KR102691148B1 - Composition for manufacturing of phenolic foam and phenolic foam manufactured therefrom - Google Patents

Abstract

The present invention relates to a composition for producing phenol foam containing zeolite and a phenol foam manufactured using the composition. Specifically, the composition for producing phenol foam according to the present invention has low hazard to the human body and the environment, neutralizes the acidic component by adding zeolite during production, neutralizes the phenol foam, and has excellent curing characteristics, such as thermal conductivity, compressive strength, and bending failure load. By manufacturing phenolic foam with excellent physical properties such as density and intact cells, it has excellent insulation properties and does not cause corrosion of metal components used together, so it can be usefully used as an eco-friendly building material.

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 zeolite and 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 with performance deterioration 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, etc. with a certain ratio of phenol resin and then curing it. However, since many acidic substances are used at this time, there is a problem that corrosion of the metal member is caused when the phenolic foam comes into contact with the metal member. In this regard, Republic of Korea Patent No. 10-2151556 discloses that an inorganic neutralizer containing aluminum hydroxide, zinc oxide, calcium carbonate, and magnesium carbonate is coated with a binder to prevent cell cracking and deterioration of insulation performance and when in contact with metal materials. A phenol foam insulation material that can suppress corrosion of metals is being disclosed.

Republic of Korea Patent No. 10-2151556

The purpose of the present invention is to provide a composition for producing phenol foam containing zeolite and a phenol foam manufactured using the composition.

In order to achieve the above object, the present invention includes a phenolic resin; Any one or more additives selected from the group consisting of foaming agents, plasticizers, curing agents, surfactants, flame retardants, and nucleating agents; And it provides a composition for producing phenol foam containing zeolite.

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 has low hazard to the human body and the environment, neutralizes acidic components by adding zeolite during production to neutralize phenol foam, and has excellent curing properties such as thermal conductivity, compressive strength, bending failure load, density, etc. By manufacturing phenolic foam with excellent physical properties and intact cells, it has excellent insulation properties and does not cause corrosion of metal components used together, so it can be usefully used as an eco-friendly building material.

Hereinafter, the present invention will be described in detail.

The present invention relates to a phenolic resin; One or more additives selected from the group consisting of foaming agents, plasticizers, curing agents, flame retardants, surfactants, and nucleating agents; And it provides a composition for producing phenol foam containing zeolite.

The term 'zeolite' used in this specification is an aluminosilicate mineral in which SiO ₄ and AlO ₄ tetrahedra are bonded while sharing oxygen atoms to form a three-dimensional network structure, and a large amount of spaces exist to form a water It is occupied by cations capable of ion exchange with molecules. Cations present in such zeolite can be easily exchanged with other cations and can exhibit various physical and chemical properties depending on the size and occupied position of the exchanged cation. The zeolite may include any one or more selected from the group consisting of natural zeolites and synthetic zeolites.

The natural zeolite is formed where volcanic rock and volcanic ash layers meet alkaline groundwater, or is crystallized over a long period of time in sedimentary layers of shallow marine basins, and exists in a mixed state with minerals, metals, and quartz. Natural zeolites included in the composition according to the present invention may include all zeolites known in the art, and more specifically, may be zeolites identified from minerals by X-ray diffraction. For example, the natural zeolites include clinoptilolite, mordenite, analcime, chabazite, heulandite, natrolite, and philipsite. (phillipsite), etc. may be included.

Meanwhile, the synthetic zeolite may include all synthetic zeolites known in the art. Specifically, the synthetic zeolite can be produced by a hydrothermal process.

The synthetic zeolite may include analogs in which silicon (Si) and aluminum (Al), which are elements forming the skeletal structure of zeolite, are partially or completely replaced with various other elements. Specifically, the zeolite analog may be an AlPO ₄ -based zeolite analog. In addition, the zeolite analog may also include all zeolite analogs prepared by partially substituting a metal element in addition to the analog skeleton. For example, the synthetic zeolite can be divided into A-type zeolite (zeolite A, LTA), X-type zeolite, Y-type zeolite (zeolite In addition, the synthetic zeolite can be divided into MCM-50 with a layered structure, MCM-41 and SBA-15 with a hexagonal structure, and MCM-48 with a cubic structure, depending on its structure.

According to one embodiment of the present invention, the zeolite may be any one or more selected from the group consisting of ZSM-5, MCM-41, and clinoptilolite.

The zeolite may be used as a neutralizing agent in the composition for producing phenol foam according to the present invention. The zeolite is used in an amount of 15 parts by weight or less, 1 to 15 parts by weight, 1 to 13 parts by weight, 1 to 11 parts by weight, 3 to 15 parts by weight, 3 to 13 parts by weight, or 3 to 11 parts by weight, based on 100 parts by weight of the phenolic resin. It may be included as a part. If the neutralizing agent composition is added in less than 1 part by weight, the pH of the produced phenol foam may be lowered, which may cause corrosion of metal members used together, and if added in more than 15 parts by weight, the viscosity of the composition for producing phenol foam increases, thereby hindering the curing process. Control can be difficult.

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 sulfuric acid and p-toluenesulfone. 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 phenolic resin may be of the 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 phenolic 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.

Additionally, 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-based 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-pentafluor 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 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 can 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 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 excess of 20 parts by weight, the pH of the phenolic foam decreases, increasing the corrosion of metal members used together. can do.

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 an amount of 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 an amount exceeding 20 parts by weight, the physical properties of the produced phenol foam may decrease and the 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 halogen-based, phosphorus-based, halogen-phosphorus-based, boron-based flame retardants, expanded graphite, 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 ), and expandable graphite.

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 less than 1 part by weight, it is difficult to properly implement the flame retardant performance of the phenol foam, and if it is added in more than 20 parts by weight, the physical properties of the manufactured phenol 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-pentafluor 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.

The nucleating agent may be added in an appropriate amount by a person skilled in the art, specifically, 0.1 to 10 parts by weight, 0.1 to 5 parts by weight, 0.1 to 3 parts by weight, 0.2 to 10 parts by weight, based on 100 parts by weight of the phenolic resin. It may be added in an amount of 0.2 to 5 parts by weight or 0.2 to 3 parts by weight. If the nucleating agent is added in an amount of less than 0.1 parts by weight, it is difficult to properly implement the performance of the nucleating agent, and if it is added in an amount exceeding 10 parts by weight, the density of the manufactured phenolic foam may be reduced.

In addition to the components described above, the composition for producing phenolic 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 zeolite. Specifically, the composition for producing phenolic foam according to the present invention may further include other additives, cotton, emulsifiers, 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; One or more additives selected from the group consisting of foaming agents, plasticizers, curing agents, flame retardants, and surfactants; and zeolite.

The curing can be performed by a person skilled in the art under appropriate conditions and methods. Specifically, the curing is performed at 90°C or lower, 50 to 90°C, 50 to 85°C, 50 to 80°C, 55 to 90°C, 55 to 85°C, 55 to 80°C, 60 to 90°C, 60 to 85°C, or It can be carried out at a temperature of 60 to 80°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 has excellent curing properties by curing in a short time, but also has excellent physical properties such as thermal conductivity, compressive strength, bending failure load, and density, and forms intact cells in the cured phenolic foam, It can be used as an eco-friendly building material that has excellent insulation properties and is safe for the human body.

Specifically, the phenolic foam may have pH 4 or higher, pH 4 to 9, pH 4 to 7, or pH 4 to 6 by adding zeolite.

In addition, the phenolic foam of the present invention has a 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. It may have a thermal conductivity of ·K or 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 200 kpa, 40 to 150 kpa, 60 to 250 kpa, 60 to 200 kpa, 60 to 150 kpa, 80 to 250 kpa, according to KS M ISO 845. It may be 80 to 200 kpa or 80 to 150 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.

Meanwhile, the phenolic foam according to the present invention may have a moisture absorption rate of 1.0 to 10.0%, 1.0 to 8.0%, 1.0 to 6.0%, 2.0 to 10.0%, 2.0 to 8.0%, or 2.0 to 6.0%. In addition, the phenol foam is 1.0 to 20.0 ng/m·s·Pa, 1.0 to 15.0 ng/m·s·Pa, 1.0 to 10.0 ng/m·s·Pa, 3.0 to 20.0 ng/m·s·Pa, It may have a water vapor permeability of 3.0 to 15.0 ng/m·s·Pa or 3.0 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%.

The phenolic foam may include zeolite in an amount of 0.5 to 15% by weight or 0.5 to 10% by weight based on 100% by weight of the phenolic foam. When zeolite is included in the above content range, the manufactured phenolic foam can prevent metal members used together from corroding, and the viscosity of the composition for producing phenolic foam is maintained at an appropriate level, making it easy to control the curing process and increasing process efficiency. It can be raised.

In other words, the phenolic foam manufactured by the manufacturing method according to the present invention is manufactured using zeolite, and can be usefully used as an eco-friendly building material that has excellent hardening characteristics and physical properties and does not cause corrosion of metal members used together.

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.

Example 1. Production of phenol foam-(1)

Phenolic foam was manufactured using ZSM-5, a zeolite-based neutralizing agent, in the following manner.

Specifically, 100 parts by weight of a phenol resin with 6.3% moisture and a viscosity of 49,000 cps at 25°C, 7 parts by weight of cyclopentane, 7 parts by weight of ether polyol, and 8 parts by weight of xylenesulfonic acid. A mixture was prepared by mixing acid), 3 parts by weight of a silicone-based surfactant, and 4 parts by weight of ZSM-5. 1.7 parts by weight of distilled water was added to the prepared mixture and stirred to obtain a foaming composition. The obtained foam composition was placed in a mold measuring 400 x 400 x 75 mm and cured at 70°C for 20 minutes. Phenolic foam to which ZSM-5 was added was prepared by aging the cured foam in an oven at 70°C for 15 hours.

Example 2. Preparation of phenolic foam-(2)

Phenolic foam to which MCM-41 was added as a neutralizing agent was prepared under the same conditions and methods as in Example 1, except that MCM-41 was added instead of ZSM-5.

Example 3. Preparation of phenol foam-(3)

Phenolic foam to which clinoptilolite was added as a neutralizing agent was prepared under the same conditions and methods as in Example 1, except that clinoptilolite was added instead of ZSM-5.

Example 4. Preparation of phenol foam-(4)

Phenol foam to which 10 parts by weight of ZMS-5 was added as a neutralizing agent was prepared under the same conditions and methods as in Example 1, except that 10 parts by weight of ZSM-5 was added instead of 4 parts by weight.

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

Phenol foam without a neutralizer was prepared under the same conditions and methods as in Example 1, except that ZSM-5 was not added.

Comparative example 2. of phenolic foam Manufacturing - (2)

Phenol foam to which calcium carbonate was added as a neutralizing agent was prepared under the same conditions and methods as in Example 1, except that calcium carbonate was added instead of ZSM-5.

Comparative example 3. of phenolic foam Manufacturing - (3)

A phenolic foam to which a metal oxide was added as a neutralizing agent was prepared under the same conditions and methods as in Example 1, except that iron oxide, a metal oxide, was added instead of ZSM-5.

Experiment example One. of phenolic foam Properties

The physical properties of the phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were confirmed as follows.

1-1. pH

The phenol foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were ground to a size of 250 ㎛ (60 mesh). After adding 200 ml of distilled water to an Erlenmeyer flask with a volume of 200 ml, 0.5 g of pulverized phenol foam was added. It was sealed and stirred at 23 ± 2°C for 12 days while the pH was measured at intervals of 1 to 2 days.

1-2. thermal conductivity

The phenol foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 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.

1-3. compressive strength

The phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 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 compressive yield point that appeared while the thickness was decreasing was recorded.

1-4. Flexural failure load

The phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 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 thereto, 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.

1-5. moisture absorption rate

The phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 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/㎤)

1-6. water vapor permeability

The phenol foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 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

1-7. density

The phenol foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 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 to 3 measured as above are shown in Table 1 below.

phenolic foam pH 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 4.12 0.020 125 31 2.9 7.3 34 Example 2 4.09 0.019 116 37 3.6 4.8 36 Example 3 4.16 0.021 102 28 2.5 6.1 37 Example 4 4.53 0.023 109 32 2.2 5.2 39 Comparative Example 1 3.24 0.020 145 35 6.9 10.4 44 Comparative Example 2 3.59 0.024 85 22 8.5 12.9 41 Comparative Example 3 3.76 0.026 68 17 5.8 9.6 33

As shown in Table 1, the phenolic foam of Examples 1 to 4 prepared by adding zeolite as a neutralizing agent showed a pH value of 4 or higher, but the phenolic foam of Comparative Example 1 without adding a neutralizing agent had a pH of 3.2, Phenol foams from 1 to 4 showed a pH closer to neutral. On the other hand, the phenol foams of Comparative Examples 2 and 3 using calcium carbonate or metal oxide as a neutralizing agent showed pH of 3.59 and 3.76, respectively.

On the other hand, when phenol foam was manufactured by adding 18 parts by weight of ZSM-5, the viscosity of the obtained foam composition increased and phenol foam was not formed.

In addition, the phenolic foams of Examples 1 to 4 are phenolic foams that do not have thermal conductivity, compressive strength, flexural failure load, and density even with the addition of zeolite, or phenolic foams manufactured by adding calcium carbonate or metal oxide as a neutralizing agent. It was better or equivalent. On the other hand, it was found that the phenolic foams of Examples 1 to 4 had significantly lower moisture absorption rate and water vapor permeability values, showing better physical properties.

Experiment example 2. Hardening characteristics

The curing characteristics of the phenolic foams prepared in Examples 1 to 4 and Comparative Examples 1 to 3 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. The time to reach the measured internal maximum curing temperature is shown in Table 2 below.

phenolic foam _Tmax (s) Example 1 331 Example 2 327 Example 3 336 Example 4 368 Comparative Example 1 324 Comparative Example 2 471 Comparative Example 3 402

As shown in Table 2, the phenol foams of Examples 1 to 4 showed a curing rate that was superior or equivalent to the phenol foam of Comparative Example 1 without the addition of a neutralizing agent. Meanwhile, the curing speed was significantly faster compared to the phenolic foams of Comparative Examples 2 and 3 in which calcium carbonate or metal oxide was added as a neutralizing agent.

Therefore, from the above results, it was confirmed that phenol foam showing excellent curing properties could be manufactured even by adding zeolite as a neutralizer.

Experiment example 3. phenolic foam Formation of my cells

By confirming the closed cell ratio of the phenolic foam prepared in Examples 1 to 4 and Comparative Examples 1 to 3, 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 3 below.

phenolic foam Closed cell rate (%) Example 1 94 Example 2 96 Example 3 93 Example 4 94 Comparative Example 1 91 Comparative Example 2 89 Comparative Example 3 86

As shown in Table 3, the bubble formation rate of the phenol foam prepared by adding zeolite in Examples 1 to 4 was high. On the other hand, the phenol foam of Comparative Example 1 prepared without adding a neutralizing agent showed a closed cell rate of 91%, while Comparative Examples 2 and 3 in which calcium carbonate or metal oxide was added as a neutralizing agent had a closed cell rate of less than 90%. It was low.

Therefore, from the above results, it was confirmed that the phenolic foam manufactured by adding zeolite as a neutralizing agent exhibited excellent thermal insulation properties due to the complete formation of cells in the phenolic foam.

Experiment example 4. phenolic foam Content of my zeolite

The content of zeolite contained in the phenolic foam prepared in Examples 1 to 4 and Comparative Examples 1 to 3 was measured by a conventional method, and the results are shown in Table 4 below.

phenolic foam Zeolite types Zeolite content (wt%) Example 1 ZSM-5 2.7 Example 2 MCM-41 2.6 Example 3 clinoptilolite 2.8 Example 4 ZSM-5 6.7 Comparative Example 1 - - Comparative Example 2 - - Comparative Example 3 - -

As shown in Table 4, the phenol foams of Examples 1 to 4 contained zeolite at the level desired by the present invention. On the other hand, the phenol foams of Comparative Examples 1 to 3 did not contain zeolite, and thus did not exhibit the same effects as the phenol foams of Examples 1 to 4.

Claims (15)

phenolic resin;
Any one or more additives selected from the group consisting of foaming agents, plasticizers, curing agents, surfactants, flame retardants, and nucleating agents; and
A composition for producing phenolic foam containing synthetic zeolite,
The phenolic resin contains 3 to 15% by weight of moisture,
A composition for producing phenolic foam, wherein the synthetic zeolite is contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the phenolic resin.
delete delete The method of claim 1, wherein the synthetic zeolite is at least one selected from the group consisting of A-type zeolite, , Composition for manufacturing phenol foam.
delete The composition for producing phenolic 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 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 phenolic 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.
A composition for producing phenol foam, wherein in claim 1, the surfactant is at least one selected from the group consisting of a siloxane compound, castor oil-ethylene oxide, an ester compound, an ether compound, a silicone compound, and a fluorine compound.
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, 4, and 6 to 11.
The method of claim 12, wherein the phenolic foam includes synthetic zeolite;
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 12, 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 12, wherein the phenolic foam includes synthetic zeolite in an amount of 0.5 to 10% by weight based on 100% by weight of the phenol foam.