KR102618891B1 - Composition for manufacturing of phenolic foam and phenolic foam manufactured therefrom - Google Patents

Abstract

The present invention relates to an additive composition for producing phenol foam containing an inorganic acid containing a metal and to a phenol foam manufactured using the composition. Specifically, the additive composition for producing phenolic foam according to the present invention cures quickly even when a low-viscosity phenolic resin is cured at a low temperature, and the phenol foam manufactured with the composition has physical properties such as thermal conductivity, compressive strength, bending failure load, and density. As it forms excellent, intact cells and has a very low level of residual formaldehyde, it has excellent insulation properties and contains almost no harmful substances, making it useful as an eco-friendly building material that is safe for the human body.

Description

Composition for producing phenolic foam and phenol foam manufactured therefrom {COMPOSITION FOR MANUFACTURING OF PHENOLIC FOAM AND PHENOLIC FOAM MANUFACTURED THEREFROM}

The present invention relates to a composition for producing phenol foam containing an inorganic acid containing a metal and to a phenol foam manufactured using the composition.

Organic insulation materials, which are used for thermal insulation and cold insulation in industrial fields such as building interior and exterior insulation, indoor interior, interior insulation of railway vehicles, power plants, and nuclear power, have poor flame retardancy and heat resistance, and especially in the event of a fire, toxic gases and smoke are generated, making fire suppression difficult. there is a problem. On the other hand, inorganic insulation materials such as gypsum board and glass fiber are harmful to the human body, have poor thermal conductivity, and have problems in that their performance deteriorates when absorbing water.

Accordingly, phenol foam is widely used to solve the above problems. Phenol foam is a thermosetting plastic foam made by curing phenol resin with thermochemically stable properties and has excellent flame retardancy, heat resistance, and low smoke properties, and is widely used in various countries around the world. It is in the spotlight as it satisfies the standards for flame retardant materials. In addition, phenol foam is known to be the safest organic plastic material against flames as it produces less smoke or harmful gases in the event of a fire.

In addition, phenolic resin, which is the raw material of phenolic foam, has excellent heat resistance at high temperatures and shows a high residual carbonization rate even when exposed to high temperatures for a long period of time. Not only does it have less strength deterioration than other foamed plastics, but it is also lightweight, rust-proof, and corrosion-resistant compared to metal materials. outstanding.

Phenol foam using such phenol resin is usually manufactured by mixing ingredients such as plasticizer, hardener, flame retardant, foam stabilizer, and nucleating agent with a certain ratio of phenol resin and then curing it. At this time, in order to increase the insulation of the manufactured phenol foam, the curing temperature must be kept low to maintain the cell structure within the phenolic foam. However, if cured at low temperature, the mechanical properties of the manufactured phenol foam may deteriorate or residual formaldehyde may be reduced. If the level is high, it can be harmful to the human body. Accordingly, in order to solve this problem, a method of using a high-viscosity phenol resin of 80,000 to 600,000 cps and producing a ring-substituted phenol content within 10% of the phenol resin has been proposed. However, because a high-viscosity phenolic resin is used, a high-viscosity phenol resin is used, and It is difficult to control the manufacturing process and it is uneconomical as it is hardened in .

In this regard, Republic of Korea Patent Publication No. 10-2015-0134939 discloses a foamed phenolic resin composition that has excellent strength and density and can be stably applied to actual construction sites and various application fields, and is an eco-friendly building material with almost no formaldehyde emissions. The phenol foam manufactured from this is disclosed.

Republic of Korea Patent Publication No. 10-2015-0134939

The purpose of the present invention is to provide a composition for producing phenol foam containing an aqueous solution of an inorganic acid containing a metal and a phenol foam manufactured using the composition.

In order to achieve the above object, the present invention includes a phenolic resin; Aqueous solutions of inorganic acids containing metals; And it provides a composition for producing phenol foam containing at least one additive selected from the group consisting of a foaming agent, a plasticizer, a curing agent, a surfactant, a flame retardant, and a nucleating agent.

Additionally, the present invention provides a phenol foam manufactured using the composition for producing phenol foam.

The composition for producing phenolic foam according to the present invention cures quickly even when a low-viscosity phenolic resin is cured at a low temperature, and the phenolic foam manufactured with the composition has excellent physical properties such as thermal conductivity, compressive strength, bending failure load, and density, It forms an intact cell and has a very low level of residual formaldehyde, so it has excellent insulation properties and contains almost no harmful substances, making it useful as an eco-friendly building material that is safe for the human body.

Hereinafter, the present invention will be described in detail.

The present invention relates to a phenolic resin; Aqueous solutions of inorganic acids containing metals; And it provides a composition for producing phenol foam containing at least one additive selected from the group consisting of a foaming agent, a plasticizer, a curing agent, a surfactant, a flame retardant, and a nucleating agent.

The composition for producing phenol foam may include an aqueous solution of an inorganic acid containing a metal as an additive. The metal may be a transition metal. The term 'transition metal' refers to elements from groups 3 to 11 of the 4th to 7th period of the periodic table, and can form complex compounds. The transition metal may include all types of transition metals known in the art, and may be, for example, one or more selected from the group consisting of manganese, molybdenum, vanadium, chromium, and tungsten. In one embodiment of the present invention, the transition metal may be manganese, molybdenum, or vanadium.

More specifically, the transition metal may be a transition metal with excellent solubility in water. When a transition metal with low solubility in water is used, the effect of adding additives may be reduced, or the physical properties of the manufactured phenolic foam may be reduced due to the addition of an excessive amount of water. For example, the transition metal may be manganese.

As used herein, the term 'inorganic acid' refers to an acid produced by a chemical reaction of an inorganic compound. The inorganic acid may include all types of inorganic acids known in the art, for example, hydrochloric acid (HCl), nitric acid (HNO ₃ ), phosphoric acid (H ₂ PO ₄ ), sulfuric acid (H ₂ SO ₄ ), and boric acid. It may be one or more selected from the group consisting of (H ₃ BO ₃ ) and carbonic acid (H ₂ CO ₃ ). In one embodiment of the present invention, the inorganic acid may be sulfuric acid.

An aqueous solution of an inorganic acid containing the metal can be prepared by mixing a transition metal in the form of a salt with an inorganic acid and reacting it. The amounts of transition metal and inorganic acid used in the above production may be appropriately selected by a person skilled in the art and may be modified as necessary. The preparation may further include filtering the reaction mixture. The filtration is a step for removing precipitates generated during the reaction, and can be performed by a commonly used method. The filtered mixture can be obtained as an aqueous solution.

The aqueous inorganic acid solution containing the metal may include the metal in an amount of 8 to 15 parts by weight based on 100 parts by weight of the aqueous inorganic acid solution. When the metal is included in the inorganic acid aqueous solution within the above range, the curing rate can be increased during the production of phenol foam, thereby improving phenol foam production efficiency.

An aqueous solution of inorganic acid containing the above metal can be used at an appropriate concentration by a person skilled in the art. Specifically, the additive composition is 10% (w/w) or more, 10 to 50% (w/w), 10 to 40% (w/w), 10 to 30% (w/w), 10 to 25%. (w/w), 15 to 50% (w/w), 15 to 40% (w/w), 15 to 30% (w/w) or 15 to 25% (w/w). there is. If the concentration of the additive composition exceeds 50% (w/w), it takes a long time to concentrate the aqueous solution of inorganic acid containing metal, making it uneconomical, and if the concentration of the additive composition is less than 10% (w/w), it is difficult to cure when manufacturing phenol foam. The performance and physical properties of the manufactured phenol foam may deteriorate.

The aqueous inorganic acid solution containing the metal may be included in an appropriate amount known in the art. Specifically, 5 parts by weight or less, 0.5 to 5 parts by weight, 0.5 to 4 parts by weight, 0.5 to 3 parts by weight, 1 to 5 parts by weight, 1 to 4 parts by weight, or 1 to 3 parts by weight, based on 100 parts by weight of the phenolic resin. It may be included by weight. If the inorganic acid aqueous solution containing the metal is added in an amount of less than 0.5 parts by weight, the effect of improving the curing speed is minimal, and if it is added in an amount exceeding 5 parts by weight, it may be difficult to control the process due to excessive heat generation during curing.

The composition for producing phenolic foam of the present invention may include a phenol-based resin. The term 'phenolic resin' refers to a thermosetting resin produced by reacting phenols and formaldehydes. The phenol-based resin can be produced by inducing addition and condensation reactions of phenol and formaldehyde at an appropriate temperature and time, and then neutralizing them with acids such as hydrochloric acid and formic acid. At this time, the phenolic resin can be used without limitation as long as it is a phenolic resin used in foam production. For example, the phenol-based resin may be a resol or novolac type.

The resol type phenolic resin is synthesized using alkali metal hydroxide or alkaline earth metal hydroxide, and may include an ammonia resol type phenol resin synthesized using ammonia. Meanwhile, the novolak-type phenol-based resin may be synthesized using an acid catalyst. Such phenol-based resin may be a mixture of resol or novolac type.

The phenol-based resin may be a low-viscosity phenol-based resin. Low-viscosity phenol-based resin has a low viscosity, making it easy to control during the process, and has excellent thermal conductivity due to the low moisture content in the resin, making it suitable as a material for insulation. For example, the low viscosity phenolic resin has a viscosity of 80,000 cps or less, 5,000 to 80,000 cps, 5,000 to 70,000 cps, 5,000 to 60,000 cps, 20,000 to 80,000 cps, 20,000 to 70,000 cps, 20,000 cps at 25°C. to 60,000 cps, to 40,000 It may have a viscosity of 80,000 cps, 40,000 to 70,000 cps, or 40,000 to 60,000 cps.

Meanwhile, the phenol-based resin may contain 3 to 15% moisture. If the moisture contained in the phenolic resin is less than 3%, the viscosity of the resin increases, making it difficult to control the process, and if it exceeds 15%, the physical properties of the manufactured phenol foam may decrease and the thermal conductivity may increase.

The composition for producing phenolic foam of the present invention may include any one or more selected from the group consisting of a foaming agent, a plasticizer, a curing agent, a surfactant, a flame retardant, and a nucleating agent.

The foaming agent may be added to facilitate foaming of the phenol resin. For example, the foaming agent may include any foaming agent known in the art to be used for foaming phenol foam. Specifically, the blowing agent may be at least one selected from the group consisting of hydrofluoroolefin (HFO)-based compounds, hydrocarbon-based compounds, and halogenated hydrocarbon-based compounds.

The hydrofluoroolefin-based compound may include a chlorinated hydrofluoroolefin-based compound, a non-chlorinated hydrofluoroolefin-based compound, or a mixture thereof. For example, the hydrofluoroolefin compound is trans 1-chloro-3,3,3-trifluoropropene (trans CF ₃ CH=CClH), cis 1-chloro-3,3,3-trifluoro Propene (cis CF ₃ CH=CClH), trans 1-chloro-2,3,3-trifluoropropene (trans CHF ₂ CF=CClH), cis 1-chloro-2,3,3-trifluoro Propene (cis CHF ₂ CF=CClH), trans 1-chloro-1,3,3-trifluoropropene (trans CHF ₂ CH-CClF), cis 1-chloro-1,3,3-trifluoro Propene (cis CHF ₂ CH=CClF), trans 2-chloro-1,3,3-trifluoropropene (trans CHF ₂ CCl-CHF), cis 2-chloro-1,3,3-trifluoro Propene (cis CHF ₂ CCl=CHF), trans 2-chloro-1,1,3-trifluoropropene (trans CH ₂ FCCl-CF ₂ ), cis 2-chloro-1,1,3-trifluoro Propene (cis CH ₂ FCCl=CF ₂ ), trans 3-chloro-1,2,3-trifluoropropene (trans CH ₂ ClCF=CF ₂ ), cis 3-chloro-1,1,2- Trifluoropropene (cis CH ₂ ClCF=CF ₂ ), trans 3-chloro-2,3,3-trifluoropropene (trans CF ₂ ClCF=CH ₂ ), cis 3-chloro-2,3, Monochlorotrifluoropropene such as 3-trifluoropropene (cis CF ₂ ClCF=CH ₂ ); 2,3,3-trifluoropropene (CHF ₂ CF=CH ₂ ), 1,1,2-trifluoropropene (CH ₃ CF=CF ₂ ), 1,1,3-trifluoropropene Trifluoropropenes such as pen (CH ₂ FCH=CF ₂ ) and 1,3,3-trifluoropropene (CHF ₂ CF=CH ₂ ); 1,2,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,3,3,3-tetrafluoro-1-propene , 1,1,2,3-tetrafluoro-1-propene, 1,1,3,3-tetrafluoro-1-propene, 1,2,3,3-tetrafluoro-1-prop Tetrafluoropropene such as pen; 1,2,3,3,3-pentafluoro-1-propene, 1,1,3,3,3-pentafluoro-1-propene, 1,1,2,3,3-pentafluorine Pentafluoropropene such as ro-1-propene; 2,3,3,4,4,4-hexafluoro-1-butene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,4,4, 4-hexafluoro-1-butene, 1,2,3,4,4,4-hexafluoro-1-butene, 1,2,3,3,4,4-hexafluoro-2-butene, 1,3,3,4,4,4-hexafluoro-1-butene, 1,2,3,4,4,4-hexafluoro-1-butene, 1,2,3,3,4, 4-hexafluoro-1-butene, 1,1,2,3,4,4-hexafluoro-2-butene, 1,1,1,2,3,4-hexafluoro-2-butene, 1,1,1,2,3,3-hexafluoro-2-butene, 1,1,1,3,4,4-hexafluoro-2-butene, 1,1,2,3,3, It may include hexafluorobutene such as 4-hexafluoro-1-butene.

Meanwhile, the hydrocarbon-based compound may include hydrocarbons having 1 to 6 carbon atoms, and specifically, the hydrocarbon-based compound may include n-butane, isobutane, n-pentane, isopentane, cyclopentane, n-hexane, etc. You can. Additionally, the halogenated hydrocarbon-based compound may be a halogen-substituted compound having 1 to 6 carbon atoms. Specifically, the halogenated hydrocarbon compounds include fluorinated hydrocarbons such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride, halogenated hydrocarbons, brominated hydrocarbons, and iodine hydrocarbon compounds. It may be any one or more selected from the group.

The foaming agent may be added in an appropriate amount by a person skilled in the art, specifically, 2 to 20 central parts, 2 to 15 central parts, 2 to 10 central parts, 4 to 20 central parts, based on 100 parts by weight of the phenolic resin. , it may be included in 4 to 15 central regions or 4 to 10 central regions. If the foaming agent is added in an amount of less than 2 parts by weight, the thermal conductivity increases, and if it is added in an amount exceeding 20 parts by weight, the density of the produced phenolic foam may decrease and the physical properties may deteriorate.

The plasticizer may be added to increase durability by preventing foaming gas from being released from bubbles formed in the manufactured phenol foam and being replaced with air. The plasticizer may be any type of plasticizer known in the art. For example, the plasticizer may be an aromatic diol or aromatic monoalcohol such as ester, ester polyol, ether polyol, phosphorus compound, resorcinol, o,m,p-cresol, catechol, hydroquinone, salicyl alcohol, or epoxy resin. And it may be any one or more selected from the group consisting of fluorine-based compounds.

The plasticizer can be added in an appropriate amount by those skilled in the art, specifically, 2 to 30 parts by weight, 2 to 20 parts by weight, 2 to 15 parts by weight, and 2 to 10 parts by weight based on 100 parts by weight of the phenolic resin. , 4 to 30 parts by weight, 4 to 20 parts by weight, 4 to 15 parts by weight, or 4 to 10 parts by weight. If the plasticizer is added in less than 2 parts by weight, the flexibility of the manufactured phenolic foam may be reduced, and if it is added in more than 30 parts by weight, the physical properties and flame retardancy of the manufactured phenol foam may be reduced.

The curing agent may be added to help the phenol foam harden at a desired foaming rate, improve the appearance of the product, and maintain mechanical strength. The curing agent may be any curing agent known to be capable of curing phenolic resins. For example, the curing agent may be any one or more selected from the group consisting of phenolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, naphthalenesulfone, arylsulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. there is.

The curing agent may be added in an appropriate amount by a person skilled in the art, specifically, 2 to 20 central parts, 2 to 15 central parts, 2 to 10 central parts, 4 to 20 central parts per 100 central parts of the phenolic resin. , it may be included in 4 to 15 central regions or 4 to 10 central regions. If the curing agent is added in an amount of less than 2 parts by weight, it does not harden, so the physical properties of the manufactured phenolic foam deteriorate and the thermal conductivity increases, and if it is added in an amount exceeding 20 parts by weight, the pH of the phenolic foam may decrease and corrosion may increase.

The surfactant may be added to uniformize the cells in the phenolic foam and increase hydrophobicity. The surfactant may be any type of surfactant known in the art. Specifically, it may be composed of an alkylether, an ionic surfactant, or a non-ionic surfactant may be used, and the component may be used alone or Can be used by mixing. For example, the surfactant may include a siloxane-based compound, castor oil-ethylene oxide, ester compound, ether compound, silicone-based compound, fluorine-based compound, etc.

The surfactant can be added in an appropriate amount by those skilled in the art, specifically, 1 to 20 parts by weight, 1 to 15 parts by weight, 1 to 10 parts by weight, and 1 to 5 parts by weight based on 100 parts by weight of the phenolic resin. parts, 2 to 20 parts by weight, 2 to 15 parts by weight, 2 to 10 parts by weight, or 2 to 5 parts by weight. If the surfactant is added in less than 1 part by weight, the cell size formed in the produced phenol foam may become irregular and moisture permeability may increase, and if it is added in excess of 20 parts by weight, the physical properties of the produced phenol foam may decrease and thermal conductivity may decrease. It can rise.

The flame retardant may be added to improve the flame retardancy of phenol foam. The flame retardant can be used alone or in combination with all types of flame retardants known in the art. Specifically, the flame retardant may include a halogen-based, phosphorus-based, halogen-phosphorus-based, boron-based flame retardant, etc. For example, the flame retardant is TCPP (Tris (1-Chloro-2-Propyl) Phosphate), TEP (Triethyl Phosphate), TEPP (Tetraethyl piperazine-1,4-diyldiphosphoramidate), TCP (Tricresyl Phosphate), RDP (Resorcinol bis ( diphenyl phosphate)), APP (Ammonium Poly Phosphate), DOPO-HQ (10-(2,5-dihydroxyphenyl)-9,10-dihydro- 9-xa-10-phosphaphenanthrene-10-oxide), phosphazene It may include boric acid (H ₃ BO ₃ ), borax (Na ₂ B ₄ O ₇ ), expandable graphite, etc.

The flame retardant can be added in an appropriate amount by those skilled in the art, specifically, 1 to 20 parts by weight, 1 to 15 parts by weight, 1 to 10 parts by weight, and 1 to 5 parts by weight based on 100 parts by weight of the phenolic resin. , 2 to 20 parts by weight, 2 to 15 parts by weight, 2 to 10 parts by weight, or 2 to 5 parts by weight. If the flame retardant is added in an amount of less than 1 part by weight, it is difficult to properly implement the flame retardant performance of the phenolic foam, and if it is added in an amount exceeding 20 parts by weight, the physical properties of the manufactured phenolic foam deteriorate and the viscosity increases, making process control difficult.

In addition, the composition for producing phenol foam according to the present invention may further include a nucleating agent to improve the function of the surfactant and insulation performance. The nucleating agent can be used alone or in combination with all types of nucleating agents known in the art, specifically, silane-based compounds, siloxane-based compounds, perfluoroalkane-based compounds, hydrofluoroalkane-based compounds, and hydrofluoroether-based compounds. Compounds, chlorinated hydrofluoroolefin-based compounds, non-chlorinated hydrofluoroolefin-based compounds, hydrochloroalkenes, etc. can be used. More specifically, the nucleating agent is BSmethyldisilazane, dimethoxydimethylsilane, hexadimethyldisiloxane, trans 1-chloro-3,3,3-trifluoropropene, cis 1-chloro-3,3,3 -trifluoropropene, trans 1-chloro-2,3,3-trifluoropropene, cis 1-chloro-2,3,3-trifluoropropene, trans 1-chloro-1,3, 3-trifluoropropene, cis 1-chloro-1,3,3-trifluoropropene, trans 2-chloro-1,3,3-trifluoropropene, cis 2-chloro-1,3 ,3-trifluoropropene, trans 2-chloro-1,1,3-trifluoropropene, cis 2-chloro-1,1,3-trifluoropropene, trans 3-chloro-1, 2,3-trifluoropropene, cis 3-chloro-1,1,2-trifluoropropene, trans 3-chloro-2,3,3-trifluoropropene, cis 3-chloro-2 , monochlorotrifluoropropene such as 3,3-trifluoropropene; Trees such as 2,3,3-trifluoropropene, 1,1,2-trifluoropropene, 1,1,3-trifluoropropene, 1,3,3-trifluoropropene fluoropropene; 1,2,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,3,3,3-tetrafluoro-1-propene , 1,1,2,3-tetrafluoro-1-propene, 1,1,3,3-tetrafluoro-1-propene, 1,2,3,3-tetrafluoro-1-prop tetrafluoropropene such as pen; 1,2,3,3,3-pentafluoro-1-propene, 1,1,3,3,3-pentafluoro-1-propene, 1,1,2,3,3-pentafluorine Pentafluoropropene such as ro-1-propene; 2,3,3,4,4,4-hexafluoro-1-butene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,4,4, 4-hexafluoro-1-butene, 1,2,3,4,4,4-hexafluoro-1-butene, 1,2,3,3,4,4-hexafluoro-2-butene, 1,3,3,4,4,4-hexafluoro-1-butene, 1,2,3,4,4,4-hexafluoro-1-butene, 1,2,3,3,4, 4-hexafluoro-1-butene, 1,1,2,3,4,4-hexafluoro-2-butene, 1,1,1,2,3,4-hexafluoro-2-butene, 1,1,1,2,3,3-hexafluoro-2-butene, 1,1,1,3,4,4-hexafluoro-2-butene, 1,1,2,3,3, Hexafluorobutene such as 4-hexafluoro-1-butene; Difluoromethane, fluoroethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, pentafluoropropane, hexafluoropropane, pentafluoropropane, pentafluorobutane, hexafluoropropane It may include fluorobutane and its isomers, 1,1,2,2-tetrafluoroethyl methyl ether, phenylperfluorobutyl ether, dichloroethene, dichloropropene, dichlorobutene, etc.

In addition to the components described above, the composition for producing phenol foam according to the present invention may further include at least one additive known in the art within a range that does not impair the effect of the aqueous solution of inorganic acid containing a metal. Specifically, the composition for producing phenol foam according to the present invention may further include a neutralizing agent, a neutralizing agent, an emulsifier, etc. These may be used alone or in combination of two or more, and the content of these additives may be appropriately selected by a person skilled in the art.

Additionally, the present invention provides a phenol foam manufactured using the composition for producing phenol foam.

The phenol foam can be manufactured by a method including the step of putting the composition for producing phenolic foam of the present invention having the characteristics described above into a mold and curing it. For example, the composition for producing phenolic foam includes a phenol-based resin; Aqueous solutions of inorganic acids containing metals; And it may include any one or more additives selected from the group consisting of foaming agents, plasticizers, curing agents, surfactants, flame retardants, and nucleating agents.

The curing can be performed by a person skilled in the art under appropriate conditions and methods. Specifically, the curing may be performed at a temperature of 70°C or less, 10 to 70°C, 20 to 70°C, 30 to 70°C, or 40 to 70°C. At this time, the composition for producing phenolic foam may be mixed by stirring at a constant speed and then cured in a mold. Any mold that can release moisture generated during the curing reaction of the composition for producing phenolic foam to the outside can be used. The size of the mold can be designed to an appropriate size by a person skilled in the art as needed.

In addition, the method for producing phenolic foam may further include an additional reaction step in an oven for effects such as yield and moisture discharge. The further reaction can be carried out at an appropriate temperature and time by a person skilled in the art.

The phenolic foam according to the present invention not only cures quickly and has excellent curing characteristics, but also has excellent physical properties such as thermal conductivity, compressive strength, bending failure load, and density even when manufactured by curing at low temperatures, and has an intact form within the cured phenolic foam. It forms a cell and has a very low level of residual formaldehyde, so it has excellent insulation properties and contains almost no harmful substances, so it can be used as an eco-friendly building material that is safe for the human body.

Specifically, the phenol foam may include a transition metal, and specifically, the transition metal may be one or more selected from the group consisting of manganese, molybdenum, vanadium, chromium, and tungsten. The transition metal may be included in an amount of 0.05 to 0.30% by weight based on 100% by weight of the phenolic foam. If it is included in the above content range, it may have the effect of improving phenolic foam production efficiency by increasing the curing speed when manufacturing phenol foam.

In addition, the phenolic foam is 0.010 to 0.035 W/m·K, 0.010 to 0.030 W/m·K, 0.010 to 0.025 W/m·K, 0.015 to 0.035 W/m·K, 0.015 to 0.030 W/m·K. Alternatively, it may have a thermal conductivity of 0.015 to 0.025 W/m·K. On the other hand, the phenolic foam has a compressive strength of 40 to 250 kpa, 40 to 210 kpa, 40 to 170 kpa, 80 to 250 kpa, 80 to 210 kpa, 80 to 170 kpa, 120 to 250 kpa, according to KS M ISO 845. It may be 120 to 210 kpa or 120 to 170 kpa. Additionally, the phenolic foam may have a bending failure load of 15 to 60 N, 15 to 50 N, 15 to 40 N, 25 to 60 N, 25 to 50 N, or 25 to 40 N.

On the other hand, the phenol foam according to the present invention is 1.0 to 10.0% (v/v), 1.0 to 8.0% (v/v), 1.0 to 6.0% (v/v), 2.0 to 10.0% (v/v), 2.0 It may have a moisture absorption of from 8.0% to 2.0 to 6.0% (v/v). In addition, the phenolic foam is 3.0 to 20.0 ng/m·s·Pa, 3.0 to 15.0 ng/m·s·Pa, 3.0 to 10.0 ng/m·s·Pa, 5.0 to 20.0 ng/m·s·Pa, It may have a water vapor permeability of 5.0 to 15.0 ng/m·s·Pa or 5.0 to 10.0 ng/m·s·Pa.

Furthermore, the phenolic foam according to the present invention is 20 to 60 kg/m3, 20 to 50 kg/m3, 20 to 40 kg/m3, 30 to 60 kg/m3, 30 to 50 kg/m3 or 30 to 40 kg/m3. It can have a density of Additionally, the phenolic foam may have a closed cell ratio of 60 to 99%, 60 to 95%, 70 to 99%, 70 to 95%, 80 to 99%, or 80 to 95%.

In other words, the phenol foam manufactured with the composition for producing phenolic foam according to the present invention hardens quickly at low temperature and has excellent physical properties and can be usefully used as an eco-friendly building material.

Hereinafter, the present invention will be described in detail through the following examples. However, the following examples are only for illustrating the present invention and are not intended to limit the present invention thereto. Anything that has substantially the same structure as the technical idea described in the claims of the present invention and achieves the same operation and effect is included in the technical scope of the present invention.

Manufacturing example 1. Preparation of manganese acid aqueous solution

25.0 g of barium manganate and 58.6 g of 17% dilute sulfuric acid (H ₂ SO ₄ ) were added to a 250 mL beaker and mixed with stirring for 1 hour. The mixture was passed through filter paper to remove barium sulfate precipitate, and 60.8 g of 20% (w/w) manganese acid aqueous solution was obtained.

Manufacturing example 2. Preparation of molybdic acid aqueous solution

60.8 g of 20% (w/w) molybdic acid aqueous solution was obtained under the same conditions and method as in Preparation Example 1, except that barium molybdate was used instead of barium manganate.

Manufacturing example 3. vanadic acid Preparation of aqueous solutions

60.8 g of 20% (w/w) vanadic acid aqueous solution was prepared under the same conditions and method as in Preparation Example 1, except that barium vanadate was used instead of barium manganate.

Example 1. Production of phenol foam-(1)

Phenol foam was prepared in the following manner by adding the manganese acid aqueous solution prepared in Preparation Example 1.

Specifically, 2 parts by weight of the aqueous manganese acid solution according to Example 1, 100 parts by weight of a phenol resin with a viscosity of 47,500 cps (25°C), 7 parts by weight of cyclopentane, 7 parts by weight of ether polyol, 8 A foaming mixture was prepared by mixing xylenesulfonic acid and 3 parts by weight of a silicone-based surfactant with stirring. The prepared foaming mixture was placed in a mold measuring 400×400×75 mm and cured at 55°C for 20 minutes. Phenolic foam to which an aqueous manganese acid solution was added was prepared by maturing the cured foam in an oven at 70°C for 15 hours.

Example 2. Preparation of phenolic foam-(2)

A phenolic foam to which an aqueous molybdic acid solution was added was prepared in the same manner and conditions as in Example 1, except that the aqueous molybdic acid solution prepared in Preparation Example 2 was added instead of the aqueous manganese acid solution.

Example 3. Preparation of phenol foam-(3)

A phenolic foam to which an aqueous vanadic acid solution was added was prepared in the same manner and under the same conditions as in Example 1, except that the aqueous vanadic acid solution prepared in Preparation Example 3 was added instead of the aqueous manganese acid solution.

Example 4. Preparation of phenol foam-(4)

A phenolic foam to which an aqueous manganic acid solution was added was prepared in the same manner and conditions as in Example 1, except that the foaming mixture was cured at 70°C instead of 55°C.

Comparative Example 1. Preparation of phenol foam-(1)

Phenol foam was prepared in the same manner and under the same conditions as Example 1, except that 1.7 parts by weight of distilled water was added instead of adding the aqueous manganese acid solution.

Comparative Example 2. Preparation of phenolic foam-(2)

Phenolic foam was manufactured using the same method and conditions as Comparative Example 1, except that the foaming mixture was cured at 70°C instead of 55°C.

Experimental Example 1. Physical properties of phenolic foam

The physical properties of the phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were measured as follows.

1-1. thermal conductivity

The phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were cut to a size of 300 × 300 mm to a thickness of 50 mm to obtain specimens, which were pretreated in a conventional manner. The thermal conductivity of the pretreated specimen was measured using a thermal conductivity device at a temperature of 20°C according to the method specified in KS L 9016.

1-2. compressive strength

The phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were cut to a size of 50 × 50 × 50 mm to obtain specimens, and the compressive strength was measured according to the method specified in KS M ISO 844. Specifically, the specimen was placed between the wide plates of a universal testing machine (UTM) and the testing machine was set at a speed of 5 mm/min. After starting the experiment, the strength of the first compression yield point that appeared while the thickness was decreasing was recorded.

1-3. Flexural failure load

The phenol foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were cut to a size of 250 × 100 × 20 mm to obtain specimens, and the bending failure load was measured according to the method specified in KS M ISO 1209-1. . Specifically, the specimen was placed symmetrically on the support bar of the universal testing machine (UTM) so that a load could be applied perpendicularly to it, the pressure bar was lowered, and the position was set as the no-strain point. Afterwards, a load was applied to the specimen while moving the pressure bar at a speed of 10 ± 2 mm/min, and the load (N) corresponding to a bending deformation of 20 ± 0.2 mm was recorded. At this time, if the specimen was destroyed before the bending strain reached 20 mm, the failure load and bending were recorded.

1-4. moisture absorption rate

The phenol foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were cut to a size of 150 × 150 × 75 mm to obtain specimens, and the moisture absorption rate was measured according to the method specified in KS M ISO 2896. At this time, the initial mass of the obtained specimen was measured (m1), the specimen was assembled and immersed in a mesh net, and then hung on a scale to measure the mass (m2). After leaving it for 96 hours, the mass of the deposited net was measured (m3). The dimensions of the specimen before and after immersion were measured to calculate the volume, and the moisture absorption rate was calculated according to equation 1 below.

[Equation 1]

WAv(%): Moisture absorption rate (%)

m1: initial mass of the specimen

m2: mass of specimen immediately after immersion

m3: Specimen mass after 96 hours immersion

V ₀ : Specimen volume before immersion

V ₁ : Specimen volume after immersion

ρ: Density of water (1 g/㎤)

1-5. water vapor permeability

The phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were cut to a size of 150 × 150 × 25 mm to obtain specimens, and the water vapor permeability was measured according to the method specified in KS M ISO 1663. Specifically, a desiccant was placed at a thickness of 20 mm on the bottom of the assembly container, and the obtained specimen was placed at a distance of 15 mm from it. The mass of the specimen was measured at regular intervals for 24 hours under a temperature of 23°C and humidity of 50% until the average of five continuously measured mass changes per unit time was within 2%. Using the measured values, water vapor permeability was calculated according to Equations 2 and 3 below.

[Equation 2]

Wp (ng/m·s·Pa): Water vapor permeability

G: Average of 5 G ₁₂

A: Surface area of the test piece exposed to humidity (㎠)

P: Steam pressure difference (Pa), which is 1,400 Pa under the above test conditions.

s: Specimen thickness (mm)

[Equation 3]

m2-m1: Difference in mass of specimens measured twice in succession (㎍)

t2-t1: Time difference between two consecutive measurements of the mass of the specimen (h)

G ₁₂ : Mass change per unit time (㎍/h) when the mass of the specimen was measured twice in succession

1-6. density

The phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were cut into appropriate sizes to obtain specimens, and the obtained specimens were aged at 70°C for 10 to 20 hours, and then the density was calculated by a conventional method.

The physical properties of the phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 measured as above are shown in Table 1 below.

phenolic foam thermal conductivity
(W/m·K) compressive strength
(kpa) bending destruction
Load (N) moisture
Absorption rate (%) Water vapor permeability (ng/ms·Pa) density
(kg/㎥) Example 1 0.019 154 38 3.8 7.3 34 Example 2 0.021 142 32 4.9 8.8 38 Example 3 0.021 133 31 4.4 9.9 37 Example 4 0.033 148 37 3.7 6.9 35 Comparative Example 1 0.022 81 17 8.3 12.7 31 Comparative Example 2 0.027 115 35 6.9 10.4 44

As shown in Table 1, the phenol foams of Examples 1 to 3 prepared by adding aqueous solutions of manganese acid, molybdic acid, or vanadic acid were significantly superior to the phenol foams of Comparative Example 1 in which no inorganic acid containing a metal was added. Compressive strength and bending failure load were shown. In addition, the moisture absorption rate and water vapor permeability of the phenolic foams of Examples 1 to 3 were significantly lower.

In addition, the phenol foams of Examples 1 to 3 showed physical properties similar to those of the phenol foams cured at 70°C even when cured at 55°C. However, unlike the phenol foam (Comparative Example 2) manufactured by curing at 70°C without adding additives, the phenolic foam (Comparative Example 1) manufactured by curing at 55°C without adding additives according to the present invention has an overall low Compressive strength and bending failure load were observed, and water vapor permeability was significantly high.

Therefore, from the above results, it was found that by adding an aqueous solution of an inorganic acid containing a metal during the production of phenol foam, it was possible to manufacture phenol foam showing excellent physical properties even at a low curing temperature.

Experiment example 2. Transition metal content

The transition metal content of the phenol foam prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was measured as follows.

Specifically, a fixed amount of specimen was ground into powder and treated with 95% concentrated sulfuric acid in a fume hood. After heating it, a solution of 70% or more concentrated nitric acid and perchloric acid was added and reacted until the solution became transparent. When the solution became transparent, it was determined that the organic components had been decomposed. This was diluted in distilled water and analyzed with an ICP-AES device, and the results are shown in Table 2 below.

phenolic foam Transition metal types Content (wt%) Example 1 Mn 0.12 Example 2 Mo 0.21 Example 3 V 0.16 Example 4 Mn 0.12 Comparative Example 1 - - Comparative Example 2 - -

Experiment example 3. Curing characteristics (process efficiency)

The curing characteristics (process efficiency) of the phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were confirmed by measuring the time to reach the internal maximum curing temperature (T _max ) during curing. The experiment was conducted in a conventional manner, and it was judged that the shorter the time to reach T _max , the better the curing characteristics (process efficiency) were. The time to reach the measured internal maximum curing temperature is shown in Table 3 below.

phenolic foam _Tmax (s) Example 1 205 Example 2 227 Example 3 224 Example 4 181 Comparative Example 1 324 Comparative Example 2 241

As shown in Table 2, the phenol foams of Examples 1 to 4 had excellent curing rates due to the addition of an inorganic acid containing a transition metal. On the other hand, when the inorganic acid containing the transition metal according to the present invention was not added, the curing speed was fast only when cured at a temperature of 70 ° C. (Comparative Example 2), and when cured at a temperature of 55 ° C. (Comparative Example 1) The curing speed was very slow at 324 seconds.

Therefore, from the above results, it was seen that phenolic foam showing excellent curing properties could be manufactured by adding an aqueous solution of an inorganic acid containing a metal.

Experimental Example 4. Formation of cells in phenolic foam

By checking the closed cell ratio of the phenol foam prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the shape of the cells in the produced phenolic foam was confirmed. In the experiment, specimens were obtained by cutting phenolic foam into sizes of 25 × 25 × 25 mm, and the closed cell ratio was measured using a pycnometer according to the method specified in KS M ISO 4590. The measured results are shown in Table 4 below.

phenolic foam Closed cell rate (%) Example 1 94 Example 2 90 Example 3 89 Example 4 73 Comparative Example 1 90 Comparative Example 2 91

As shown in Table 3, the phenolic foams of Examples 1 to 4 had a high bubble formation rate. In particular, the phenol foams of Examples 1 to 3 cured at a low temperature of 55°C showed a higher closed cell rate, and the phenol foams manufactured using a low concentration of manganese acid had a significantly lower closed cell rate.

Therefore, from the above results, it was found that the phenol foam manufactured by adding an aqueous solution of an inorganic acid containing a metal exhibited excellent thermal insulation properties due to the complete formation of cells within the phenol foam.

Experiment example 5. Safety

By measuring the level of residual formaldehyde (FFA) contained in the phenol foam prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the safety of the phenol foam was confirmed. The experiment was conducted using samples prepared in accordance with the provisions of KS M 0000-1 (Measurement of formaldehyde and volatile organic compounds emissions from building interior materials, Part 1 General information). Dissipation amount measurement was performed according to the method specified in Part 2 (small chamber method). The measured levels of residual formaldehyde are shown in Table 5 below.

phenolic foam Residual formaldehyde (mg/㎥·h) Example 1 0.007 Example 2 0.009 Example 3 0.010 Example 4 0.006 Comparative Example 1 0.016 Comparative Example 2 0.012

As shown in Table 4, the phenol foams of Examples 1 to 4 showed a very small level of residual formaldehyde, but when the additive according to the present invention was not added or was added at a low concentration, the residual formaldehyde level was high. It was significantly high.

Therefore, from the above, it can be seen that phenol foam manufactured by adding an aqueous solution of inorganic acid containing metal contains almost no harmful substances, is safe for the human body, and can be usefully used as an eco-friendly building material.

Claims (19)

phenolic resin;
Aqueous solutions of inorganic acids containing metals; and
A composition for producing phenol foam, which is at least one selected from the group consisting of foaming agents, plasticizers, curing agents, surfactants, flame retardants and nucleating agents,
A composition for producing phenol foam, wherein the metal is at least one selected from the group consisting of manganese, molybdenum, vanadium, chromium, and tungsten.
delete delete The method of claim 1, wherein the inorganic acid is hydrochloric acid (HCl), nitric acid (HNO ₃ ), phosphoric acid (H ₂ PO ₄ ), sulfuric acid (H ₂ SO ₄ ), boric acid (H ₃ BO ₃ ), and carbonic acid (H ₂ CO ₃ ). ) A composition for producing phenol foam, which is at least one selected from the group consisting of.
The composition for producing phenolic foam according to claim 1, wherein the aqueous inorganic acid solution contains metal in an amount of 8 to 15 parts by weight based on 100 parts by weight of the aqueous inorganic acid solution.
The composition for producing phenol foam according to claim 1, wherein the aqueous inorganic acid solution is an aqueous solution with a concentration of 10% by weight or more.
The composition for producing phenolic foam according to claim 1, wherein the aqueous solution of inorganic acid containing the metal is contained in an amount of 5 parts by weight or less based on 100 parts by weight of the phenolic resin.
The composition for producing phenolic foam according to claim 1, wherein the phenol-based resin is a low-viscosity phenol-based resin.
The composition for manufacturing phenolic foam according to claim 8, wherein the low-viscosity phenolic resin has a viscosity of 80,000 cps or less at 25°C.
The composition for producing phenol foam according to claim 1, wherein the foaming agent is at least one selected from the group consisting of hydrofluoroolefin (HFO)-based compounds, hydrocarbon-based compounds, and halogenated hydrocarbon-based compounds.
The method of claim 1, wherein the plasticizer is an aromatic diol or aromatic monoalcohol such as ester, ester polyol, ether polyol, phosphorus compound, resorcinol, o,m,p-cresol, catechol, hydroquinone and salicyl alcohol, A composition for producing phenolic foam, which is at least one selected from the group consisting of epoxy resins and fluorine-based compounds.
The method of claim 1, wherein the curing agent is any selected from the group consisting of phenolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, naphthalenesulfone, arylsulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. At least one composition for producing phenolic foam.
The composition for producing phenol foam according to claim 1, wherein the surfactant is at least one selected from the group consisting of siloxane-based compounds, castor oil-ethylene oxide, ester compounds, ether compounds, silicone-based compounds, and fluorine-based compounds.
The method of claim 1, wherein the flame retardant is TCPP (Tris(1-Chloro-2-Propyl)Phosphate), TEP (Triethyl Phosphate), TEPP (Tetraethyl piperazine-1,4-diyldiphosphoramidate), TCP (Tricresyl Phosphate), RDP ( Resorcinol bis(diphenyl phosphate)), APP(Ammonium Poly Phosphate), DOPO-HQ(10-(2,5-dihydroxyphenyl)-9,10-dihydro- 9-xa-10-phosphaphenanthrene-10-oxide), phosphazene A composition for producing phenol foam, which is at least one selected from the group consisting of (phosphazene)-based, boric acid (H ₃ BO ₃ ), borax (Na ₂ B ₄ O ₇ ), and expandable graphite.
The method of claim 1, wherein the nucleating agent is a silane-based compound, a siloxane-based compound, a perfluoroalkane-based compound, a hydrofluoroalkane-based compound, a hydrofluoroether-based compound, a chlorinated hydrofluoroolefin-based compound, or a non-chlorinated hydrofluorocarbon compound. A composition for producing phenol foam, which is at least one selected from the group consisting of olefin-based compounds and hydrochloroalkenes.
A phenolic foam manufactured using the composition for producing phenolic foam according to any one of claims 1 and 4 to 15.
The method of claim 16, wherein the phenolic foam is:
Contains one or more transition metals selected from the group consisting of manganese, molybdenum, vanadium, chromium, and tungsten; and
A phenolic foam having a moisture absorption rate of 1.0 to 10.0%, a water vapor permeability of 3.0 to 20.0 ng/m·s·Pa, a density of 20 to 60 kg/m3, and a closed cell rate of 60 to 99%.
The phenolic foam of claim 16, wherein the phenolic foam has a thermal conductivity of 0.010 to 0.035 W/m·K, a compressive strength of 40 to 250 kPa, and a bending failure load of 15 to 60 N.
The phenolic foam of claim 16, wherein the phenolic foam contains a transition metal in an amount of 0.05 to 0.30% by weight based on 100% by weight of the phenolic foam.