Phenolic foam and method for manufacturing the same

Abstract

Phenolic foam and its manufacturing method are described. The phenolic foam is composed of at least one chlorinated hydrofluoroolefin, at least one hydrofluoroolefin, and at least one hydrocarbon. The phenolic foam has excellent thermal insulation properties and excellent fire retardant properties.

Description

Technical Field

[0001] The present invention relates to a phenolic foam and a method for producing the same. The phenolic foam of the present invention has excellent reaction and resistance performance against fire in combination with excellent heat insulation performance.

Background Art

[0002] The Paris Agreement aims to limit the increase in the global average temperature to no more than 2°C above the pre-industrial level. To achieve this goal, it is essential to reduce energy consumption. The construction of energy-efficient buildings and the renovation of existing buildings into energy-efficient ones are necessary to reduce the energy required to maintain such buildings. Thermal insulation materials are the key to reducing the energy consumption requirements of buildings.

[0003] A wide variety of thermal insulation materials are commercially available for numerous applications, including roof systems, building panels, building facades, floor systems, and refrigeration applications. The selection of the most suitable type of thermal insulation product for a given application involves the evaluation of a number of criteria, such as thermal insulation properties (i.e., thermal conductivity), compressive strength, dimensional stability, water resistance, fire protection performance, the thickness of the thermal insulation product, and the expected life of the thermal insulation product. For example, vacuum insulation panels have excellent thermal insulation performance and a long life span of about 20 years. However, generally speaking, vacuum insulation panels are not very robust, and if there are holes in the outer skin, the thermal insulation performance will be significantly reduced. Therefore, when used in refrigeration applications such as refrigerators, the holes are prevented by the freezer liner. In other applications where there is a high risk of holes during construction and / or use, such as in hollow walls, the use of vacuum insulation panels is not common.

[0004] Enclosing a building with a building envelope or facade is an efficient way to protect the building from natural forces and insulate the building, and such a building methodology has expanded the scope of design expression.

[0005] Therefore, using a heat-insulating material with excellent fireproof performance is a very advisable measure in building facades. Desirably, heat-insulating products in building facades should combine excellent heat-insulating performance with excellent fireproof performance.

[0006] Aerogel is a material that combines good fireproof performance with excellent heat insulation. However, these products are currently relatively costly, and thus, extensive use of aerogel in building applications is not commercially feasible at present.

[0007] Artificial mineral wool (MMMW) heat-insulating materials have excellent fireproof performance, while closed-cell polymer foams have high-quality heat-insulating performance. As a result, to achieve a given U-value, the thickness of MMMW heat-insulating materials is usually significantly greater than that of closed-cell polymer foams.

[0008] Closed-cell heat-insulating materials such as polyurethane / polyisocyanurate (PUR / PIR), extruded polystyrene (XPS), and phenolic foam (PF) provide better heat-insulating values compared to MMMW. Closed-cell polymer foams are generally formed by expanding a low-thermal-conductivity blowing agent in a polymer resin or prepolymer reactant that reacts to form a polymer resin. The gas cells contain the blowing agent, and its low thermal conductivity imparts excellent heat-insulating performance to the foam. The closed-cell structure of the foam ensures that these gases do not leak from the product.

[0009] A scanning electron micrograph of a typical closed-cell structure of phenolic foam is shown in Figure 1.

[0010] Historically, phenolic resins have been preferred thermosetting resins for use in foamed insulation materials where low toxicity, low smoke emission, and self-extinguishing capabilities in fire situations are required. Phenolic foams are known to combine excellent fire resistance with high thermal insulation at a commercially viable cost without requiring flame retardant additives that may be harmful in terms of toxicity. In contrast, foams such as PIR and XPS have inferior fire resistance, which hinders their use in certain applications, and require the use of significant levels of flame retardants to meet minimum fire resistance standards in other applications.

[0011] While the use of flame retardants (FRs) can improve fire resistance, their use is not always desirable. This is due to various factors. One major concern is that flame retardants may have other undesirable effects on the foam.

[0012] For example, some flame retardants (FRs), particularly liquid flame retardants, can plasticize foam cells. Plasticizing foam cells can reduce the compressive strength of the foam, especially at high ambient temperatures. Plasticizing foam cells can cause low-thermal-conductivity blowing agents within the foam cells to evaporate, thus negatively impacting the foam's thermal conductivity. Such effects have been observed with phenolic foam and liquid flame retardants.

[0013] Some solid flame retardants, particularly granular flame retardants, tend to negatively affect the thermal conductivity of foam over time. This depends on the chemical properties of the specific flame retardant and the amount of flame retardant added to the foaming composition.

[0014] There are also concerns about the toxicity of some flame retardants.

[0015] Therefore, when flame retardants are added to insulating foam, this is done as a compromise between improving fire resistance and improving insulation performance, but it is necessary to accept that achieving improved fire resistance will come with adverse effects on insulation performance, and also to accept that there are concerns about toxicity due to the presence of flame retardants.

[0016] The most important chemical families of flame retardants are those based on bromine, chlorine, phosphorus, nitrogen, antimony, certain metal salts, and hydrated inorganic hydroxides.

[0017] Flame retardants inhibit or even suppress the combustion process. They can act chemically and / or physically in the solid, liquid, or gas phase. They interfere with combustion during certain stages of the combustion process, for example, during heating, ignition, flame propagation, or decomposition of the material.

[0018] Since blowing agents (which may be flammable) can be released from the bubble cell at temperatures higher than the blowing agent's boiling point, for example above 100°C, the flame retardant needs to function at temperatures around this range. Some flame retardants, such as aluminum trihydrate, have high decomposition temperatures at which they release their hydrated water, and therefore the flammable blowing agent is released before the flame retardant can exert its flame-retardant effect. Consequently, such flame retardants have only a limited effect in reducing flame propagation and fire response.

[0019] Many common flame retardants are bromides. Some brominated products have adverse effects on the environment and health, and are currently being phased out as part of various environmental initiatives worldwide. Therefore, alternative insulation products that do not require the use of such brominated flame retardants and possess excellent thermal insulation and fire protection properties are desirable.

[0020] Figure 2 shows the process of heat generation as a function of time in an actual fire situation. If the initial area where heat generation is fuel-controlled can be expanded, the risk of casualties in a fire can be reduced. In the case of buildings consisting of facades, the structure of the facade and the materials used therein can significantly influence the growth of the fire.

[0021] Extensive fire tests have been developed to determine the fire resistance performance of thermal insulation materials. The main problem with these tests is that the correlation between the material's performance in many of these fire tests and its actual fire resistance performance in real fires is limited. The main reason for this is that it is extremely difficult to simulate the intensity of heat on a smaller scale. Examples of standardized small-scale fire tests include the standards EN13823, ISO 13785-1, ISO 21367, and PN-B-02867. Examples of standardized large-scale fire tests include the standards DIN 4102-20, ISO 9705, SP105, BS8414-1, MSZ 14800-6, LePIR-II, JIS A 1310, and NFPA 285.

[0022] The fire behavior of closed-cell insulation materials can be classified into two categories: "reaction to fire" and "resistance to fire." The first category is an indicator of the rate at which fire propagates after the material is ignited by a heat source. The second category indicates the resistance of the foamed insulation material to fire propagation.

[0023] When closed-cell foam is exposed to a heat source, the temperature of the gas inside the foam cells rises. As the temperature rises, the volume of the gas increases, the pressure inside the cells rises, and ultimately the cell walls burst due to the release of the cell gas.

[0024] When the foaming agent in the gas bubbles is flammable, the gas released from the product will ignite and generate heat. This effect accelerates the propagation of the fire and shortens the time between initial ignition and the peak of the fire.

[0025] The rupture of the bubble walls begins at temperatures exceeding approximately 100°C, potentially leading to the formation of flammable decomposition gases from the chemical foam matrix.

[0026] The release of flammable blowing agents, and the subsequent combustion, raises the temperature of the foam matrix, accelerating its decomposition. As a result, the rate of fire propagation increases.

[0027] Polyurethane, polyisocyanurate, and phenolic laminated foams are generally manufactured with a surface protective layer called a facer. Fire-resistant facers can delay the release of foam gases in the very early stages of a fire. Airtight facers applied to the foam core are particularly effective in protecting the foam core in a fire. Examples of airtight facers include (non-porous) aluminum foil and steel sheet faceters.

[0028] For example, in the case of polyisocyanurate foam, to improve the fire resistance of the insulation product, aluminum foil with a thickness of approximately 30 μm (up to 200 μm in some cases) can be used as a faceter on the polyisocyanurate foam core.

[0029] However, in the case of phenolic resin foam, these airtight facers are generally not used in the manufacturing process because it is necessary to remove the moisture generated during the condensation polymerization of the phenolic resin to prevent the formation of voids in the foam matrix. Airtight facers applied during foam manufacturing would hinder this moisture removal. Airtight facers can be applied to the phenolic foam by secondary bonding after the moisture has been removed during the manufacturing process. However, this is cost-inefficient.

[0030] In many standard fire resistance testing methods, products are tested without removing the facer. However, the use of a facer is only helpful in preventing the spread of fire in the case of a limited heat / ignition source, such as a burning trash can. The ability of a facer to prevent or stop the spread of a larger fire is limited. In terms of fire resistance, a facer provides no protection, as the aluminum foil will burn out in just a few seconds.

[0031] The presence of facets on polymer foam can distort the performance results of foam in small-scale fire tests to such an extent that they do not reflect the foam's performance in large-scale tests. Therefore, the most realistic way to simulate the performance of foam insulation products in actual fires is to test the foam core, rather than the complete insulation product including facets. The most reliable way to obtain a realistic assessment of the performance of insulation products including facets is probably to conduct large-scale fire tests. The disadvantages of these large-scale fire tests are that they are very expensive and time-consuming to conduct. Furthermore, the availability of appropriate test rigs for conducting such tests is limited.

[0032] To simulate actual fire resistance performance, a wide variety of fire tests, ranging from small-scale to large-scale, are used.

[0033] Examples of laboratory fire tests include the "Cone Calorimeter Heat Release test" (ISO 5660-1), the "Limiting Oxygen Index" (LOI) test (ISO 4589-2), the "Heat of Combustion" test (ISO 1716), and the "Ignitability of Products Subjected to Direct Impingement of Flame test" (ISO 11925-2).

[0034] The problem with most of these laboratory-scale fire tests is that the correlation between the fire resistance performance of the materials tested in such laboratory tests and their actual fire resistance performance in large-scale fire tests or in actual real fire situations is very limited. Firstly, in some of these experiments, the products are not exposed to flames but to a different heat source. Secondly, the output of the heat source is very low compared to actual fire conditions.

[0035] For example, in the test method of standard EN ISO 11925-2, "Reaction to fire tests - Ignitability of building products subjected to direct impingement of flame - Part 2: Single-flame source test," the product under test is exposed to a small flame comparable to that of a cigarette lighter. The foam, facets, and edges of the insulation product are exposed to this flame for 15 to 30 seconds. The flame height is limited to 150 mm or less. Because a small flame is used in this test, the correspondence between the product's performance in actual fire conditions is limited.

[0036] The Limiting Oxygen Index (LOI) test according to standard ISO 4589-2 involves supporting a small test sample in a vertical glass column and introducing a slow flow of an oxygen / nitrogen mixture of known composition into the glass column. The upper end of the test sample is ignited, and the sample is observed and its burning length recorded while it burns. The test is continued with additional samples, varying the calibrated mixture of oxygen and nitrogen, until the minimum oxygen concentration (as a percentage) that properly maintains combustion is determined. A higher LOI indicates lower flammability. Air contains approximately 21% oxygen, and therefore materials with an LOI of less than 21% will likely maintain combustion in outdoor conditions.

[0037] While the LOI value represents a fundamental property of a material, it does not provide sufficient information about how the material actually reacts to combustion in an open atmosphere. LOI testing is not directly related to actual fires in which materials ignite. LOI testing only studies the extinguishing behavior in a gas mixture of oxygen-rich (or oxygen-insufficient) nitrogen.

[0038] Notwithstanding the above, large-scale fire tests and several small-scale fire tests such as those specified in standards EN13823, ISO13785-1, ISO21367, and PN-B-02867 provide more reliable information regarding the fire protection performance of products in actual fire conditions.

[0039] A particularly useful evaluation method for assessing the fire resistance performance of insulation materials in real fire conditions is the Single Burning Item (SBI) test (standard EN13823). This test method measures flame propagation length and mean heat rate (HRR). av ), including measuring the total heat generated (THR), the tendency for flame dripping, and the smoke rate (SPR) after "t" seconds. This test procedure simulates the performance of insulation products fixed to the walls and ceiling of a small room, with a single combustion ignition source in the corner of the room having a nominal heat output of 30 kW. This burner is equivalent to a burning trash can in the corner of the room. Thus, standard EN13823 is a test method that simulates a real fire situation and provides very useful information regarding the fire resistance performance of insulation materials in a real fire situation.

[0040] The performance of the sample is evaluated over a 20-minute exposure period. During this test, the heat rate of reaction (HRR) is measured using oxygen consumption calorimetry. The smoke rate of reaction (SPR) is measured in the exhaust duct based on light attenuation. For the first 600 seconds of exposure, flame dripping or particle fall is visually observed. Lateral flame propagation is also measured.

[0041] The fire resistance performance of a material is evaluated according to standard EN13823 by monitoring the fire growth rate and smoke generation rate after the thresholds for the average heat generation rate, total heat generation rate, average smoke generation rate, and total smoke generation rate exceed the standard values ​​defined in the specification.

[0042] The fire protection performance classification parameters for the SBI test are the Fire Growth Rate Index (FIGRA), Lateral Flame Propagation (LFS), and Total Heat Generation Rate (THR) over 600 seconds. 600s ) Additional classification parameters for smoke generation are the Smoke Growth Rate Index (SMOGRA) and the Total Smoke Generation Rate (TSP) in 600 seconds. 600s ) are defined according to their occurrence during the first 600 seconds of the test. [Overview of the Initiative] [Problems that the invention aims to solve]

[0043] The performance of closed-cell insulation foam in SBI testing varies considerably depending on the chemical type of the foam resin being tested, the type of blowing agent retained in the foam, and the presence or absence of flame retardants.

[0044] The Euroclass system for evaluating the fire resistance of building materials includes a classification of building materials into seven classes based on their reaction characteristics to fire. These classes are A1, A2, B, C, D, E, and F. The Euroclass system classifies the fire resistance of materials based on their performance in several standard test methods, including standards EN ISO 11925-2; EN 13823; EN ISO 1716 and EN ISO 1182. Products in Euroclass "A" include inorganic and ceramic products that contain little to no organic matter. An example of a product in Euroclass "B" is gypsum board with a thin facing material. The classification of closed-cell insulation products varies depending on the properties of the organic polymer resin from which the foam is formed, the type of blowing agent, and the presence or absence of flame retardants. As mentioned above, the phenolic resin matrix of phenolic foam is inherently less flammable than the resin matrices of polystyrene foam, polyurethane foam, and polyisocyanurate foam. Even if it is not possible to achieve Euro Class "A" classification for closed-cell foam formed from thermosetting resins or thermoplastic resins, it is desirable to provide closed-cell foam that achieves Euro Class "B" or at least Euro Class "C" classification and also realizes excellent thermal insulation performance. The present invention solves these and other requirements.

[0045] In this regard, it is important to note that there is a clear distinction between "reaction to fire" (combustion behavior) and "resistance to fire." In particular, a material with good "fire reaction" characteristics does not necessarily have good "fire resistance," and vice versa.

[0046] Here, we will describe a specific standardized test, but the differences between the two can be understood in the following simple conceptual terms.

[0047] "Fire resistance" is a measure of the time it takes for a fire to burn away an insulating material. This aspect of fire is important when the fire is indoors and the time it takes for it to reach the next room is critical. Consider the example of two rooms separated by a wall insulated with phenolic foam. The first room is burning, and there are people in the second room. The fire resistance of the wall structure determines the time it takes for the wall structure to disappear. This time is noteworthy because it provides time for people to leave the building unharmed.

[0048] However, "fire response" (combustion behavior) is another measure of how quickly a fire spreads. This aspect of fire is the speed at which it propagates. Consider the example of a trash can catching fire and starting a fire in a room. If there are people in this room, slowing down the rate of fire propagation is important because it gives people time to leave the room. Combustion behavior is a very important property when it comes to foam insulation.

[0049] As a general example, PIR foam exhibits very good fire resistance because the product forms a very dense char layer. However, its combustion behavior is relatively poor. For this reason, PIR foam is not suitable for applications such as facades, but it is a relatively good solution for other applications where combustion behavior is not critical, such as flat roofs.

[0050] Therefore, it remains necessary to provide foam insulation materials with improved properties in combustion behavior tests, such as preventative and limiting properties. In this application, combustion behavior properties are measured by SBI, particularly FIGRA tests. [Means for solving the problem]

[0051] In one aspect, according to the present invention, red phosphorus is used as a formaldehyde scavenger in a phenol foam, wherein the phenol foam is formed from a foaming phenol resin composition comprising a foaming agent, and the phenol foam is When the red phosphorus concentration in the phenol form is measured by the ICP-OES method described herein, It consists of 1-5% red phosphorus by weight, based on the weight of the phenolic foam, at 10 kg / m³. 3 From 100 kg / m 3 FIGRA has a density of 120 W / s or less, measured according to the standard ASTM D6226, and has a closed-cell content of at least 85% as measured according to the European standard EN13823. 0.2MJ The use of red phosphorus in a phenolic foam is provided, having a thermal conductivity of 0.023 W / mK or less at 10°C in accordance with European standard EN13166:2012. Preferably, the phenolic foam has a thermal conductivity of 0.20 W / mK or less at 10°C in accordance with European standard EN 13166:2012.

[0052] According to the present invention, closed-cell foam is provided as a minimum Euro Class "C" classification capable of achieving Euro Class "B" or providing similarly excellent thermal insulation performance. This represents a substantial step forward, as improvements in fire resistance often come with the aforementioned loss of thermal insulation performance.

[0053] Red phosphorus can function not only as a flame retardant but also as a formaldehyde scavenger. For example, in the phenolic foam of the present invention, formaldehyde emissions from the foam can be reduced by up to 50% compared to a control foam of the same phenolic foam in which red phosphorus particles are not present. Such emissions are tested according to the European standard EN16516.2017.

[0054] The use of blowing agents in the manufacture of phenolic foam is generally a negative factor in terms of combustion behavior. This invention overcomes this problem with phenolic foam containing a highly effective flame retardant. This is especially true in combination with a specific density and / or specific moisture content. The combustion behavior of such foam is particularly good.

[0055] The phenolic foam preferably has a density of from about 15 kg / m 3 to about 60 kg / m 3 ; for example, from about 20 kg / m 3 to about 50 kg / m 3 ; preferably from about 24 kg / m 3 to about 48 kg / m 3 In particular, it has been found that foams having a density of, for example, from 34.5 g / m 3 to 40 kg / m 3 ; for example, from 35 kg / m 3 to 39 kg / m 3 ; for example, from 36 kg / m 3 to 38 kg / m 3 provide desirable fire protection performance, for example with respect to combustion behavior. Such a density provides desirable fire protection performance, for example a FIGRA of 120 W / s or less when measured according to European standard EN13823.

[0056] The phenolic foam preferably has a density of from about 15 kg / m 3 to about 60 kg / m 3 ; for example, from about 20 kg / m 3 to about 50 kg / m 3 ; preferably from about 24 kg / m 3 to about 48 kg / m 3 In particular, it has been found that foams having a density of, for example, from 34.5 g / m 3 to 40 kg / m 3 ; for example, from 35 kg / m 3 to 39 kg / m 3 ; for example, from 36 kg / m 3 to 38 kg / m 3 provide desirable fire protection performance, for example with respect to combustion behavior. Such a density provides desirable fire protection performance, for example a FIGRA of 120 W / s or less when measured according to European standard EN13823. 0.2MJ is obtained.

[0057] ​​The phenolic foam of the present invention may contain 2 to 5 parts by weight of red phosphorus based on 100 parts by weight of the cured phenolic foam. For example, it may contain 3 to 4 parts by weight of red phosphorus based on 100 parts by weight of the cured phenolic foam.

[0058] The foaming agent comprises at least one saturated or unsaturated C3-C6 hydrocarbon and at least one saturated or unsaturated C3-C6 hydrocarbon that is substituted at least once with one or more fluorine or chlorine atoms, such as isopropyl chloride. compound It may include at least one of the following.

[0059] Preferably, the foaming agent consists of at least one of isopropyl chloride or saturated C3-C6 hydrocarbons such as pentane, which is isopentane, for example.

[0060] The phenolic foam of the present invention, when measured according to the European standard EN13823, has a power output of 110 W / s or less, for example, 100 W / s or less, for example, 90 W / s or less, as measured in FIGRA. 0.2MJ It has.

[0061] The phenolic foam of the present invention may contain 2 to 4 parts by weight of red phosphorus based on 100 parts by weight of the phenolic foam. All references to phenolic foam refer to the cured final product unless otherwise stated.

[0062] Preferably, the blowing agent comprises at least one hydrofluoroolefin or chlorinated hydrofluoroolefin.

[0063] The blowing agent comprises at least one saturated or unsaturated C3-C6 hydrocarbon and one or more fluorine or It may contain at least one saturated or unsaturated C3-C6 compound, such as isopropyl chloride, which is substituted at least once with chlorine.

[0064] For example, the blowing agent may include a mixture of at least one hydrofluoroolefin or chlorinated hydrofluoroolefin and a C3-C6 hydrocarbon such as pentane, which is isopentane.

[0065] The phenolic foam of the present invention has a ferrous flux of 100 W / s or less, for example, 90 W / s or less, or 80 W / s or less, or 70 W / s or less, when measured according to the European standard EN13823 FIGRA. 0.2MJ It may have.

[0066] The phenolic foam of the present invention preferably has a compressive strength of at least 95 kPa.

[0067] In the foam of the present invention, it is desirable that the red phosphorus be in particulate form, for example, in the form of fine powder. For example, the red phosphorus may be in particulate form with a number-average particle diameter in the range of 0.5 μm to 10 μm when observed with a scanning electron microscope. Refer to Figure 5, a representative SEM image of a phenol foam in which red phosphorus is dispersed, has the above-mentioned number-average particle diameter, and is present in the above-mentioned amount.

[0068] Preferably, each of the at least one hydrofluoroolefin and the at least one chlorinated hydrofluoroolefin has a thermal conductivity of 0.0135 W / mK or less at 10°C.

[0069] According to the present invention, a foam is provided that incorporates a flame retardant without significant toxicity concerns, thereby improving the fire resistance of the foam without compromising its thermal insulation performance. Red phosphorus can function simultaneously in both the gas phase and the condensed phase.

[0070] Surprisingly, the presence of 2-5% by weight of red phosphorus, with a particle size of 0.5-10 μm, pre-dispersed in the phenolic resin before the addition of surfactants, acid catalysts, and foaming agents, was found to reduce the fire growth rate (FIGRA) while maintaining the stable thermal conductivity of the foam. Red phosphorus has relatively low oral toxicity, with an LD50 of 15,000 mg / kg in rats.

[0071] The red phosphorus may have a coating layer on its surface. The red phosphorus may have a coating layer made of a metal oxide and / or a metal hydroxide and / or a resin. Preferably, the coating may contain a phenolic resin such as phenol-formaldehyde resin. Preferably, the coating may contain aluminum hydroxide. More preferably, the red phosphorus has a coating layer made of phenol-formaldehyde and / or aluminum hydroxide. In the present invention, the red phosphorus used may have various coatings, but preferred coatings are phenol-formaldehyde and / or aluminum hydroxide, including those on the red phosphorus in the following examples.

[0072] Preferably, each of the at least one hydrofluoroolefin and the at least one chlorinated hydrofluoroolefin has a thermal conductivity of 0.0125 W / mK or less. For example, each of the at least one hydrofluoroolefin and the at least one chlorinated hydrofluoroolefin has a thermal conductivity of 0.0125 W / mK or less at 25°C.

[0073] The phenolic foam may have a total heat generation rate of 7.5 MJ or less, for example, 7.0 MJ or less, or 6.5 MJ or less, or 6.25 MJ or less, or 6.0 MJ or less, or 5.75 MJ or less, or 5.5 MJ or less, or 5.25 MJ or less, or 5.15 MJ or less, or 5.0 MJ or less, or 4.8 MJ or less, or 4.6 MJ or less, or 4.4 MJ or less, when measured according to the European standard EN13823.

[0074] The phenolic foam preferably has a closed-cell content of 90% or more, for example 95% or more, and more preferably 98% or more, as measured according to the standard ASTM D6226.

[0075] The bubbles in the phenol foam may have an average bubble diameter in the range of 50 to 250 μm, preferably in the range of 80 to 180 μm.

[0076] Preferably, the thermal conductivity of the phenolic foam is 0.020 W / mK or less, preferably 0.018 W / mK or less, more likely 0.0175 W / mK or less, or 0.0170 W / mK or less, or 0.0165 W / mK or less, or 0.0162 W / mK or less, when measured at an average temperature of 10°C according to the European standard EN13166:2012.

[0077] The phenolic foam may have a limiting oxygen index of 34% or more, preferably 35% or more, more preferably 36% or more, for example, 37% or more, as measured according to standard ISO 4589-2.

[0078] Preferably, the phenolic foam has a critical oxygen index of 34% or higher, optionally 35% or higher, preferably 36% or higher, for example 37% or higher, as measured according to the standard ISO 4589-2 - "Thermal insulating products for building applications: conditioning to moisture equilibrium under specified temperature and humidity conditions".

[0079] If the stable moisture content exceeds 5%, there is a risk that the thermal conductivity of the foam will increase over time with application. If the stable moisture content is less than 3%, FIGRA may increase. Therefore, the optimal stable moisture content of phenolic foam can help achieve a low FIGRA over long periods in its thermal insulation applications without compromising low thermal conductivity.

[0080] The aforementioned at least one chlorinated hydrofluoroolefin can be selected from 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd).

[0081] The HCFO-1233zd may be an E isomer, a Z isomer, or a mixture thereof; that is, the HCFO-1233zd may be HCFO-1233zd(E), HFCO-1233zd(Z), or a mixture thereof. For example, the HCFO-1233zd may consist of 90% by weight or more (e.g., 95% by weight or more) of HCFO-1233zd(E), or the HCFO-1233zd may consist of 90% by weight or more (e.g., 95% by weight or more) of HFCO-1233zd(Z). Preferably, the HCFO-1233zd consists of 95% by weight or more of HCFO-1233zd(E).

[0082] The HCFO-1224yd may be an E isomer, a Z isomer, or a mixture thereof; that is, the HCFO-1224yd may be HCFO-1224yd(E), HFCO-1224zd(Z), or a mixture thereof. For example, the HCFO-1224yd may consist of 90% by weight or more (e.g., 95% by weight or more) of HCFO-1224yd(E), or the HCFO-1224yd may consist of 90% by weight or more (e.g., 95% by weight or more) of HFCO-1224yd(Z). Preferably, the HCFO-1224yd consists of 95% by weight or more of HFCO-1224yd(Z).

[0083] The at least one hydrofluoroolefin preferably consists of 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz). The HFO-1336mzz may be an E isomer, a Z isomer, or a mixture thereof; that is, the HFO-1336mzz may be HFO-1336mzz(E), HFO-1336mzz(Z), or a mixture thereof. For example, the HFO-1336mzz may consist of 90% by weight or more (e.g., 95% by weight or more) of HFO-1336mzz(E), or the HFO-1336mzz may consist of 90% by weight or more (e.g., 95% by weight or more) of HFO-1336mzz(Z). Preferably, the HFO-1336mzz consists of 95% by weight or more of HFO-1336mzz(Z). The aforementioned at least one alkyl halide may consist of, for example, isopropyl chloride.

[0084] The at least one (saturated) C3-C6 hydrocarbon may consist of, for example, butane which is isobutane, and / or pentane which is preferably isopentane.

[0085] The aforementioned at least one (unsaturated) C3-C6 hydrocarbon may consist of butene and / or pentene.

[0086] Preferably, each blowing agent used has a thermal conductivity of 0.0125 W / mK or less at 25°C. When a mixture of blowing agents is used, one or more blowing agents in the mixture may not have a thermal conductivity of 0.0125 W / mK or less at 25°C. In such cases, it is desirable that the thermal conductivity of the mixture used is 0.0125 W / mK or less at 25°C.

[0087] Preferably, the mixture consists of at least one hydrofluoroolefin or at least one chlorinated hydrofluoroolefin, or at least one alkyl halide or at least one chlorinated alkene, each having a thermal conductivity of 0.0125 W / / mK or less at 25°C, and at least one C3-C6 hydrocarbon. For example, the components of the foaming agent, namely the at least one hydrofluoroolefin, at least one chlorinated hydrofluoroolefin, at least one alkyl halide, or at least one chlorinated alkene, and at least one C3-C6 hydrocarbon, can be blended before mixing with the phenolic resin.

[0088] Furthermore, according to the present invention, red phosphorus is used as a formaldehyde scavenger in a phenol foam, wherein the phenol foam is formed by foaming and curing a foamable phenol resin composition, and the foamable phenol resin composition comprises a phenol resin, a surfactant, an acid catalyst, a foaming agent, and When the red phosphorus concentration in the phenol form is measured by the ICP-OES method described herein, Based on the weight of the phenolic foam, it consists of 1 to 5% by weight of red phosphorus, and the phenolic foam is 10 kg / m³ 3 From 100 kg / m 3 The density of the phenolic foam, measured according to standard ASTM D6226, has a closed-cell content of at least 85%, and the phenolic foam has a strength of 120 W / s or less when measured according to European standard EN13823. 0.2MJ The use of red phosphorus in a phenolic foam is provided, wherein the phenolic foam has a thermal conductivity of 0.023 W / mK or less at 10°C in accordance with the European standard EN13166:2012.

[0089] The blowing agent may consist of at least one hydrofluoroolefin and at least one chlorinated hydrofluoroolefin, and the blowing agent may further consist of at least one C3-C6 hydrocarbon.

[0090] The aforementioned at least one chlorinated hydrofluoroolefin may consist of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and / or 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd).

[0091] The aforementioned at least one hydrofluoroolefin may consist of 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz).

[0092] The at least one C3-C6 hydrocarbon may consist of butane, preferably isobutane, and / or pentane, preferably isopentane.

[0093] Preferably, the foaming agent comprises 1-chloro-3,3,3-trifluoropropene and / or 1-chloro-2,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene.

[0094] Preferably, the phenolic resin has a weight-average molecular weight of about 700 to about 2000, and / or the number-average molecular weight of the phenolic resin is about 330 to about 800, for example, about 350 to about 700.

[0095] Preferably, the molar ratio of phenol groups to aldehyde groups in the phenol resin is in the range of about 1:1 to about 1:3, preferably in the range of about 1:1.5 to about 1:2.3. The phenol may be a substituted phenol such as cresol. Naturally occurring phenols, including naturally occurring phenol polymers, can be used. Other aldehydes, including dialdehydes such as glyoxal, can be used. The above molar ratio can be adjusted considering the aldehyde functionality.

[0096] The water content of the phenolic resin foaming composition can be in the range of approximately 5 wt% to 12 wt%, for example, 5 wt% to 10 wt%, for example, 7 to 10 wt%, based on the total weight of the phenolic resin foaming composition.

[0097] The phenolic resin used to form the phenolic resin foam composition of the present invention may have a water content in the range of about 7.5 wt% to about 14 wt% in its uncured state.

[0098] The viscosity of the phenolic resin can range from approximately 2,500 mPa·s to approximately 18,000 mPa·s when measured at 25°C, for example from approximately 3,500 mPa·s to approximately 16,000 mPa·s when measured at 25°C, or for example from approximately 4,000 mPa·s to approximately 8,000 mPa·s when measured at 25°C.

[0099] The foaming agent is preferably present in an amount of about 5 to about 20 parts by weight per 100 parts by weight of the phenolic resin.

[0100] The phenolic foam of the present invention may further contain an inorganic filler. For example, calcium carbonate may be added as a filler and / or to increase the pH. The high pH value of the phenolic foam ensures a reduction in residual acid, along with the benefit of reducing the risk of corrosion of metal materials in contact with the phenolic foam. Calcium carbonate may be added to the foaming composition forming the phenolic foam of the present invention.

[0101] This invention provides 2 to 5 parts by weight of finely powdered (particle size 0.5 μm to 10 μm) red phosphorus flame retardant present in 100 parts by weight of cured phenolic foam, which exhibits excellent fire resistance and FIGRA (0.2 MJ threshold) < 150 W / s and SMOGRA < 20 m 2 / s 2The present invention relates to a phenolic foam that provides a foam insulation product having low smoke emission, stable thermal insulation performance (<0.023 W / mK), and a high closed-cell content (>85%). Another aspect of the present invention is that the presence of 2 to 5 parts by weight of finely powdered (particle size 0.5 μm to 10 μm) red phosphorus flame retardant present in 100 parts by weight of the phenolic foam provides a phenolic foam insulation product in which formaldehyde emissions from the phenolic foam product are reduced by 30 to 60% as measured by the standards EN717-1 / EN16516 / ISO16000-11.

[0102] The compressive strength of the phenolic foam may range from approximately 95 kPa to approximately 200 kPa, as measured according to the European standard EN826. [Brief explanation of the drawing]

[0103] [Figure 1] Figure 1 shows a scanning electron microscope image of closed-cell phenol foam. [Figure 2] Figure 2 shows the progression of heat generation as a function of time in an actual fire. [Figure 3] Figure 3 is a schematic diagram showing the setup for the SBI test according to European standard EN13823. [Figure 4] Figure 4 shows the effect of temperature on the thermal conductivity (lambda value) of phenolic foam blown with three different weight ratios of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and isopentane mixtures. [Figure 5] Figure 5 is a representative SEM image of the phenol foam, in which red phosphorus is dispersed, has the number-average particle size described above, and is present in the amount described above. This phenol foam is the same as that of Example 3 below. 1- [Modes for carrying out the invention]

[0104] [Definition] The expression "at least one X selected from the group consisting of A, B, C and combinations thereof" is defined such that X includes "at least one A", "at least one B", or "at least one C", or includes "at least one A combined with at least one B", or "at least one A combined with at least one C", or "at least one B combined with at least one C", or "at least one A combined with at least one B and at least one C".

[0105] The expression "Y can be selected from A, B, C and combinations thereof" includes the fact that Y can be A, B, C, A+B, A+C, B+C, or A+B+C.

[0106] The term "foaming agent" is defined as a propellant used to blow foaming compositions to form a foam. For example, a foaming agent can be used to blow / expand a resin to form a foam.

[0107] [Characteristics] The following describes a suitable test method for measuring the physical properties of phenolic foam. (i) Form density This was measured according to the European standard BS EN 1602:2013 - “Thermal insulating products for building applications - Determination of the apparent density”. (ii) Thermal conductivity of foam A foam test specimen measuring 300 mm in length and 300 mm in width was placed between a 20°C high-temperature plate and a 0°C low-temperature plate in a thermal conductivity test apparatus (Inventech Benelux BV, LaserComp Type FOX314 / ASF). The thermal conductivity (TC) of the test specimen was measured according to the European standard EN 12667: “Thermal performance of building materials and products - Determination of thermal resistance by means of guarded hot plate and heat flow meter methods, Products of high and medium thermal resistance”. (iii) Thermal conductivity of foam after accelerated aging This was measured using the European standard BS EN 13166:2012 - “Thermal insulation products for buildings - Factory made products of phenolic foam (PF)” - Specification Annex C section 4.2.3. Thermal conductivity was measured after the foam sample was exposed to 70°C for 25 weeks and stabilized to a constant weight at 23°C and 50% relative humidity. This thermal aging serves to provide an estimated thermal conductivity over a 25-year period at ambient temperatures. Alternatively, thermal conductivity over time can be measured after the foam sample was exposed to 110°C for 2 weeks and stabilized to a constant weight at 23°C and 50% relative humidity. (iv) pH pH was measured according to the European standard BS EN13468. (v) Closed cell content The closed-cell content can be measured using gas pycnometry. Preferably, the closed-cell content can be measured according to the test method of standard ASTM D6226. (vi) Form vulnerabilities Vulnerabilities are measured according to the test method of the standard ASTM C421-08(2014). (vii) Image conversion of forms A piece of foam was roughly cut from one coated surface to the other, measuring approximately 20 mm x 10 mm. The surface of this foam piece was trimmed with a razor blade to approximately 8 mm square. Next, the foam was sharply snapped to reveal a clean surface, and most of the sample was removed, leaving a thin (~1 mm) fragment. This fragment was fixed onto an aluminum sample stub using double-sided conductive adhesive tabs. The aforementioned sample was then coated with a thin (~2.5 angstroms (0.25 nm)) gold / palladium conductive film using an ion sputtering system, Bio-Rad SC500. The reasons for coating the sample were (a) to remove charge by adding a conductive surface, and (b) to increase density and sharpen the image. At the magnification level used in this study, the effect of the coating is negligible. The aforementioned samples were imaged using a scanning electron microscope FEI XL30 ESEM FEG and a secondary electron detector under the following conditions: acceleration voltage 10kV, working distance ~10mm, and spot size 4. The images were saved at the following magnifications: ×350, ×1200, and ×5000, and stored on disk as .tiff files. The image at magnification ×350 shows the general size distribution of the bubbles, while the higher magnifications of ×1200 and ×5000 show the properties of the bubble surface. Images obtained for both samples at a magnification of ×350 generally show a size range of ~100 to 200 μm. In the preparation of foam samples for evaluation by electron microscopy, manual snapping (breaking) of the foam sample—forming the surface to be examined—may cause some damage to the bubble walls. Images collected at magnifications of ×1200 and ×5000 are virtually free of defects or holes. (viii) Average bubble diameter The flat portion of the foam is obtained by thinly slicing the middle section of the foam board in a direction parallel to the top and bottom surfaces of the foam board. A 50x magnified copy photograph is obtained of the cut surface of the foam. Four straight lines 9 mm long are drawn on the copy photograph. The number of bubbles present on each straight line is counted according to the test method of standard JIS K6402 to determine the average number of bubbles. Dividing by this average number, the average bubble diameter is determined to be 1800 μm. (ix) Viscosity of resin The viscosity of the resin used in the manufacture of the foam of the present invention was measured by a method known to those skilled in the art, for example, using a Brookfield viscometer (Model DV-II+Pro) equipped with a temperature-controlled water bath, maintaining the sample temperature at 25°C and maintaining an intermediate torque acceptable for viscosity reading accuracy at a spindle number S29 rotating at 20 rpm or an appropriate rotation speed and spindle type or a suitable test temperature. (x) Percent moisture content of phenolic resin The phenolic resin was dissolved in anhydrous ethanol (manufactured by Honeywell Speciality Chemicals) in a concentration ranging from 25% to 75% by mass. The water content of the phenolic resin was calculated from the water content measured in this solution. The instrument used for the measurement was a Metrohm 870 KF Titrino Plus. For the measurement of the water content, Hydranal® Composite 5, manufactured by Honeywell Speciality Chemicals, was used as the Karl Fischer reagent, and Hydranal® Methanol Rapid, also manufactured by Honeywell Speciality Chemicals, was used for the Karl Fischer titration. Hydranal® Water Standard 10.0, manufactured by Honeywell Speciality Chemicals, was used to measure the titration volume of the Karl Fischer reagent. The measured water content was determined by Titer IPol using the method set on the instrument. (xi) Phosphorus concentration in phenolic foam The phosphorus concentration in phenolic foam can be measured by any suitable analytical method. One method for measuring phosphorus concentration in phenolic foam is the use of inductively coupled plasma emission spectrometry (ICP-OES). The procedure for measuring phosphorus concentration by ICP-OES is as follows: Before use, all glass and plastic products were acid-washed overnight with 1.5 M hydrochloric acid, followed by rinsing with MilliQ® (primary deionized water). All reagents were Primar Plus Trace Metal Grade (Fisher Scientific). Fragmented foam samples were dried in an oven at 70°C for 1 hour, then cooled in a drying oven. 0.1 g (±0.01 g) of foam was weighed and placed in a 55 ml Teflon® high-frequency decomposition tube. 4.5 ml of 68% nitric acid, 1 ml of 37% hydrochloric acid, and 0.5 ml of 30% hydrogen peroxide were added to the tube, and the sample was reacted for 10 minutes to allow foaming to subside. A replica of the sample and a procedural blank containing the reagents but without foam were processed in parallel. The tubes were sealed with PTFE pressure seals, stoppersed, and transferred to a CEM Mars 5 high-frequency decomposition system equipped with a sample carousel. The high-frequency decomposition apparatus was heated to 190°C for 10 minutes, maintained at 190°C for another 15 minutes, and then cooled to room temperature. The decomposed sample was transferred to a 15 ml centrifuge tube, and then 1 ml aliquots were diluted with 4 ml of Milli-Q water to make a 20% acid solution. Next, aliquots of this solution were diluted to 2% acidity and filtered through a 0.45 μm surfactant-free cellulose acetate filter. The filtered sample was processed for phosphorus using a Thermo ICAP Duo ICP 6300 ICP-OES elemental analyzer. This instrument was calibrated in the range of 0.5–20 mg / L using a 7-point calibration. The accuracy of the instrument was measured by three injections of the same sample, and the relative standard was found to be 0.244% of the average value. All samples were blank-corrected, and the results were as follows:

[0108] [Table A]

[0109] (xii) Fire resistance of the foam Figure 3 shows a schematic of the setup (equipment) for the SBI test according to standard EN13823. The test sample consists of two wall sections (formed from the material to be tested) installed to form a vertical 90° corner. The dimensions of the wall sections are as follows: Short wall - 1.5m high x 0.5m long Long wall - 1.5m high x 1.0m long

[0110] The propane burner is positioned on the base of the corner formed by the sample, with a horizontal gap of 40 mm between the edge of the burner and the lower edge of the sample.

[0111] Airflow extraction speed 0.6m 3 Set to / s. Install the sampling probe inside the extraction duct and sample the CO of the combustion exhaust gas passing through. X The concentration of O2 is measured. The heat generation rate is continuously calculated using the oxygen consumption method. The light obscuration caused by smoke in the combustion emissions passing through the exhaust duct is measured using a white light lamp and a photocell system.

[0112] At the beginning of the test procedure, reference data (e.g., temperature at various locations in the test setup) is recorded for 3 minutes. Next, the burner is ignited and a 30kW flame is applied to the test sample for 21 minutes. The performance of the sample is evaluated over a period of 20 minutes.

[0113] The fire growth rate (FIGRA) index is defined as the maximum value of the quotient of mean heat generation as a function of time.

number

[0114] The aforementioned quotient is HRR av And it is calculated only for the portion of the exposure time that exceeds the THR threshold. If, during the exposure time, one or both of the FIGRA index thresholds cannot be exceeded, the FIGRA index is equal to zero. FIGRA 0.2MJ and FIGRA 0.4MJ Two different THR thresholds are used. The time when these thresholds can be exceeded (the timing) is defined as follows: (a) HRR av >3kW at the first time after t=300s (b) The first time after t=300s when THR>0.2MJ and / or THR>0.4MJ

[0115] Total heat generation (THR) occurs during the first 10 minutes after ignition of the burner. 600s ) will be measured.

[0116] Standard EN13823 defines the smoke growth rate index (SMOGRA) as the maximum value of the quotient of the average smoke growth rate as a function of time. The quotient is the average smoke growth rate SPR av It is calculated only for the portion of the exposure time in which the threshold for the total smoke generation rate (TSP) is exceeded. SMOGRA is equal to zero if, during the exposure time, one or both thresholds cannot be exceeded.

number

[0117] The time when the aforementioned threshold can be exceeded (the opportune moment) is defined as follows: (a) SPR av >0.1m 2 The first time after t=300s, where / s (b) When "t" is between 300s and 1500s, TSP(t) > 6m 2

[0118] The SMOGRA index is measured throughout the entire period of the aforementioned test. Total Smoke Generation (TSP) 600 This is measured during the first 10 minutes after the burner is ignited (i.e., between 300 and 900 seconds).

[0119] As explained above, the SBI test is comparable to a fire that occurs in a wastebasket in the corner of a room.

[0120] Table 1 shows examples of the fire resistance performance of various commercially available foam insulation materials tested according to standard EN13823.

[0121] [Table 1]

[0122] Prior to testing the foam core, the foam sample was conditioned at 23°C and 50% relative humidity according to European standard EN13823, and then the facer was carefully peeled off the foam surface as thoroughly as possible. All remaining facer was carefully removed by sanding with very fine abrasive paper.

[0123] Phenolic foam generally has the highest fire resistance (grade) among all foam insulation products. The flame retardancy of a foam is influenced by the properties of the blowing agent used to expand the foam and that remains within the foam's air bubbles. As mentioned above, the thermal insulation performance of a foam also largely depends on the blowing agent and its thermal conductivity. Chlorofluorocarbons (CFCs) and hydrofluorocarbons (HFCs) represent a grade of blowing agent that offers a highly desirable combination of low thermal conductivity and excellent fire resistance. However, the use of such blowing agents is declining due to their negative environmental impacts, particularly their high ozone depletion potential and global warming potential. Hydrocarbon blowing agents have a lower environmental impact and are used as an alternative to CFCs and HFCs, although hydrocarbons inherently have higher thermal conductivity than CFCs and HFCs. In the last decade, hydrofluoroolefins and chlorinated hydrofluoroolefins have emerged as a grade of blowing agent that combines low thermal conductivity, good fire resistance, and low environmental impact.

[0124] Hydrofluoroolefins (HFOs) and hydrochlorofluorocarbons (HCFCs) are unsaturated short-chain haloolefins that have been introduced as substitutes for saturated hydrofluorocarbons (HFCs) as foaming agents due to their extremely low GWP (Global Warming Potential) and zero ODP (Ozone Depletion Potential).

[0125] The introduction of HFOs (hydrofluoroolefins) and hydrochlorofluoroolefins (HCFOs) has made it possible to use a range of blowing agents to improve fire resistance. The main advantages of these particular blowing agents are their low thermal conductivity in the gas phase and favorable environmental performance.

[0126] HCFOs are also preferred as blowing agents due to their low thermal conductivity in the gas phase and their solubility in correspondence with phenolic resins.

[0127] HFOs tend to have slightly higher thermal conductivity values ​​in the gas phase than HCFOs.

[0128] Table 2 below outlines the main foaming agents mentioned in this invention.

[0129] [Table 2] TIFF0007837874000006.tif254170

[0130] When considering which blowing agent to use when manufacturing foam, the end use of the foam must be taken into account, and generally, the properties of the blowing agent must be matched to the end use. Properties that can be considered in the selection process of a given blowing agent include thermal conductivity in the gas phase, boiling point, compatibility with the chemical matrix, flammability, toxicity, and price.

[0131] One of the most important criteria is the thermal conductivity (i.e., lambda) of each blowing agent component (comp). A simple model for evaluating the adiabatic value of a two-component gas mixture containing components A and B is shown below.

number

[0132] This model also first calculates the thermal conductivity of the two components in the foaming agent mixture, and then the λ of the two-component mixture. mix This can also be used to evaluate the thermal conductivity of more complex blowing agent mixtures by using it as a lambda input value for the mixture of the two-component mixture with a third blowing agent.

[0133] The bubble gas inside the foam bubbles may begin to condense when the foam temperature is at or below the boiling point of the blowing agent. Reference mean temperature (T) for lambda measurement of foam according to European standard EN 12667. mean ) is, for example, 10°C. Within the heat flow meter, the temperature setting of the plate is this T mean These are temperatures 10°C higher and 10°C lower. The temperature at which the bubble gas begins to condense will have a significant impact on the thermal conductivity of the product.

[0134] Figure 4 shows the effect of temperature on the thermal conductivity of phenolic foam blown with three different weight ratios of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and isopentane mixtures.

[0135] Foaming agents are generally selected to prevent condensation within the foam's air bubbles during use, specifically by avoiding condensation at temperatures above 10°C. Condensation leads to a decrease in insulation performance.

[0136] Foaming agents can also be classified based on their flammability. Standard ISO 817 classifies foaming agents based on their flammability.

[0137] [Table 3]

[0138] Several key parameters characterize the flammability level of a blowing agent (1, 2L, 2, and 3), including the burning rate (BV), upper and lower flammability limits (UFL and LFL), minimum ignition energy (MIE), and heat of combustion (HOC). 1) BV, combustion rate: This is the speed at which a flame propagates. 2) LFL, Lower Flammability Limit: The minimum concentration of a gas or vapor that can propagate a flame in a homogeneous mixture of the gas or vapor and air. 3) UFL, Upper Flammability Limit: The maximum concentration of a gas or vapor that can propagate a flame in a homogeneous mixture of the gas or vapor and air. 4) MIE, Minimum Ignition Energy: Indicates how much energy is required from an ignition source (e.g., a spark or open flame) to initiate ignition of a gas or vapor. 5) HOC (Heat of Combustion): This is the energy released as heat when a specific amount of a substance undergoes complete combustion under standard conditions.

[0139] Class 3 blowing agents have significantly lower LFL and significantly higher BV than Class 2L blowing agents. Therefore, the use of HCFOs and HFOs as blowing agents in phenolic resins should facilitate the manufacture of insulating products with excellent fire-resistant properties. Surprisingly, the inventors of this application have found that this is not the case.

[0140] The inventors of this application prepared various blowing agents in phenolic foams in which red phosphorus was pre-dispersed in a foaming phenolic resin mixture, and investigated their fire resistance and thermal conductivity. They found a particular blowing agent that can be used to form an insulating phenolic foam with remarkably excellent thermal conductivity and fire resistance. This effect is observed for the various blowing agents described herein and, in particular, in relation to the ternary mixture of blowing agents described herein.

[0141] Resin preparation Preparation of resin A In the reaction vessel, 50.0 pbw of phenol, 1-4 pbw of water, and 0.9 ± 0.2 pbw of 50% potassium hydroxide were added by weight (pbw = parts by weight) at 20°C. The temperature was raised to 70-76°C, and 35 ± 2 pbw of 91% paraformaldehyde was slowly added over 1-3 hours to dissipate the heat from the reaction heating wire. Next, the temperature was raised to 82-85°C and maintained within that temperature range until the viscosity of the resin reached 7500 mPa·s ± 1500 mPa·s. Cooling was started while neutralizing the pH with 0.3 pbw of 90% formic acid. As the temperature was reduced to below 60°C, the next items, namely 2-6 pbw of polyester polyol plasticizer and 3-6 pbw of urea, were added sequentially. After the urea was dissolved, 2-5 pbw of ethoxylated castor oil (surfactant) was added at 30-40°C. The resulting phenolic resin composition contained 10-13 wt% water, less than 4 wt% free phenol, and less than 1 wt% free formaldehyde. Preparation of resin P In a reaction vessel, 50.0 pbw of phenol, 1-4 pbw of water, and 0.9 ± 0.2 pbw of 50% potassium hydroxide were added by weight (pbw = parts by weight) at 20°C. The temperature was raised to 70-76°C, and 35 ± 2 pbw of 91% paraformaldehyde was slowly added over 1-3 hours to dissipate the heat from the reaction heating wire. Next, the temperature was raised to 82-85°C and maintained within that temperature range until the viscosity of the resin reached 7500 mPa·s ± 1500 mPa·s. Cooling was started while adding 0.3 pbw of 90% formic acid to neutralize the pH. When the temperature reached 70 ± 3°C, water was removed by vacuum distillation until the water content was 7.9-8.4%, as measured by Karl Fischer analysis. When the temperature was below 60°C, the following items were added sequentially: 2-6 lbw of polyester polyol plasticizer and 3-6 lbw of urea. Once the urea was dissolved, 7.6 ± 1.5 parts of a 50% ± 2% aqueous solution of red phosphorus were added and mixed until uniformly dispersed. Next, 2-5 lbw of ethoxylated castor oil (surfactant) was mixed at 30-40°C. The resulting phenolic resin composition, resin P, contains 10-13 wt% water, less than 4 wt% free phenol, and less than 1 wt% free formaldehyde.

[0142] Preparation of phenolic foam A general procedure for manufacturing phenol foam board is described in Comparative Example (CE) 1 below. Comparative Example 1 (CE1) - The foaming agent (BA) is isopropyl chloride:isopentane (iPC:iP, weight ratio 80+ / -5:20+ / -5).

[0143] To a resin A with a viscosity of 110 ± 5 pbw at 15°C to 19°C, calcium carbonate powder with a viscosity of 5 ± 2 pbw is added and mixed at 300 ± 100 rpm until the calcium carbonate is uniformly dispersed. The mixed resin mixture is pumped into a high-speed mixer, where an iPC:iP foaming agent with a viscosity of 9 ± 3 pbw at 1 to 3°C and a toluenesulfonic acid:xylenesulfonic acid catalyst in a 2:1 weight ratio with a viscosity of 20 ± 3 pbw at 8 to 15°C are quickly mixed into the resin mixture. Homogeneous mixing is achieved using high-speed mixing at 1000 to 4000 rpm to produce a foamed composition. Next, the foamed composition is poured into a suitable facing such as a nonwoven glass mat at a predetermined foaming resin flow rate and filled to a desired foam thickness of 20 to 150 mm, for example, 35 kg / m². 3 The desired final foam curing density is obtained. Next, the foaming mixture is transported by a horizontally moving conveyor belt to a conventional slat-type double conveyor foam lamination machine. The oven can be at a uniform temperature such as 70°C, or it can include several different temperature ranges. Just before entering the foam lamination machine, the top facing is introduced onto the foam resin composition. The moving foam material passes through a heated oven press, pressurizing the expanding foam at 40-50 kPa in a constant gap to obtain the desired foam board thickness. The expansion and initial curing of the foam in the oven press takes 4 to 15 minutes. The partially cured foam exiting the lamination machine is cut to the required length. The foam board is then placed in a secondary oven at 70-90°C until fully cured. Table 4 shows details of foam boards manufactured using such a method.

[0144] Comparative Example 6 (CE6) - The foaming agent (BA) is identified as resin "P / 2" and is an isopropyl chloride:isopentane (iPC:iP weight ratio 80+ / -5:20+ / -5) containing half the amount of red phosphorus used in resin P of Examples Ex1 to Ex6.

[0145] [Table 4]

[0146] Comparative Example 2 (CE2) - The foaming agent was HCFO-1233zd(E). Here, the same procedure as outlined in Comparative Example 1 was used, except that the blowing agent was changed to 14.8 parts by weight of HCFO-1233zd(E) blowing agent at 1-3°C. The density of the manufactured foam board was 35.6 kg / m³ 3 That was the case.

[0147] Comparative Example 3 (CE3) - Foaming agent: HCFO-1233zd(E):IP(70:30) It is identical to CE2, except that the foaming agents are HCFO-1233zd(E) at 8.47 pbw and isopentane at 3.63 pbw.

[0148] Comparative Example 4 (CE4) - The foaming agent is HCFO-1233zd(E):HFO-1336mzz(Z)(95:5) It is identical to CE2, except that the foaming agents are HCFO-1233zd(E) with a foaming agent of 13.18 pbw and HFO-1336mzz(Z) with a foaming agent of 0.76 pbw.

[0149] Comparative Example 5 (CE5) - Foaming agent: HCFO-1233zd(E):HFO-1336mzz(Z):isopentane (65:5:30) It is identical to CE2, except that the blowing agents are HCFO-1233zd(E) at 7.5 pbw, HFO-1336mzz(Z) at 0.58 pbw, and isopentane at 3.47 pbw.

[0150] [Table 5]

[0151] Example 1 (Ex1) - Foaming agent: HCFO-1233zd(E):IP(95:5) by weight ratio It is identical to CE2, except that the resin used is resin P and the foaming agent is 13.8 parts HCFO-1233zd(E) and 0.73 parts isopentane.

[0152] Example 2 (Ex2) - Foaming agent: HCFO-1233zd(E):IP(95:5) by weight ratio The reproducibility of the SBI fire test was evaluated, confirming it to be identical to Ex1. Therefore, the blowing agents are HCFO-1233zd(E) at 13.8 pbw and isopentane at 0.73 pbw.

[0153] Example 3 (Ex3) - Foaming agent is isopropyl chloride, iPC:IP (80:20) by weight ratio It is identical to Ex1, except that the foaming agents are isopropyl chloride at 6.8 pbw and isopentane at 1.7 pbw.

[0154] Example 4 (Ex4) - Foaming agent is isopropyl chloride, iPC:IP (80:20) by weight ratio It is identical to Ex1, except that the foaming agents are isopropyl chloride at 6.8 pbw and isopentane at 1.7 pbw.

[0155] Example 5 (Ex5) - Foaming agent is isopropyl chloride, iPC:IP (80:20) by weight ratio It is identical to Ex1, except that the foaming agents are isopropyl chloride at 6.8 pbw and isopentane at 1.7 pbw.

[0156] Example 6 (Ex6) - Foaming agent is isopropyl chloride, iPC:IP (80:20) by weight ratio It is identical to Ex1, except that the foaming agents are isopropyl chloride at 7.9 pbw and isopentane at 2.0 pbw.

[0157] [Table 6]

[0158] Examination of Comparative Examples and Examples The physical properties and fire resistance performance of the comparative and example foams are shown in Tables 4, 5, and 6.

[0159] The blowing agent for CE1 is a mixture of isopropyl chloride and isopentane in a weight ratio of 80:20. CE1 exhibits desirable initial and time-dependent thermal conductivity values, and its fire resistance classifies the CE1 foam as a Euro Class C product. CE6 has the same chemical composition as CE1, except that the weight of red phosphorus introduced into the foaming phenolic resin is half that of Ex1 to Ex6. As a result, the weight of red phosphorus in the cured foam is halved. While the cured foam does not achieve a Euro Class B fire resistance rating, the FIGRA 0.2MJ value is substantially reduced.

[0160] The blowing agent in CE2 is HCFO-1233zd (a non-flammable Class 1 blowing agent according to ISO 817 standard). CE2 exhibits excellent initial and long-term thermal conductivity. However, the fire resistance performance of CE2 is inferior to that expected when using a non-flammable blowing agent. When CE2 foam boards were evaluated according to BS EN13823 standard, high FIGRA values ​​of 0.2 MJ and 0.4 MJ were observed. Therefore, despite the use of a non-flammable blowing agent, the fire resistance performance of CE2 is worse than that of CE1, which consists of flammable isopentane and flammable isopropyl chloride. CE2 is classified as a Euro Class D fire growth rate product with "d0" indicating no smoke emission or dripping of Class "C2".

[0161] CE3 consists of a foaming agent mixture of HCFO-1233zd and isopentane, and exhibits desirable performance in initial and time-dependent thermal conductivity values, as well as improved fire resistance compared to CE2. However, despite this improvement, CE3 is classified as a Euro Class C product, not a Euro Class B product.

[0162] CE4 consists of a blowing agent mixture of HCFO-1233zd and HFO-1336mzz. HFO-1336mzz is also classified as a non-flammable Class 1 blowing agent according to standard ISO 817. The initial and time-dependent thermal conductivity values ​​of CE4 are excellent. Despite having two flame-retardant blowing agents, the FIGRA 0.2MJ and FIGRA 0.4MJ values ​​are: These levels are surprisingly higher than those observed for CE3 containing flammable isopentane.

[0163] CE5 consists of a ternary blowing agent mixture of HCFO-1233zd, HFO-1336mzz, and isopentane. Despite the inclusion of highly flammable isopentane, the desired low initial and time-dependent thermal conductivity values ​​remain nearly constant, and despite the FIGRA 0.2MJ value remaining above 150 W / s (Euro Class C), there is a clear and dramatic improvement in fire resistance.

[0164] In contrast, E1 to E6 demonstrate that when a specific ternary mixture consisting of chlorinated hydrofluoroolefin, hydrofluoroolefin, and hydrocarbons is used in a phenolic foaming chemical mixture, along with 2 to 5 parts by weight of fine particles (particle size 0.5 to 10 μm) of red phosphorus based on 100 parts by weight of cured phenolic foam, a FIGRA value of less than 150 W / s or 0.2 MJ can be achieved. This demonstrates excellent fire resistance and FIGRA (0.2 MJ threshold) < 150 W / s and SMOGRA < 20 m 2 / s 2 This results in foam insulation products with low smoke emission as defined by [definition]. In fact, E1 to E6 each exhibit FIGRA 0.2MJ values ​​of less than 120 W / s, and are therefore classified as having the desirable Euro Class B fire resistance performance rating. This is achieved without adversely affecting the low thermal conductivity of the foam. The present invention relates to stable thermal insulation performance (<0.023 W / m·K) and a high closed-cell content (>85%).

[0165] The blowing agent used to form the phenol foam of the present invention comprises at least one chlorinated hydrofluoroolefin, or at least one hydrofluoroolefin, at least one alkyl halide, or at least one chlorinated alkene and at least one C3-C6 hydrocarbon, and combinations thereof. The at least one chlorinated hydrofluoroolefin, or the at least one alkyl halide, or the at least one chlorinated alkene, or combinations thereof, is preferably present in an amount of about 62 wt% to 95 wt% based on the total weight of the blowing agent. The hydrofluoroolefin is preferably present in an amount of about 5 to 15 wt% based on the total weight of the blowing agent. The at least one C3-C6 hydrocarbon is present in an amount of 4 to 25 wt% based on the total weight of the blowing agent.

[0166] As demonstrated by comparing CE1, which does not contain red phosphorus in the foam, with CE6, which contains half the optimal amount present in "Resin P," the FIGRA 0.2 MJ value obtained for CE6 is substantially improved despite the presence of highly flammable isopropyl chloride and isopentane in the phenolic foam. However, even with this reduction in the amount of red phosphorus in the foam, only Euro Class C is achieved. To achieve Euro Class B, the weight of red phosphorus in the foam must be within the range used in Examples 1 to 6 obtained from "Resin P." Adding an excessive amount of red phosphorus, more than 5 parts by weight per 100 parts by weight of cured foam, will increase the SMOGRA value and risk compromising low, stable thermal conductivity over time. The proposed range of red phosphorus amounts, 2 to 5 parts by weight with a particle size of 0.5 to 10 μm per 100 parts by weight of cured phenolic foam, ensures the necessary conditions for stable improvement in thermal insulation and fire resistance. Adding too much red phosphorus to the aforementioned foaming resin mixture can lead to problems in foam manufacturing due to the excessively high viscosity of the chemical mixture during mixing. Historically, improvements in the fire resistance of foams have been achieved by the presence of organic or inorganic phosphorus compounds in the foam. The concentration of phosphorus per unit weight is higher than that of red phosphorus in other organic or inorganic phosphorus compounds. Obtaining 2 to 5 parts by weight of phosphorus per 100 parts by weight of phenol foam requires a higher loading of these other phosphorus compounds. Such high additions may plasticize the foam bubbles if the organophosphorus compound is liquid, or damage the foam bubbles during the mechanical mixing process if the organophosphorus compound is solid. A detrimental effect on thermal insulation foam is an undesirably high thermal conductivity.

[0167] For example, 5 parts ammonium polyphosphate particles per 100 parts of uncured phenolic resin increase the initial and time-dependent lambda of the foam. Table 7 below shows that the unit weight of elemental phosphorus is higher than that of other phosphorus-based compounds, allowing for less flame retardant to be required in the cured foam, and thus without compromising thermal insulation.

[0168] [Table 7]

[0169] Generally, 2 to 5 parts by weight of red phosphorus per 100 parts by weight of cured phenolic foam is required to obtain a Euro Class B foam insulation product with appropriate types of blowing agents and surfactants.

[0170] However, if the amount of hydrocarbons exceeds approximately 25% by weight of the blowing agent composition, it can negatively affect the fire resistance of the foam, making it impossible to achieve Euro Class B foam. Furthermore, as indicated by CE2 and CE4, if hydrocarbons are present at less than approximately 5% by weight, the fire resistance is also adversely affected.

[0171] If less than approximately 3 wt% of hydrofluoroolefin is present, the fire resistance of the product decreases, and if more than approximately 20 wt% of hydrofluoroolefin is present, the thermal conductivity of the foam product increases.

[0172] Therefore, when the blowing agent consists of the aforementioned ternary mixture, optimal thermal insulation and fire resistance performance are achieved.

[0173] In the form of the present invention, the % vulnerability is less than 30%, for example less than 25%, as measured according to the test method ASTM C421-08(2014).

[0174] A further desirable aspect of the present invention is that the presence of 2-5% by weight of particulate (particle size 0.5-10 μm) red phosphorus flame retardant per 100 parts by weight of cured phenol foam results in a phenol foam insulation product in which formaldehyde emissions from the phenol foam product are reduced by 30-60% as measured according to the standards EN717-1 / EN16516 / ISO16000-11. Table 8 below shows the formaldehyde scavenging effect of red phosphorus present in phenol foam, regardless of the type of blowing agent.

[0175] [Table 8]

[0176] As described above, the at least one chlorinated hydrofluoroolefin is present in an amount of about 65 wt% to about 92 wt% based on the total weight of the blowing agent used to form the phenol foam of the present invention. Preferably, the chlorinated hydrofluoroolefin is present in an amount of about 72 wt% to about 92 wt% based on the total weight of the blowing agent. More preferably, the chlorinated hydrofluoroolefin is present in an amount of about 72 wt% to about 88 wt% based on the total weight of the blowing agent, and even more preferably, the chlorinated hydrofluoroolefin is present in an amount of about 72 wt% to about 82 wt% based on the total weight of the blowing agent.

[0177] The at least one hydrofluoroolefin is present in an amount of about 5 wt% to about 20 wt% based on the total weight of the blowing agent used to form the phenol foam of the present invention. Preferably, the hydrofluoroolefin is present in an amount of about 5 wt% to about 15 wt%, such as about 8 wt% to about 14 wt% based on the total weight of the blowing agent.

[0178] The C3-C6 hydrocarbon is present in an amount of about 4 wt% to about 25 wt% based on the total weight of the blowing agent used to form the phenol foam of the present invention. Preferably, the C3-C6 hydrocarbon is present in an amount of about 5 wt% to about 20 wt%, such as about 8 wt% to about 18 wt%, based on the total weight of the blowing agent.

[0179] Preferably, the chlorinated hydrofluoroolefin is selected from HCFO-1233zd and HCFO-1224yd.

[0180] The chlorinated hydrofluoroolefin can be HCFO-1233zd-(E) and / or HCFO-1233zd-(Z). For example, the HCFO-1233zd can be at least 90 wt% of the E-isomer (HCFO-1233zd-(E)), for example, at least 95 wt% of the E-isomer (HCFO-1233zd-(E)).

[0181] The hydrofluoroolefin is preferably HFO-1336mzz. The HFO-1336mzz may be HFO-1336mzz-(Z) and / or HFO-1336mzz-(E). For example, the HFO-1336mzz may be at least 90 wt% of the Z-isomer (HFO-1336mzz-(Z)), for example, at least 95 wt% of the Z-isomer (HFO-1336mzz-(Z)).

[0182] Preferably, the C3-C6 hydrocarbon is propane, butane, pentane, hexane, or an isomer thereof. More preferably, the C3-C6 hydrocarbon consists of butane and / or pentane. Preferably, the butane is isobutane. Preferably, the pentane is isopentane.

[0183] Advantageously, the foams of Examples 1 to 6 each exhibit stable low thermal conductivity under prolonged exposure to temperature and other conditions, as well as excellent fire resistance. The foams of Examples 1 to 6 are each Euro Class B products.

[0184] In this specification, the terms “comprises / comprising” and “having / including” as used in relation to the present invention are used to identify the presence of specified features, integers, steps (processes) or components, but do not preclude the presence or addition of one or more other features, integers, steps, components or sets thereof.

[0185] Certain features of the present invention, for clarity, can be described in separate embodiments, but can be combined to form a single embodiment. Conversely, various features of the present invention, for simplicity, can be described in a single embodiment, but can be provided separately or in any appropriate partial combination.

Claims

1. The use of red phosphorus as a formaldehyde scavenger in phenolic foam, The phenol foam is formed from a foaming agent and a foamable phenolic resin composition. The phenol foam, when its red phosphorus concentration is measured by the ICP-OES method described herein, consists of 1 to 5% by weight of red phosphorus based on the weight of the phenol foam, and the concentration is 10 kg / m³. ３ From 100 kg / m ３ It has a density of 120 W / s or less, measured according to the standard ASTM D6226, and has a closed-cell content of at least 85%, measured according to the European standard EN13823. 0.2MJ The use of red phosphorus in phenolic foam, which has a thermal conductivity of 0.023 W / mK or less at 10°C according to European standard EN13166:2012.

2. The use of red phosphorus in the phenolic foam according to claim 1, wherein the phenolic foam comprises 2 to 5% by weight of red phosphorus based on the weight of the phenolic foam.

3. The blowing agent is at least one saturated or unsaturated C ３ -C ６ A hydrocarbon and at least one saturated or unsaturated carbon atom substituted at least once with one or more fluorine or chlorine atoms. ３ -C ６ Use of red phosphorus in the phenol form according to claim 1 or 2, comprising at least one compound.

4. The blowing agent is at least one of isopropyl chloride or saturated C ３ -C ６ Use of red phosphorus in the phenolic foam according to any one of claims 1 to 3, which consists of at least one of hydrocarbons.

5. The aforementioned foaming agent is isopropyl chloride and saturated C ３ -C ６ Use of red phosphorus in a phenolic form according to any one of claims 1 to 4, comprising a mixture with hydrocarbons.

6. The phenolic foam, measured according to European standard EN13823, has a FIGRA of 110 W / s or less. 0.2MJ The use of red phosphorus in a phenolic form according to any one of claims 1 to 5.

7. The use of red phosphorus in a phenolic foam according to any one of claims 1 to 6, wherein the foaming agent comprises at least one hydrofluoroolefin or chlorinated hydrofluoroolefin.

8. The aforementioned blowing agent further comprises at least one saturated or unsaturated C ３ -C ６ A hydrocarbon and at least one saturated or unsaturated carbon atom substituted at least once with one or more fluorine or chlorine atoms. ３ -C ６ Use of red phosphorus in the phenol form according to claim 7, comprising at least one compound.

9. The blowing agent comprises at least one hydrofluoroolefin or chlorinated hydrofluoroolefin, and C ３ -C ６ Use of red phosphorus in a phenolic form according to claim 7 or 8, comprising a mixture with hydrocarbons.

10. The phenolic foam, when measured according to European standard EN13823, has a FIGRA of 100 W / s or less. 0.2MJ The use of red phosphorus in a phenolic form according to any one of claims 1 to 9.

11. The use of red phosphorus in the phenol foam according to any one of claims 1 to 10, wherein the phenol foam has a compressive strength of at least 95 kPa.

12. The use of red phosphorus in a phenolic foam according to any one of claims 1 to 11, wherein the red phosphorus is in particulate form with a number-average particle diameter in the range of 0.1 μm to 25 μm.

13. The use of red phosphorus in the phenolic foam according to any one of claims 1 to 12, wherein the phenolic foam has a total heat generation rate of 7.5 MJ or less when measured in accordance with the European standard EN13823.

14. The use of red phosphorus in the phenol foam according to any one of claims 1 to 13, wherein the closed-cell content of the phenol foam is 90% or more when measured according to the standard ASTM D6226.

15. The use of red phosphorus in the phenol foam according to any one of claims 1 to 14, wherein the average bubble diameter of the bubbles in the phenol foam is in the range of 50 to 250 μm.

16. The use of red phosphorus in the phenolic foam according to any one of claims 1 to 15, wherein the thermal conductivity of the phenolic foam is 0.020 W / mK or less when measured at an average temperature of 10°C in accordance with the European standard EN13166:2012.

17. The use of red phosphorus in the phenolic foam according to any one of claims 1 to 16, wherein the phenolic foam has a limiting oxygen index of 34% or higher as measured in accordance with the standard ISO 4589-2.

18. The use of red phosphorus in the phenolic foam according to any one of claims 1 to 17, wherein the phenolic foam has a stable water content of 3% to 8% by weight as measured at a temperature of (23±2)°C and a relative humidity of (50±5)% in accordance with the European standard EN1249:1998.

19. The use of red phosphorus in a phenolic form according to any one of claims 7 to 18, wherein the at least one chlorinated hydrofluoroolefin is selected from 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd).

20. The use of red phosphorus in a phenolic form according to any one of claims 7 to 19, wherein the at least one hydrofluoroolefin is 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz).

21. The use of red phosphorus in a phenolic foam according to any one of claims 3 to 20, wherein the foaming agent comprises at least one saturated or unsaturated C3-C6 hydrocarbon, which comprises at least one butane and / or at least one pentane.

22. The use of red phosphorus as a formaldehyde scavenger in phenolic foam, The phenol foam is formed by foaming and curing a foamable phenol resin composition, the foamable phenol resin composition comprising a phenol resin, a surfactant, an acid catalyst, a foaming agent, and, when the red phosphorus concentration in the phenol foam is measured by the ICP-OES method described herein, 1 to 5% by weight of red phosphorus based on the weight of the phenol foam. The phenolic foam is 10 kg / m³ ３ From 100 kg / m ３ The density of the phenolic foam, measured according to standard ASTM D6226, has a closed-cell content of at least 85%, and the phenolic foam has a strength of 120 W / s or less when measured according to European standard EN13823. 0.2MJ The use of red phosphorus in a phenolic foam, wherein the phenolic foam has a thermal conductivity of 0.023 W / mK or less at 10°C in accordance with the European standard EN13166:2012.

23. The blowing agent comprises at least one hydrofluoroolefin and at least one chlorinated hydrofluoroolefin, and the blowing agent further comprises at least one C ３ -C ６ Use of red phosphorus in the phenolic form according to claim 22, which consists of hydrocarbons.

24. The use of red phosphorus in the phenol form according to claim 23, wherein the at least one chlorinated hydrofluoroolefin is selected from 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd).

25. The use of red phosphorus in the phenolic form according to claim 23 or 24, wherein the at least one hydrofluoroolefin is 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz).

26. The at least one type of C ３ -C ６ The use of red phosphorus in a phenolic form according to any one of claims 23 to 25, wherein the hydrocarbon comprises at least one butane and / or at least one pentane.

27. The use of red phosphorus in a phenolic foam according to any one of claims 1 to 26, wherein the foaming agent comprises 1-chloro-3,3,3-trifluoropropene and / or 1-chloro-2,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene.

28. The use of red phosphorus in a phenol foam according to any one of claims 1 to 27, wherein the foaming phenol resin composition comprises a phenol resin having a weight-average molecular weight of 700 to 2000, and / or the number-average molecular weight of the phenol resin is 330 to 800.

29. The use of red phosphorus in a phenol foam according to any one of claims 1 to 28, wherein the foamed phenol resin composition comprises a phenol resin having a molar ratio of phenol groups to aldehyde groups in the range of 1:1 to 1:

3.

30. The use of red phosphorus in a phenolic foam according to any one of claims 1 to 29, wherein the water content of the foaming phenolic resin composition is in the range of 5 wt% to 12 wt% based on the total weight of the foaming phenolic resin composition.

31. The use of red phosphorus in a phenol foam according to any one of claims 1 to 30, wherein the foaming phenol resin composition comprises a phenol resin, and the water content of the phenol resin is in the range of 7.5 wt% to 14 wt% based on the weight of the phenol resin.

32. The use of red phosphorus in a phenolic foam according to any one of claims 1 to 31, wherein the foaming phenolic resin composition comprises a phenolic resin having a viscosity of 2,500 mPa·s to 18,000 mPa·s when measured at 25°C.

33. The use of red phosphorus in a phenol foam according to any one of claims 1 to 32, wherein the foaming phenol resin composition consists of a phenol resin, and the foaming agent is present in an amount of 1 to 20 parts by weight per 100 parts by weight of the phenol resin.

34. The use of red phosphorus in the phenol foam according to any one of claims 1 to 33, wherein the phenol foam has a compressive strength in the range of 95 kPa to 200 kPa as measured in accordance with the European standard EN826.

35. The phenolic foam is 15 kg / m³ ３ From 60 kg / m ３ Use of red phosphorus in a phenolic foam according to any one of claims 1 to 34 having a density.

36. The phenolic foam is 34.5 kg / m³ ３ From 40 kg / m ３ Use of red phosphorus in a phenolic foam according to any one of claims 1 to 35 having a density.

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