shows a case where a primary polyol compound is prepared by reacting the triglycidyl isocyanurate with ethylene glycol, and then a secondary polyol compound is finally prepared using propylene oxide. In the primary polyol compound, hydroxyl groups all have the same first order reaction order, but in the second polyol compound, hydroxyl groups form a first order reaction order and a second order reaction order.

2). Highly flammable low reactive aromatic polyester polyol synthesis:

The present invention provides a method for producing an aromatic polyester polyol having a high stiffness and a low reactivity. The aromatic polyester polyol may be usefully used for producing a highly flame-retardant polyurethane foam.

The present invention relates to a method for producing a highly flame-retardant polyurethane foam, which comprises subjecting a glycol compound having a different reaction order to a condensation reaction with an aromatic organic acid to obtain an aromatic polyester having high reactivity and low reactivity, To prepare a polyol.

The present invention relates to a process for preparing a polyol compound by reacting a glycol compound with an organic acid, wherein the glycol compound is selected from a modified glycol compound having a first reaction order and a second reaction order and having a large number of hydroxyl groups (-OH) . This means that the modified glycol compound in which the hydroxyl group (-OH) has the first order reaction order and the second order reaction order is used as a raw material for producing the polyol compound for urethane production. When the polyol compound having the first order reaction order is used, the reaction rate with the isocyanate group is high, so that the workability is poor and the defective rate of the final product is also increased. Thus, by including the hydroxyl group having the second order reaction degree, To control the speed.

In the present invention, ethylene glycol, diethylene glycol, triethylene glycol, butylene glycol, and neopentyl glycol may be used alone or in combination as the glycol compound Can be used. The glycol compound preferably has a low functional group because of the high viscosity of the synthesized polyester polyol. As such commonly known glycols are primary hydroxyl groups, they are preferably modified and used.

In the present invention, such a glycol is modified and used as a raw material for synthesizing a polyester polyol having low reactivity. Specifically, for example, propylene oxide is added to a glycol compound such as ethylene glycol or diethylene glycol having both hydroxyl groups at both terminal ends thereof, and the resulting product is reacted at one end It is preferable to prepare a glycol modified with a secondary hydroxyl group.

In the present invention, an organic acid which reacts with the glycol compound is selected as an aromatic organic acid. The aromatic organic acid means a compound containing an aromatic group in an organic acid compound. The aromatic organic acid is preferably an organic acid such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, and pyromellitic dianhydride, Or may be used in combination.

The present invention produces a polyester polyol compound for urethane synthesis by condensation reaction between the modified glycol compound and the aromatic organic acid having different reaction orders. The modified glycol compound is a glycol compound containing a large number of hydroxyl groups having different reaction orders, and is a glycol compound which undergoes a condensation reaction with the aromatic organic acid, so that the reaction degree of the hydroxyl group is different, Respectively.

In general, the synthesis of a polyester polyol increases the number of moles of glycol to more than the number of moles of organic acid so that both ends of the polyol are in a hydroxyl state. A modified glycol compound and an organic acid are reacted with a glycol compound having a different reaction order after the glycol is modified with propylene oxide so that the primary hydroxyl group of the modified glycol reacts with the aromatic organic acid, Both ends become secondary hydroxyl groups. Polyester polyols having a secondary hydroxyl group are reacted very slowly with isocyanate.

In the present invention, an aromatic polyester polyol having excellent flame retardancy was synthesized by this method to solve the problem of quick reactivity. This modified polyester polyol satisfies both productivity and quality stability by enabling work processes similar to conventional PPG systems.

Fig. 2 shows a reaction formula relating to a glycol modification reaction and a polyester synthesis reaction. 2, ethylene glycol has two hydroxyl groups having a first order reaction and is subjected to an addition reaction with propylene oxide to obtain a modified glycol having first order and second order on both ends thereof And then reacting it with an organic acid to synthesize an aromatic polyester polyol.

3). Polyol system formulation and rigid urethane foam board manufacture:

The present invention provides a method for producing a polyurethane foam having a high flame retardancy and a high heat resistance and at the same time various performances.

The present invention relates to a process for preparing a polyol mixture by mixing the isocyanuric polyol, the aromatic polyester polyol and a polyol compound for urethane production in an appropriate mixing ratio, adding a foaming agent and an additive to the polyol mixture and reacting with the isocyanate to produce a flame retardant, Thereby producing a urethane foam board having excellent stability.

The present invention relates to a method for producing an isocyanuric polyol compound, which comprises reacting an epoxy group-bonded triglycidyl isocyanurate compound with a glycol compound having a first-order reaction sequence and a second-order reaction sequence to form an isocyanuric polyol compound having a high heat- A glycol compound having a different reaction order is condensed with an aromatic organic acid to prepare a high-yielding and low-reacting aromatic polyester polyol having a large number of hydroxyl groups with different reaction orders; 30 to 60 parts by weight of the high heat-resistant low-reactive isocyanuric polyol compound and 40 to 70 parts by weight of a foaming agent, a catalyst, a flame retardant, and an additive are mixed to prepare a polyol composition for urethane production, 20 to 50 parts by weight of an aromatic polyester polyol compound and 50 to 80 parts by weight of a foaming agent, a catalyst, a flame retardant, an additive and the like are mixed to prepare a polyol composition for urethane production, or the isocyanuric polyol compound 25 to 35 35 to 50 parts by weight of an aromatic polyester polyol compound having high hardness and low reactivity and 25 to 30 parts by weight of a foaming agent, a catalyst, a flame retardant, an additive and the like are blended to prepare a polyol composition for urethane production, To react with an aromatic polyisocyanate to prepare a rigid urethane foam board.

The present invention relates to a triglycidyl isocyanurate compound having an epoxy group bonded thereto and a glycol compound having a first order reaction and a second order reaction to form an isocyanuric polyol compound having a high heat resistance and low reactivity. Since the method of forming the isocyanuric polyol compound having a high heat-resistant low-reactivity has been described in detail above, it will not be described repeatedly.

The present invention relates to an aromatic polyester polyol having a high reactivity and a low reactivity, in which a glycol compound having a different reaction order is condensed with an aromatic organic acid to thereby contain a large number of hydroxyl groups having different reaction orders. The method for producing the aromatic polyester polyol having the high hardness and low reactivity has been described in detail above, and therefore, it will not be described repeatedly.

In the present invention, 30 to 60 parts by weight of the high heat-resistant low-reactive isocyanuric polyol compound and 40 to 70 parts by weight of a blowing agent, a catalyst, a flame retardant, an additive and the like can be used as a polyol mixture for polyurethane production. When the isocyanuric polyol compound having a high heat resistance and low reactivity is used in an amount of 30 parts by weight or less, there is a problem in dimensional stability of the foam. When the amount is 60 parts by weight or more, it is difficult to control the viscosity of the compound. The isocyanuric polyol having a high heat-resistant low-reactivity is preferably used in an amount of 40 to 50 parts by weight. Such blending is advantageous when the urethane foam is intended to enhance high heat resistance performance.

In the present invention, 20 to 50 parts by weight of aromatic polyester polyol having high hardness and low reactivity and 50 to 80 parts by weight of a foaming agent, a catalyst, a flame retardant, an additive and the like may be mixed and used as a polyol mixture for polyurethane production. When the aromatic polyester polyol compound having the high hardness and low reactivity is blended in an amount of 20 parts by weight or less, the viscosity of the entire polyol mixture becomes high. When the blend is used in an amount of 50 parts by weight or more, the dimensional stability may deteriorate, I can not resist. Preferably, 30 to 40 parts by weight of the aromatic polyester polyol compound having the high hardness and low reactivity is used. This formulation is advantageous when the urethane foam is intended to enhance the hardness performance.

The present invention relates to a process for producing an aromatic polyester polyol compound comprising 25 to 35 parts by weight of an isocyanuric polyol compound having a high heat resistance and a low reactivity and 35 to 50 parts by weight of an aromatic polyester polyol compound having the above- To 30 parts by weight may be blended and used as a polyol mixture for producing polyurethane. This combination is advantageous when the urethane foam is intended to enhance both high heat resistance and high flame retardancy.

In the present invention, the polyol mixture for polyurethane production is formulated to prepare a polyurethane composition for urethane production, and then the rigid urethane foam board is prepared by reacting with an aromatic polyisocyanate in a building interior material production line. Such a method can be carried out in a method used in a method for producing a urethane foam.

4). Manufacture of flame retardant urethane foam panels:

The present invention relates to a polyurethane foam having high flame retardancy and high heat resistance and at the same time capable of realizing various performances, and an aluminum sheet or a glass fabric aluminum sheet is adhered to the surface of the polyurethane foam, ≪ RTI ID = 0.0 > a < / RTI > rigid urethane foam panel.

The present invention relates to a method for producing a polyisocyanate compound, which comprises reacting an epoxy group-bonded triglycidyl isocyanurate compound with a glycol compound having a first-order reaction sequence and a second-order reaction sequence to form an isocyanuric polyol compound having a high heat- A glycol compound having a different reaction order is condensed with an aromatic organic acid to produce an aromatic polyester polyol having a high reactivity and a low reactivity and containing a large number of hydroxyl groups with different reaction orders;

 30 to 60 parts by weight of the high heat-resistant low-reactive isocyanuric polyol compound and 40 to 70 parts by weight of a foaming agent, a catalyst, a flame retardant, and an additive are mixed to prepare a polyol composition for urethane production, 20 to 50 parts by weight of an aromatic polyester polyol compound and 50 to 80 parts by weight of a foaming agent, a catalyst, a flame retardant, an additive and the like are mixed to prepare a polyol composition for urethane production, or the isocyanuric polyol compound 25 to 35 35 to 50 parts by weight of an aromatic polyester polyol compound having high hardness and low reactivity and 25 to 30 parts by weight of a foaming agent, a catalyst, a flame retardant, an additive and the like are blended to prepare a polyol composition for urethane production, Reacting with an aromatic polyisocyanate to prepare a rigid urethane foam board; An aluminum sheet or a glass fabric aluminum sheet is attached to the surface of the rigid urethane foam board to produce a urethane foam panel having excellent flame retardance, heat resistance, dimensional stability and workability.

The present invention relates to a triglycidyl isocyanurate compound having an epoxy group bonded thereto and a glycol compound having a first order reaction and a second order reaction to form an isocyanuric polyol compound having a high heat resistance and low reactivity. The method of forming the isocyanuric polyol compound having a high heat-resistant low-reactivity and the performance of the final product have already been described in detail above.

The present invention relates to an aromatic polyester polyol having a high reactivity and a low reactivity, in which a glycol compound having a different reaction order is condensed with an aromatic organic acid to thereby contain a large number of hydroxyl groups having different reaction orders. The process for producing the aromatic polyester polyol having the high hardness and low reactivity as well as the performance of the final product are as described in detail above.

In the present invention, 30 to 60 parts by weight of the high heat-resistant low-reactive isocyanuric polyol compound and 40 to 70 parts by weight of a blowing agent, a catalyst, a flame retardant, an additive and the like may be blended as a polyol mixture. The compounding ratio of the above components and the performance of the final product are as described above.

In the present invention, 20 to 50 parts by weight of the aromatic polyester polyol having high hardness and low reactivity and 50 to 80 parts by weight of a foaming agent, a catalyst, a flame retardant, an additive and the like may be blended as a polyol mixture. The compounding ratio of the above components and the performance of the final product are as described above.

The present invention relates to a process for producing an aromatic polyester polyol compound comprising 25 to 35 parts by weight of an isocyanuric polyol compound having a high heat resistance and a low reactivity and 35 to 50 parts by weight of an aromatic polyester polyol compound having the above- To 30 parts by weight may be blended to prepare a polyol mixture. This combination is advantageous when the urethane foam is intended to enhance both high heat resistance and high flame retardancy.

The present invention relates to a method for producing a urethane foamable polyurethane foam sheet by preparing a polyol composition for polyurethane production by blending the polyol mixture and then reacting the aromatic polyisocyanate with an aromatic polyisocyanate in a building interior material production line to produce a hard urethane foam board, To produce a rigid urethane foam panel. Such a method can be carried out in a method used in a method for producing a urethane foam.

The present invention has the advantage of being lightweight and having excellent flame retardancy by producing an aluminum sheet or a glass fabric aluminum sheet on the surface of the hard urethane foam. The aluminum sheet used in the production of the urethane foam board of the present invention preferably has a thickness of 0.08 mm to 0.18 mm and the fabric aluminum sheet preferably has a thin and flexible material having a thickness of 0.12 mm to 0.16 mm.

In order to be judged according to the domestic flame retardancy test standard, not only the flame retardancy of the polyol but also the material for protecting the foam must be made of a steel sheet such as steel. However, it is difficult to use a urethane foam panel product formed of a metal steel sheet as an interior material of a building in this state.

Hereinafter, the present invention will be described in more detail and in detail. It is apparent that the specific numerical values or concrete examples provided in the embodiments of the present invention are described as preferred embodiments of the present invention, and the present invention is not limited thereto.

1) High heat-resistant low-reactive isocyanuric polyol Synthesis:

[ Example  One]

89.19 kg of triglycidyl isocyanurate, 74.49 kg of ethylene glycol, and 810 g of acetylacetoacetonate as a catalyst were placed in a reaction tank and reacted at 120 ° C for 7 hours while stirring. The reaction was completed by confirming the residual peak of triglycidyl isocyanurate by GC analysis. Unreacted ethylene glycol was recovered by distillation under reduced pressure at 120 ° C and 40 torr for 3 hours.

145.05 kg of the synthesized polyol was transferred to a high-pressure reactor, and 53.10 kg of propylene oxide was injected at a constant rate under an alkaline catalyst. After 12 hours, 198.15 kg of a highly heat resistant low-reactive isocyanuric polyol was obtained. The viscosity of the obtained polyol was 11,300 cps at 25 ° C and the pale brown resinous phase with a hydroxyl value of 510.00 mgKOH / g.

[Example 2]

89.19 kg of triglycidyl isocyanurate, 91.31 kg of propylene glycol, and 900 g of acetylacetoacetonate as a catalyst were added to the reaction tank, and reacted at 120 ° C for 8 hours while stirring. The reaction was completed by confirming the residual peak of triglycidyl isocyanurate by GC analysis. The unreacted propylene glycol was recovered by distillation under reduced pressure at 120 DEG C and 40 torr for 3 hours to obtain 157.63 kg of a polyol. The viscosity of the synthesized polyol was 13,900 cps at 25 ℃ and the colorless resin was 640.56 mgKOH / g.

2) Synthesis of low-reactivity low-reactive aromatic polyester polyol:

[ Example  3]

65.17 kg of ethylene glycol was charged into a high-pressure reactor and 61.95 kg of propylene oxide was added thereto under an alkaline catalyst to obtain 127.12 kg of ethylenepropylene glycol. 127.12 kg of ethylene propylene glycol synthesized in the ester polymerization reactor, 83.07 kg of terephthalic acid and 210 g of a catalyst were charged and the reaction was carried out for 12 hours by stepwise raising operation to obtain 186.14 kg of an aromatic polyester polyol. As a result of measurement, a pale yellow resinous polyol having a viscosity of 3,800 cps and a hydroxyl value of 351.60 mgKOH / g at 25 캜 was obtained.

[ Example  4]

111.43 kg of diethylene glycol was charged into a high-pressure reactor, and 61.95 kg of propylene oxide was added thereto under an alkaline catalyst to obtain 173.38 kg of diethylene propylene glycol. 173.38 kg of diethylene propylene glycol synthesized in the ester polymerization reactor, 83.07 kg of terephthalic acid and 256 g of a catalyst were charged and the reaction was carried out for 12 hours by stepwise raising operation to obtain 230.21 kg of an aromatic polyester polyol. As a result of measurement, a pale yellow resinous polyol having a viscosity of 2,900 cps and a hydroxyl value of 325.5 mgKOH / g was obtained at 25 ° C.

3) Preparation of polyol composition for urethane production and rigid urethane foam board:

[ Example  5]

60.0 kg of the high heat-resistant low-reactive isocyanuric polyol prepared in Example 1, 84.0 kg of the poorly soft low-reactivity aromatic polyester polyol prepared in Example 3, 26.0 kg of foaming agent HCFC-141b, kg of a flame retardant, 20.0 kg of a flame retardant TCPP, 2.0 kg of a catalyst PC-5, 3.0 kg of T-45 and 1.0 kg of water to prepare 200 kg of a polyol system composition.

In a urethane foam production line, 240 kg of polyisocyanate was mixed with 200 kg of the polyol system composition using a high-pressure foaming machine to prepare a rigid urethane foam foam.

[ Example  6]

90.0 kg of the high heat-resistant low-reactive isocyanuric polyol prepared in Example 2, 54.0 kg of the poorly soft low-reactivity aromatic polyester polyol prepared in Example 4, 26.0 kg of the foaming agent HCFC-141b, kg of a flame retardant, 20.0 kg of a flame retardant TCPP, 2.0 kg of a catalyst PC-5, 3.0 kg of T-45 and 1.0 kg of water to prepare 200 kg of a polyol system composition.

In a urethane foam production line, 240 kg of polyisocyanate was mixed with 200 kg of the polyol system composition using a high-pressure foaming machine to prepare a rigid urethane foam foam.

4). Manufacture of flame retardant urethane foam panels:

[ Example  7]

60.0 kg of the high heat-resistant low-reactive isocyanuric polyol prepared in Example 1, 84.0 kg of the poorly soft low-reactivity aromatic polyester polyol prepared in Example 3, 26.0 kg of foaming agent HCFC-141b, kg of a flame retardant, 20.0 kg of a flame retardant TCPP, 2.0 kg of a catalyst PC-5, 3.0 kg of T-45 and 1.0 kg of water to prepare 200 kg of a polyol system composition.

In a urethane foam production line, 240 kg of polyisocyanate was mixed with 200 kg of the above polyol system composition using a high-pressure foaming machine to prepare a hard urethane foam board. The surface of the hard urethane foam board was finished with 0.08 mm thick aluminum sheet, A urethane foam board product was obtained.

[ Example  8]

90.0 kg of the high heat-resistant low-reactive isocyanuric polyol prepared in Example 2, 54.0 kg of the poorly soft low-reactivity aromatic polyester polyol prepared in Example 4, 26.0 kg of the foaming agent HCFC-141b, kg of a flame retardant, 20.0 kg of a flame retardant TCPP, 2.0 kg of a catalyst PC-5, 3.0 kg of T-45 and 1.0 kg of water to prepare 200 kg of a polyol system composition.

In a urethane foam production line, 240 kg of polyisocyanate was mixed with 200 kg of the polyol system composition using a high-pressure foaming machine to prepare a rigid urethane foam board. The surface of the rigid urethane foam board was finished with a 0.12 mm thick fabric aluminum sheet A rigid urethane foam board product was obtained.

The rigid urethane foam board prepared in Example 7 and the rigid urethane foam board prepared in Example 8 were each tested by the Korea Shipbuilding & Marine Engineering Institute to evaluate the flame retardant properties. It was as follows.

  Test Specification    Flammability rating Heat release rate KS F ISO 5660-1: 2008
Gas hazard KS F 2271: 2006   Semi-incombustible material (flame retardant grade 2) suitable

FIGS. 3A and 3B show the hard polyurethane foam board manufactured according to the seventh embodiment to the Korea Shipbuilding & Marine Engineering Research Institute, and scan a copy of the test report issued there.

The urethane foam foam produced according to the present invention is excellent in flame retardancy and heat resistance, and thus can be very usefully used for providing a polyurethane foam heat insulation board used as an interior material for apartment complexes and buildings.

The present invention relates to a process for producing a urethane foam, which uses an epoxy-bonded triglycidyl isocyanurate compound, which has not been attempted so far, and which can control the reaction rate using glycol compounds having different reaction orders, A polyurethane foam board capable of improving flame retardancy and heat resistance can be manufactured.

In addition, the polyurethane foam according to the present invention was subjected to a test by the Korea Shipbuilding & Marine Equipment Research Institute and it was clearly proved that the flame retardancy was excellent.

As described above, the present invention provides a method for producing a polyol compound for producing a high heat and low-reactivity polyurethane according to the present invention, a method for producing a polyol compound for producing a high- and low-reactivity polyurethane, A method for producing a polyurethane foam foam using a polyol compound for producing soft and low reactive polyurethanes and a method for manufacturing a board for the polyurethane foam foam have been described in detail. However, the present invention is not limited to the description of the most preferred embodiments of the present invention, It is to be understood that the invention is not limited thereto and that the scope thereof is determined and defined by the appended claims.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope of the present invention.

Claims (6)

Reacting a triglycidyl isocyanurate compound having an epoxy group bonded thereto with a glycol compound having a first order reaction to prepare a triglycidyl isocyanurate polyol having a first reaction order;
A triglycidyl isocyanurate polyol having a first order reaction sequence and propylene oxide are reacted with the triglycidyl isocyanurate polyol so as to have a second order reaction degree to the triglycidyl isocyanurate polyol, Forming a diallyl isocyanurate polyol; To
A method for producing an isocyanuric polyol compound for producing a polyurethane having high heat resistance and low reactivity.
The method according to claim 1,
The glycol compound may be selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,4-butanediol (1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and mixtures thereof. The polyisocyanate composition according to claim 1, A method for producing an anionic polyol compound.
3. The method of claim 2,
Wherein the glycol compound is ethylene glycol, diethylene glycol, or propylene glycol. 7. The method for producing an isocyanuric polyol compound for polyurethane according to claim 1, wherein the glycol compound is ethylene glycol, diethylene glycol, or propylene glycol.
Reacting a triglycidyl isocyanurate compound having an epoxy group bonded thereto with a glycol compound having a first order reaction to prepare a triglycidyl isocyanurate polyol having a first reaction order;
A polyurethane having a high heat-resistant low-reactivity, which reacts the triglycidyl isocyanurate polyol having the first order reaction degree with propylene oxide to have a second order reaction with the triglycidyl isocyanurate polyol Preparing an isocyanuric polyol compound for preparation;
30 to 60 parts by weight of an isocyanuric polyol compound for producing polyurethane having a high heat resistance and low reactivity and 40 to 70 parts by weight of a foaming agent, a catalyst, a flame retardant and an additive were blended to prepare a polyol composition for urethane production. Reacting with isocyanate; To
By weight based on the weight of the hard polyurethane foam board.
Reacting a triglycidyl isocyanurate compound having an epoxy group bonded thereto and a glycol compound having a first order reaction order to produce a triglycidyl isocyanurate polyol having a first order reaction degree, Heat-resistant low-reactivity isocyanuric polyol compound for polyurethane production, which reacts a syndiotactic isocyanurate polyol with propylene oxide to have a secondary reaction order to the triglycidyl isocyanurate polyol ; ≪ / RTI >
A propylene oxide adduct is added to a glycol compound having a terminal hydroxyl group at the terminal thereof to form a modified glycol compound having a first order reaction order and a second order order, Condensing an aromatic organic acid to produce a polyester polyol compound for producing a highly reactive and low-reactivity polyurethane having hydroxyl groups of a second order reaction at both ends thereof;
25 to 35 parts by weight of an isocyanuric polyol compound for producing polyurethane having a high heat resistance and a low reactivity, 35 to 50 parts by weight of an aromatic polyester polyol compound having a high hardness for producing polyurethane and having low reactivity and a blowing agent, And 25 to 30 parts by weight of an aromatic polyisocyanate to prepare a polyol composition for urethane production, followed by reaction with an aromatic polyisocyanate in a building interior material production line; To
By weight based on the weight of the hard polyurethane foam board.
Reacting a triglycidyl isocyanurate compound having an epoxy group bonded thereto and a glycol compound having a first order reaction order to produce a triglycidyl isocyanurate polyol having a first order reaction degree, Heat-resistant low-reactivity isocyanuric polyol compound for polyurethane production, which reacts a syndiotactic isocyanurate polyol with propylene oxide to have a secondary reaction order to the triglycidyl isocyanurate polyol ; ≪ / RTI >
A propylene oxide adduct is added to a glycol compound having a terminal hydroxyl group at the terminal thereof to form a modified glycol compound having a first order reaction order and a second order order, Condensing an aromatic organic acid to produce a polyester polyol compound for producing a highly reactive and low-reactivity polyurethane having hydroxyl groups of a second order reaction at both ends thereof;
25 to 35 parts by weight of an isocyanuric polyol compound for producing polyurethane having a high heat resistance and a low reactivity, 35 to 50 parts by weight of an aromatic polyester polyol compound having a high hardness for producing polyurethane and having low reactivity and a blowing agent, 25 to 30 parts by weight of a polyol composition to form a polyol composition for urethane production, followed by reaction with an aromatic polyisocyanate in a building interior material production line;
Preparing a polyurethane foam board by reacting with an aromatic polyisocyanate in the building interior material production line, and attaching an aluminum sheet or a fabric aluminum sheet to the surface of the polyurethane foam board; To
Wherein the hard polyurethane foam panel further comprises a thermoplastic resin.

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