Foaming Agent Composition for Polyurethane and Method of Preparing Polyurethane Foam Using the Same

Abstract

The polyurethane blowing agent composition according to the present invention comprises a certain proportion of a physical blowing agent (physico-chemical blowing agent) and a chemical blowing agent, glycerol carbonate, and the polyurethane foam produced using this has the effect of having very low global warming potential and ozone depletion potential, while simultaneously having improved thermal conductivity, water absorption, flexural strength, and compressive strength properties that meet the standards of rigid urethane foam insulation.

Description

Technology Field

[0001] The present invention relates to a polyurethane foaming agent composition and a method for manufacturing a polyurethane foam using the same. More specifically, the invention relates to a polyurethane foaming agent composition comprising a certain proportion of a physical foaming agent and a chemical foaming agent, glycerol carbonate, which has a very low global warming potential and ozone depletion potential, and a method for manufacturing a polyurethane foam using the same, which has improved thermal conductivity, water absorption, flexural strength, and compressive strength properties that meet the standards of rigid urethane foam insulation. Background Technology

[0003] Low-density rigid polyurethane foams are used in various fields, such as bedding (mattresses and pillows), cushioning (household chairs and automotive seats), roofing systems, and building insulation (building panels). A key factor in the large-scale commercial use of rigid polyurethane foams is their ability to provide excellent balance characteristics. Rigid polyurethane foams are known to offer superior structural properties due to their excellent thermal insulation, superior heat resistance, and significantly low density. The foam industry has utilized liquid fluorocarbon blowing agents due to the ease of processing conditions.

[0004] In the industry, foams manufactured using fluorine-containing olefin compounds as blowing agents, such as HFO-1234ze (1,3,3,3-tetrafluoropropene), HCFO-1233zd (1-chloro-3,3,3-trifluoropropene), HFC-245fa (pentafluoropropane), and HCFC-141b (1,1-dichloro-1-fluoroethane), have been widely used because they exhibit excellent physical properties, such as low thermal conductivity and high dimensional stability. However, the above fluorine-containing olefin compounds not only have high costs as blowing agents but also have a very high global warming potential (GWP), so their use has been decreasing recently as environmental issues are becoming increasingly important.

[0005] To compensate for the disadvantages of these fluorine-containing olefin compounds, hydrocarbon blowing agents such as iso-pentane, normal-pentane, and cyclopentane may be used. Hydrocarbon blowing agents are environmentally friendly blowing agents as they have an ozone depletion potential (ODP) of 0 and a very low global warming potential. However, foams produced from these blowing agents have the disadvantage of lower thermal insulation efficiency compared to foams produced using fluorine-containing olefin compounds as blowing agents. Furthermore, hydrocarbon blowing agents are uneconomical because they lack sufficient miscibility with materials and additives essential for the manufacture of polyurethane foams, such as polyols, which complicate processes and equipment. Additionally, when additives are included in the composition to improve various physical properties of the polyurethane foam, the mechanical properties of the final polyurethane foam are degraded. Furthermore, in the case of cyclopentane, handling it in actual processes is difficult due to its inherent flammability.

[0006] In addition, trans-1,2-dichloroethylene, another compound that can compensate for the disadvantages of fluorine-containing olefin compounds, is a non-toxic substance that is liquid at room temperature because it has a boiling point of 48°C. It does not destroy the ozone layer and has a very low ozone depletion potential because its atmospheric lifetime is very short. U.S. Patent No. 7,144,926 discloses a composition comprising trans-1,2-dichloroethylene and a hydrofluorocarbon compound, and Korean Registered Patent No. 10-1532221 discloses a polyol premix composition comprising a mixture of a hydrohaloolefin blowing agent including trans-1,2-dichloroethylene, a polyol, a surfactant component that is a non-silicone surfactant and substantially free of silicone surfactants, and a tertiary amine catalyst. However, the above patents have the problem of containing hydrofluorocarbons (HFCs) with high GWP and hydrohaloolefins (HFOs), which are difficult to access economically due to their high cost, although they cause fewer environmental problems.

[0007] Meanwhile, methyl formate can also be used as a blowing agent. Published Patent No. 2016-0023050 discloses a composition for forming a rigid polyurethane foam that includes a polyester polyol and / or a polyether polyol and a methyl formate blowing agent. When a polyurethane foam is manufactured using methyl formate, the foam shrinks significantly, resulting in poor dimensional stability. Additionally, it has the disadvantage of unstable miscibility and storage stability with materials essential for manufacturing polyurethane foam, such as polyols.

[0008] In addition, research has been conducted using glycerol carbonate (glycerine carbonate or 4-hydroxymethyl-2-oxo-1,3-dioxolane) as a blowing agent (Matthieu O. Sonnati et al., "Glycerol carbonate as a versatile building block for tomorrow: synthesis, reactivity, properties and applications", Green Chem., 2013, 15, 283-306; U.S. Patent No. 5,703,136; European Patent No. 0 419 114 A2). However, when glycerol carbonate, a chemical blowing agent, is used alone, there are problems such as foam destabilization (splitting) and rapid reactivity caused by the generation of internal heat.

[0009] Therefore, there is a need for a novel blowing agent that minimizes the disadvantages of existing blowing agents used in the manufacture of polyurethane foams while providing excellent physical properties to the polyurethane foam produced using it, as well as a composition for manufacturing polyurethane foam containing the same.

[0010] Accordingly, the inventors of the present invention have made diligent efforts to solve the above problems and have confirmed that when a polyurethane foam is manufactured using a polyurethane blowing agent composition (Physico-chemical Blowing Agent) containing a physical blowing agent such as methyl formate and a chemical blowing agent such as glycerol carbonate in a certain ratio, the physical properties such as thermal conductivity, water absorption, flexural strength, and compressive strength are very suitable for the specifications of rigid polyurethane foam insulation, and at the same time, an eco-friendly polyurethane foam can be manufactured with very low global warming potential and ozone depletion potential, thereby completing the present invention. Prior art literature

[0012] U.S. Patent No. 5,703,136, European Patent Published No. 0 419 114 A2

[0013] Matthieu O. Sonnati et al., “Glycerol carbonate as a versatile building block for tomorrow: synthesis, reactivity, properties and applications”, Green Chem., 2013, 15, 283-306 The problem to be solved

[0014] The objective of the present invention is to provide a polyurethane foaming agent composition capable of producing a polyurethane foam having very low global warming potential and ozone depletion potential, and having improved performance such as thermal conductivity, water absorption, flexural strength, and compressive strength to meet the specifications of rigid polyurethane foam insulation, and a method for producing a polyurethane foam using the same. means of solving the problem

[0016] In order to achieve the above objectives,

[0017] The present invention provides a polyurethane foaming agent composition comprising glycerol carbonate and a physical foaming agent.

[0018] The above physical blowing agent is methyl formate, chloropropene, 1-chloropropene, 2-chloropropene, 3-chloropropene, 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, cis-1,1,1,4,4,4-hexafluoro-2-butene, pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 1,1-dichloro-1-fluoroethane, It is preferable to select one or more from the group consisting of trans-1,2-dichloroethylene, chloropropane, methylal, c-pentane, n-pentane, and i-pentane.

[0019] It is preferable to include the physical foaming agent in an amount of 20 to 40 parts by weight per 100 parts by weight of the composition.

[0020] The above may additionally include more than 0 parts by weight and less than or equal to 10 parts by weight of methyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate or more than 0 parts by weight and less than or equal to 5 parts by weight of bis ((2-oxo-1,3-dioxolan-4-yl)methyl) carbonate) with respect to 100 parts by weight of glycerol carbonate.

[0021] The above may additionally include 0.01 to 30 parts by weight of glycerol with respect to 100 parts by weight of glycerol carbonate.

[0022] The above physical foaming agent is methyl formate, and

[0023] It is preferable to include the methyl formate in an amount of 20 to 30 parts by weight per 100 parts by weight of the composition.

[0024] The above physical foaming agent is chloropropene, and

[0025] It is preferable to include the above chloropropene in an amount of 20 to 40 parts by weight per 100 parts by weight of the composition.

[0026] The above physical foaming agent is 1-chloro-3,3,3-trifluoropropene (1-chloro-3,3,3-trifluoropropene, HFO-1233zd), and

[0027] It is preferable to include the above 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) in an amount of 20 to 40 parts by weight per 100 parts by weight of the composition.

[0028] The above physical foaming agents are chloropropene and 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), and

[0029] It is preferable to include 15 to 20 parts by weight of the chloropropene per 100 parts by weight of the composition, and 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) per 100 parts by weight of the composition.

[0030] In addition, the present invention

[0031] (a) a step of preparing a first liquid comprising a polyol, a surfactant, water, a catalyst, trichloropropyl phosphate, and the polyurethane foaming agent composition of the present invention;

[0032] (b) a step of mixing 100 parts by weight of a first solution and 100 to 150 parts by weight of a second solution containing polyisocyanate relative to 100 parts by weight of the first solution; and

[0033] (c) a step of reacting a mixture of the first liquid and the second liquid to produce a polyurethane foam; a method for producing a polyurethane foam is provided.

[0034] The thermal conductivity of the above polyurethane foam is greater than 0.018 and less than or equal to 0.023 W / m·K, and the water absorption is greater than 0 and 3.0 g / 100cm 2 Below, flexural failure load is greater than 25 N and less than or equal to 100 N, and compressive strength is greater than 15 and less than or equal to 25 N / cm 2 It is as follows. Effects of the invention

[0036] The polyurethane foam produced using the polyurethane foaming agent composition according to the present invention has the effect of having very low global warming potential and ozone depletion potential, while simultaneously possessing improved physical properties of thermal conductivity, water absorption, flexural strength, and compressive strength to a level that meets the standards of rigid urethane foam insulation.

[0037] In addition, it is particularly advantageous for spray applications due to its rapid post-curing, and it is suitable for ester polyols, which improves flame retardancy and reduces costs. It can provide shrinkage prevention without using sorbitol-based ether polyols, which are used to prevent foam shrinkage but are problematic due to their high viscosity.

[0038] In addition, it is an eco-friendly foaming agent that has storage stability after system manufacturing and excellent compatibility during system manufacturing. Brief explanation of the drawing

[0040] Figure 1 is a photograph of the cell size during foaming according to Comparative Example 2 of the present invention. Figure 2 is a photograph of the cell size at foaming according to Example 8 of the present invention. Figure 3 is a graph comparing the thermal conductivity of Examples 1 to 15 of the present invention. Specific details for implementing the invention

[0041] The present invention will be described in detail below. In describing the present invention, detailed descriptions of related known components or functions may be omitted.

[0042] Terms and words used in this specification and claims are not to be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a sense and concept consistent with the technical details of the present invention.

[0043] The embodiments described in this specification and the configurations illustrated in the drawings are preferred embodiments of the present invention and do not represent all technical aspects of the present invention; therefore, various equivalents and modifications that can replace them may exist at the time of filing this application.

[0045] The present invention will be described in more detail below through examples. These examples are solely for the purpose of more specifically explaining the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the invention.

[0047] In the present invention, it was confirmed that when a polyurethane foaming agent composition containing a certain proportion of a chemical foaming agent, glycerol carbonate, and a physical foaming agent, methyl formate, is used in the process of manufacturing a polyurethane foam, physical properties such as thermal conductivity, water absorption, flexural strength, and compressive strength are improved to a level that meets the standards of rigid polyurethane foam insulation, while also having excellent storage stability and compatibility, and very low global warming potential and ozone depletion potential, it is possible to manufacture an eco-friendly polyurethane foam.

[0048] Accordingly, in one aspect, the present invention relates to a polyurethane blowing agent composition (Physico chemical Blowing Agent) comprising glycerol carbonate and a physical blowing agent.

[0049] In another aspect, the present invention also relates to a method for manufacturing a polyurethane foam, comprising the steps of: (b) preparing a first liquid comprising a polyol, a surfactant, water, a catalyst, trichloropropyl phosphate, and the polyurethane foaming agent composition; (b) mixing 100 parts by weight of the first liquid with 100 to 150 parts by weight of a second liquid comprising a polyisocyanate relative to 100 parts by weight of the first liquid; and (c) reacting the mixture of the first liquid and the second liquid to produce a polyurethane foam.

[0051] Hereinafter, the polyurethane foaming agent composition according to the present invention and the method for manufacturing a polyurethane foam using the same will be described in detail.

[0053] The present invention relates to a foaming agent composition comprising glycerol carbonate, a chemical foaming agent for manufacturing polyurethane foam, wherein the composition includes glycerol carbonate, a chemical foaming agent for polyurethane foam, in an appropriate and ideal ratio with a physical foaming agent such as methyl formate, thereby optimizing the function as a composite foaming agent by controlling the destabilization (splitting) and rapid reactivity of the foam caused by internal heat that occurs when glycerol carbonate, a chemical foaming agent, is used alone, with methyl formate, a physical foaming agent.

[0054] In other words, glycerol carbonate, a chemical blowing agent, exhibits a mechanism in which foaming occurs simultaneously with polyurethane bonding due to the release of carbon dioxide through the rapid reaction between the cyclic carbonate contained in its structure and the NCO of the isocyanate, thereby forming internal cells. The polyurethane foam generated by the carbon dioxide produced through these chemical changes increases the formation of urethane cross-links associated with NCO bonds, thereby increasing the strength of the foam surface and interior. However, the reduction in initial foaming power and foam splitting caused by internal exothermic reactions are considered major problems associated with this reaction. Therefore, the mixed use of a physical blowing agent, which utilizes low boiling point properties for rapid foaming power, can be considered the discovery of a stable mixed blowing agent (physico-chemical blowing agent) that leverages the mutual advantages.

[0055] It was confirmed that the formation of foam using a mixed blowing agent exhibits the formation of very small and uniform cells, which significantly affects thermal conductivity and predicts excellent properties as an insulating material. Furthermore, the completion of a rapid cross-linking reaction can serve as a significant advantage for foams used in polyurethane boards and spray applications.

[0057] The present invention first provides a foaming agent composition that simultaneously satisfies the criteria for a very low global warming potential and an ozone depletion potential.

[0058] ODP (Ozone Depletion Potential) is a numerical representation of the ozone-depleting ability of chemical substances that are directly or indirectly involved in ozone depletion. ODP sets the ozone-depleting ability of 1 kg of trichlorofluorocarbon (CFC-11), a type of chlorofluorocarbon, as 1 and expresses the ozone-depleting ability of other chemical substances as a ratio. In other words, it is calculated as (amount of ozone destroyed by 1 kg of a certain chemical substance / amount of ozone destroyed by 1 kg of CFC-11), and the higher the ODP number, the greater the degree of ozone depletion.

[0059] The degree to which greenhouse gases contribute to global warming varies; generally, the contribution of each gas relative to carbon dioxide is specified as the Global Warming Potential (GWP), and countries calculate greenhouse gas emissions in units of CO2 tons, taking into account the GWP of each gas.

[0060] "GWP" is a measurement taken over a 100-year period relative to carbon dioxide, as defined in "The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project."

[0061] The mixed blowing agent composition according to the present invention has a global warming potential of 0 to 50 or less. Glycerol carbonate, a chemical blowing agent, has a GWP value of 0 (zero) and also has an ozone depletion potential of 0 (zero). The mixed physical blowing agent has very low values, that is, it is an eco-friendly blowing agent having GWP and ODP values ​​close to "0".

[0063] The polyurethane foaming agent composition of the present invention comprises glycerol carbonate and a physical foaming agent.

[0064] In the present invention, the physical blowing agent is methyl formate, chloropropene, 1-chloropropene, 2-chloropropene, 3-chloropropene, 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, cis-1,1,1,4,4,4-hexafluoro-2-butene, pentafluoropropane, 1,1,1,3,3-pentafluorobutane, One or more may be selected from the group consisting of 1,1-dichloro-1-fluoroethane, trans-1,2-dichloroethylene, chloropropane, methylal, c-pentane, n-pentane, and i-pentane. Preferably, methyl formate, chloropropene, 1-chloropropene, 2-chloropropene, 3-chloropropene, 1-chloro-3,3,3-trifluoropropene, pentafluoropropane (HCFC-245fa), 1,1,1,3,3-pentafluorobutane (HCFC-365mfc), and 1,1-dichloro-1-fluoroethane (HCFC-141b) may be used, but are not limited thereto.In particular, methyl formate is preferably used because it has the advantages of being inexpensive and eco-friendly, and similar functions can be achieved by applying other types of physical foaming agents.

[0065] In the present invention, glycerol carbonate is referred to as glycerin carbonate or 4-(hydroxymethyl)-1,3-dioxolan-2-one and has the structure of Formula 1. Methyl formate has the structure of Formula 2.

[0067] [Chemical Formula 1]

[0068]

[0070] [Chemical Formula 2]

[0071]

[0073] In the polyurethane foaming agent composition of the present invention, it is preferable to include the physical foaming agent in an amount of 20 to 40 parts by weight per 100 parts by weight of the composition.

[0074] In the polyurethane foaming agent composition according to the present invention, as the content of the physical foaming agent decreases, the degree of urethane crosslinking increases, resulting in higher values ​​for density and compressive strength.

[0075] If the content of the above physical foaming agent is less than 20 parts by weight, cracking occurs due to internal heat of the foam and there is a problem that it is difficult to control the reaction rate, and if it exceeds 40 parts by weight, there are problems such as storage stability of the system and shrinkage of the foam.

[0076] When the physical foaming agent is methyl formate, it is preferable to include 20 to 30 parts by weight of the methyl formate per 100 parts by weight of the composition.

[0077] In the case where the physical foaming agent is chloropropene, it is preferable to include 20 to 40 parts by weight of chloropropene per 100 parts by weight of the composition.

[0078] When the above physical foaming agent is 1-chloro-3,3,3-trifluoropropene (1-chloro-3,3,3-trifluoropropene, HFO-1233zd), it is preferable to include 20 to 40 parts by weight of 1-chloro-3,3,3-trifluoropropene (1-chloro-3,3,3-trifluoropropene, HFO-1233zd) per 100 parts by weight of the composition.

[0079] The above physical foaming agents are chloropropene and 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), and

[0080] It is preferable to include 15 to 20 parts by weight of the chloropropene per 100 parts by weight of the composition, and 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) per 100 parts by weight of the composition.

[0081] In the polyurethane foaming agent composition of the present invention, more than 0 parts by weight and less than or equal to 10 parts by weight of methyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate of Formula 3, preferably 0.01 to 10 parts by weight, or more than 0 parts by weight and less than or equal to 5 parts by weight of bis ((2-oxo-1,3-dioxolan-4-yl)methyl) carbonate of Formula 4, preferably 0.01 to 5 parts by weight, may be additionally included with respect to 100 parts by weight of glycerol carbonate, wherein the above components are components included as by-products during manufacturing and serve as separate cross-links through the stable supply of CO2 and the combination of MDI with NCO.

[0083] [Chemical Formula 3]

[0084]

[0086] [Chemical Formula 4]

[0087]

[0089] In the polyurethane foaming agent composition of the present invention, while a large amount of glycerol carbonate, which is the main foaming agent, is required, there is no problem at all even if a very small amount of methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate or bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate is added as a byproduct. However, if the amount of methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate added exceeds 10 parts by weight or the amount of bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate added exceeds 5 parts by weight, there is a problem that the role of the foaming agent is hindered by excessive cross-linking.

[0090] The above glycerol carbonate may additionally contain 0.01 to 30 parts by weight of glycerol per 100 parts by weight. Glycerol is also known as propane-1,2,3-triol, has the structure of Formula 5, and acts as a cross link in the polyurethane foam.

[0092] [Chemical Formula 5]

[0093]

[0095] In the polyurethane foaming agent composition according to the present invention, if the amount of glycerol added is less than 0.01 parts by weight, the functionality of the polyol is lowered, which causes the foam strength to be low and thus causes shrinkage; if it exceeds 30 parts by weight, a large amount of MDI is required, and there is a problem of making the surface of the foam rough.

[0096] The thermal conductivity of the polyurethane foam manufactured using the polyurethane foaming agent composition of the present invention is 0.023 W / m·K or less, and the water absorption is 3.0 g / 100 cm 2 Below, the flexural failure load is 25 N or more, and the compressive strength is 15 N / cm² 2 It could be more than that.

[0097] The thermal conductivity, which is one of the most important physical properties of Type 2 No. 2 insulation material (density 35 or higher) in the rigid polyurethane foam insulation material standard (according to KS M 3809), is required to be 0.023 or lower, and the polyurethane foaming agent composition according to the present invention has the effect of satisfying this.

[0099] In addition, the present invention

[0100] (a) a step of preparing a first liquid comprising a polyol, a surfactant, water, a catalyst, trichloropropyl phosphate, and the polyurethane foaming agent composition of the present invention;

[0101] (b) a step of mixing 100 parts by weight of a first solution and 100 to 150 parts by weight of a second solution containing polyisocyanate relative to 100 parts by weight of the first solution; and

[0102] (c) a step of reacting a mixture of the first liquid and the second liquid to produce a polyurethane foam; a method for producing a polyurethane foam is provided.

[0103] In the present invention, the polyol may be a mixture of one or more polyol components, and any polyol component comprising two or more reactive groups, preferably OH groups, in particular a polyether alcohol and / or polyester alcohol having a hydroxyl group value in the range of 200 to 600 mg KOH / g. A specific example is a polyol mixture comprising 25% to 35% by weight of a polyol with a hydroxyl value of 450 to 500 mg KOH / g obtained by adding glycerin and propylene glycol to sucrose, 15% to 25% by weight of a sucrose polyol with a hydroxyl value of 360 to 400 mg KOH / g obtained by adding glycerin and propylene glycol to sucrose, 15% to 25% by weight of a sorbitol polyol with a hydroxyl value of 460 to 520 mg KOH / g obtained by adding propylene glycol to sorbitol, and 25% to 35% by weight of a polyether polyol with a hydroxyl value of 300 to 350 mg KOH / g obtained by adding ethylene oxide and propylene oxide to bromine-substituted glycerin. Alternatively, it may be a polyol mixture comprising 30% by weight of a polyol with a hydroxyl value of 450 to 500 mg KOH / g obtained by adding glycerin and propylene glycol to sucrose, 20% by weight of a sucrose polyol with a hydroxyl value of 360 to 400 mg KOH / g obtained by adding glycerin and propylene glycol to sucrose, 20% by weight of a sorbitol polyol with a hydroxyl value of 460 to 520 mg KOH / g obtained by adding propylene glycol to sorbitol, and 30% by weight of a polyether polyol with a hydroxyl value of 300 to 350 mg KOH / g obtained by adding ethylene oxide and propylene oxide to bromine-substituted glycerin.

[0104] In the present invention, the catalyst promotes the reaction between the isocyanate group in the polyisocyanate and the active hydrogen-containing group in the polyol. As such a reaction catalyst, amines such as dimethylcyclohexylamine and salts such as potassium octoate are used together. The amount of these reaction catalysts combined is the amount typically used to promote the reaction. Additionally, the catalyst may be used alone or as any preferred mixture as needed. A specific example is using dimethylcyclohexylamine and potassium octoate in equal weights. It is preferable that the amine catalyst and potassium octoate each be included in an amount of 0.5 to 2 parts by weight based on 100 parts by weight of the polyol. If included in an amount less than 0.5 parts by weight, the reaction-promoting effect is insufficient, and if included in an amount exceeding 2 parts by weight, there is a disadvantage of reduced catalyst efficiency.

[0105] In the present invention, the above surfactant is included, preferably a silicone-based surfactant, and a specific example is L-6900. A commercially available product may be used. It is preferable that the silicone-based surfactant be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of polyol. If the silicone-based surfactant is less than 1 part by weight, the surfactant effect is negligible, and if it exceeds 5 parts by weight, it results only in waste of raw materials without additional surfactant effect.

[0107] The present invention will be described in more detail below through examples. These examples are solely for the purpose of illustrating the present invention, and it will be obvious to those skilled in the art that the scope of the present invention is not limited by these examples.

[0109] [Example]

[0111] Examples 1–5 and Comparative Example 1: Preparation of polyurethane foam (spray foam)

[0112] As listed in Table 1, 75 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (product of Seho Co., Ltd.)), 10 parts by weight of polyester polyol (Polyester polyol, OHV=400, RA-4001, product of SKC)), 15 parts by weight of polyester polyol (Polyester polyol, OHV=360, NT-360, product of KPC)), 10 parts by weight of silicone-based surfactant (silicon surfactant, 8409B), 6 parts by weight of water, 20 parts by weight of TCPP (Tris(1-Chloro-2-Propyl)Phosphate, flame retardant), 10 parts by weight of DEOA (Diethanolamine, crosslinking agent), 1.5 parts by weight of CAT 1 (DC-2), 1.5 parts by weight of CAT 2 (PC-5), CAT 2 parts by weight of 3 (DMEA (Dimethylethanolamine)) were added. To this, Nexgener and methyl formate were added in the amounts listed in Table 1 to prepare a polyurethane foam.

[0113] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate (B) + glycerol.

[0115] Examples 6–10 and Comparative Example 2: Preparation of Polyurethane Foam (Spray Foam)

[0116] As indicated in Table 2, 75 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (product of Seho Co., Ltd.)), 10 parts by weight of polyester polyol (Polyester polyol, OHV=400, RA-4001, product of SKC)), 15 parts by weight of polyester polyol (Polyester polyol, OHV=360, NT-360, product of KPC)), 10 parts by weight of silicone-based surfactant (silicon surfactant, 8409B), 6 parts by weight of water, 20 parts by weight of TCPP (Tris(1-Chloro-2-Propyl)Phosphate, flame retardant), 10 parts by weight of DEOA (Diethanolamine, crosslinking agent), 1.5 parts by weight of CAT 1 (DC-2), 1.5 parts by weight of CAT 2 (PC-5), CAT 2 parts by weight of 3 (DMEA (Dimethylethanolamine)) were added. To this, Nexgener and chloropropene were added in the amounts listed in Table 2 to prepare a polyurethane foam.

[0117] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate (B) + glycerol.

[0119] Examples 11–15 and Comparative Example 3: Preparation of Polyurethane Foam (Spray Foam)

[0120] As indicated in Table 3, 75 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (product of Seho Co., Ltd.)), 10 parts by weight of polyester polyol (Polyester polyol, OHV=400, RA-4001, product of SKC)), 15 parts by weight of polyester polyol (Polyester polyol, OHV=360, NT-360, product of KPC)), 10 parts by weight of silicone-based surfactant (silicon surfactant, 8409B), 6 parts by weight of water, 20 parts by weight of TCPP (Tris(1-Chloro-2-Propyl)Phosphate, flame retardant), 10 parts by weight of DEOA (Diethanolamine, crosslinking agent), 1.5 parts by weight of CAT 1 (DC-2), 1.5 parts by weight of CAT 2 (PC-5), CAT 2 parts by weight of 3 (DMEA (Dimethylethanolamine)) were added. To this, Nexgener, HFO-1233zd (Honeywell product, LBA) was added in the amounts listed in Table 3 to prepare a polyurethane foam.

[0121] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate (B) + glycerol.

[0123] Examples 16–20 and Comparative Example 4: Preparation of polyurethane foam (discontinuous foam)

[0124] As described in Table 4, 100 parts by weight of polyester polyol (OHV=320, SP-320G (product of Seho Co., Ltd.)), 2.5 parts by weight of silicon surfactant (AK8805), 3.6 parts by weight of water, 1.5 parts by weight of DEOA (Diethanolamine, crosslinking agent), and 0.3 parts by weight of CAT (PC-3) were added. To this, Nexgener and methyl formate were added in the amounts listed in Table 4 to prepare a polyurethane foam.

[0125] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate (B) + glycerol.

[0127] Examples 21–25 and Comparative Example 5: Preparation of polyurethane foam (discontinuous foam)

[0128] As described in Table 5, 100 parts by weight of polyester polyol (OHV=320, SP-320G (product of Seho Co., Ltd.)), 2.5 parts by weight of silicon surfactant (AK8805), 3.6 parts by weight of water, 1.5 parts by weight of DEOA (Diethanolamine, crosslinking agent), and 0.3 parts by weight of CAT (PC-3) were added. To this, Nexgener and chloropropene were added in the amounts listed in Table 5 to prepare a polyurethane foam.

[0129] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate (B) + glycerol.

[0131] Examples 26–30 and Comparative Example 6: Preparation of polyurethane foam (discontinuous foam)

[0132] As described in Table 6, 100 parts by weight of polyester polyol (OHV=320, SP-320G (product of Seho Co., Ltd.)), 2.5 parts by weight of silicone surfactant (silicon surfactant, AK8805), 3.6 parts by weight of water, 1.5 parts by weight of DEOA (Diethanolamine, crosslinking agent), and 0.3 parts by weight of CAT (PC-3) were added. To this, Nexgener HFO-1233zd (product of Honeywell, LBA) was added in the amounts listed in Table 6 to prepare a polyurethane foam.

[0133] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate (B) + glycerol.

[0135] Example 31 and Comparative Example 7: Preparation of Polyurethane Foam (Spray Foam, Use of Two Physical Foaming Agents)

[0136] As indicated in Table 7, 75 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (product of Seho Co., Ltd.)), 10 parts by weight of polyester polyol (Polyester polyol, OHV=400, RA-4001, product of SKC)), 15 parts by weight of polyester polyol (Polyester polyol, OHV=360, NT-360, product of KPC)), 10 parts by weight of silicone-based surfactant (silicon surfactant, 8409B), 6 parts by weight of water, 20 parts by weight of TCPP (Tris(1-Chloro-2-Propyl)Phosphate, flame retardant), 10 parts by weight of DEOA (Diethanolamine, crosslinking agent), 1.5 parts by weight of CAT 1 (DC-2), 1.5 parts by weight of CAT 2 (PC-5), CAT 2 parts by weight of 3 (DMEA (Dimethylethanolamine)) were added. To this, Nexgener, chloropropene, and HFO-1233zd were added in the amounts listed in Table 7 to prepare a polyurethane foam.

[0137] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolane-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolane-4-yl)methyl)carbonate (B) + glycerol.

[0139] [Test Example]

[0140] Test Example 1: Measurement of Apparent Density of Polyurethane Foam

[0141] The measurement of apparent density is performed in accordance with KS M ISO 845 and as follows. The insulation board is made to have the same thickness as the sample, and three test specimens of approximately 100mm x 100mm are cut from the sample.

[0142] Density (kg / m³) 3 ) = m / V

[0144] Test Example 2: Measurement of shrinkage rate of polyurethane foam

[0145] For the measurement of shrinkage rate, three test specimens were cut from the foam sample into exact 50*50*50 cubes. The change in volume of the foam was measured by leaving it at approximately minus 30 degrees (freezer compartment) for 48 hours.

[0146] Volume change rate (shrinkage rate, %) = (V1-V2) / V1 * 100

[0147] The volume used the underwater flotation method.

[0149] Test Example 3: Measurement of Thermal Conductivity of Polyurethane Foam

[0150] The thermal conductivity of the polyurethane foams prepared in the above examples and comparative examples was measured according to KS L 9016 using a thermal conductivity meter (model number: MA01906) from Laser Comp.

[0152] Test Example 4: Measurement of Compressive Strength of Polyurethane Foam

[0153] The compressive strength of the polyurethane foam prepared in the above example was measured using a universal testing machine according to KS M ISO 844.

[0155] Test Example 5: Measurement of water absorption of polyurethane foam

[0156] 1) Remove the skin from the sample, make three test specimens of 100mm*100mm*25mm, and measure the dimensions.

[0157] 2) Immerse the test specimen 50 mm below the water surface of a container filled with clear water at approximately 25°C. After 10 seconds, remove the test specimen and let it stand for 30 seconds. Then, measure its weight and set it as the reference weight (C). Next, immerse it in clear water again and allow it to absorb for 24 hours, then measure its weight (B). The amount of absorption is calculated according to the following formula.

[0158] Absorption capacity (g / 100cm) 2 ) = (BC) / Surface Area * 100

[0160] Test Example 6: Measurement of Flexural Breakdown Load of Polyurethane Foam

[0161] The compressive strength of the polyurethane foam prepared in the above example was measured using a universal testing machine according to KS M ISO 1209-1 and 1209-2.

[0163] The physical properties of the polyurethane foams of Examples 1 to 5 and Comparative Example 1 are shown in Table 1.

[0165]

[0166] The physical properties of the polyurethane foams of Examples 6 to 10 and Comparative Example 2 are shown in Table 2.

[0168]

[0169] The physical properties of the polyurethane foams of Examples 11 to 15 and Comparative Example 3 are shown in Table 3.

[0171]

[0172] The physical properties of the polyurethane foams of Examples 16 to 20 and Comparative Example 4 are shown in Table 4.

[0174]

[0175] The physical properties of the polyurethane foams of Examples 21 to 25 and Comparative Example 5 are shown in Table 5.

[0177]

[0178] The physical properties of the polyurethane foams of Examples 26 to 30 and Comparative Example 6 are shown in Table 6.

[0180]

[0181] Polyurethane foam that is foamed without physical blowing agents increases internal strength by increasing the formation of urethane cross links due to NCO bonds. However, the decrease in initial foaming power, foam cracking due to internal exothermic reactions, and storage stability after a long period of time are currently major problems.

[0182] Therefore, the present invention aims to manufacture a stable foaming agent by using a mixture of a physical foaming agent with rapid foaming power utilizing its low boiling point properties.

[0183] The thermal conductivity of a polyurethane foam manufactured using the composition of the polyurethane foaming agent according to the present invention is 0.023 W / m·K or less, and the water absorption is 3.0 g / 100 cm 2 Below, the flexural failure load is 25 N or more, and the compressive strength is 15 N / cm² 2 The above has the effect of meeting the rigid polyurethane foam insulation standard (KS M 3809).

[0184] Referring to Tables 1 to 6 above, it can be seen that when the content of the physical foaming agent is 25 parts by weight, the cell size becomes small and uniform, and high compressive strength and low thermal conductivity are achieved through synergy with the foaming power of the physical foaming agent. A similar trend is observed even when the content of the physical foaming agent is 37.5 parts by weight.

[0185] However, unlike other physical blowing agents, methyl formate has a low effect on reducing thermal conductivity with increasing content, because methyl formate has a relatively high boiling point and does not affect the cell size within the polyurethane foam.

[0186] In addition, when the content of the physical foaming agent is 50 parts by weight, the cell size becomes non-uniform, and the synergistic effect is offset by the difficulty in controlling reactivity due to the stark difference in properties according to chemical reaction and boiling point.

[0187] Therefore, it can be seen that physical foaming agents (chloropropene, HFO-1233zd), excluding methyl formate which has low storage stability on its own, have improved storage stability when mixed with glycerol carbonate as the content increases.

[0189] The physical properties of the polyurethane foam of Example 31 and Comparative Example 7 are shown in Table 7.

[0191]

[0192] As shown in Table 2 or Table 5 above, when foaming was performed using only chloropropene, the foaming speed was very fast, and there was a risk of the foam bursting during curing. Therefore, by controlling the foaming speed of chloropropene with NeXgener's slow foaming speed, it is possible to manufacture a more stable polyurethane foam than foaming with chloropropene alone.

[0193] In addition, as shown in Table 3 or Table 6, when HFO-1233zd is foamed alone, there are no disadvantages in terms of shrinkage, storage stability, and thermal conductivity, but there is a problem with relatively low compressive strength. Therefore, by foaming with NeXgener to increase the degree of crosslinking, the problem of foaming HFO-1233zd alone can be compensated for.

[0194] In addition, as shown in Table 7 above, when NeXgener is added while using both of the two physical foaming agents, chloropropene and HFO-1233zd, it can have the effect of further increasing compressive strength while compensating for the difference in foaming power of the foaming agents. In particular, it was confirmed that there is excellent adhesion during spray foaming and no problems with post-foaming or shrinkage.

[0196] Overall, 20 to 40 parts by weight of the physical foaming agent relative to 100 parts by weight of the total composition is suitable for producing a synergistic effect, and more preferably, 25 to 30 parts by weight is suitable.

Claims

Claim 1 A polyurethane blowing agent composition comprising glycerol carbonate and a physical blowing agent, wherein the composition comprises 0.01 to 10 parts by weight of methyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate or 0.01 to 5 parts by weight of bis((2-oxo-1,3-dioxolan-4-yl)methyl) carbonate per 100 parts by weight of glycerol carbonate, and further comprises 0.01 to 30 parts by weight of glycerol, wherein the physical blowing agent is chloropropene, and the chloropropene is 25 parts by weight relative to 100 parts by weight of the composition A polyurethane foaming agent composition characterized by containing up to 40 parts by weight. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 A polyurethane blowing agent composition comprising glycerol carbonate and a physical blowing agent, wherein the composition comprises 0.01 to 10 parts by weight of methyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate or 0.01 to 5 parts by weight of bis((2-oxo-1,3-dioxolan-4-yl)methyl) carbonate per 100 parts by weight of glycerol carbonate, and further comprises 0.01 to 30 parts by weight of glycerol, wherein the physical blowing agent comprises chloropropene and A polyurethane foaming agent composition characterized by being 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), wherein the chloropropene is included in an amount of 15 to 20 parts by weight per 100 parts by weight of the composition, and the 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) is included in an amount of 15 to 20 parts by weight per 100 parts by weight of the composition. Claim 10 (a) a step of preparing a first liquid comprising a polyol, a surfactant, water, a catalyst, trichloropropyl phosphate, and a polyurethane foaming agent composition according to either claim 1 or claim 9; (b) a step of mixing 100 parts by weight of the first liquid with 100 to 150 parts by weight of a second liquid comprising a polyisocyanate relative to 100 parts by weight of the first liquid; and (c) a step of reacting the mixture of the first liquid and the second liquid to produce a polyurethane foam; comprising a method for manufacturing a polyurethane foam. Claim 11 In item 10, the thermal conductivity of the polyurethane foam is greater than 0.018 and less than or equal to 0.023 W / m·K, and the water absorption is greater than 0 and less than or equal to 3.0 g / 100cm 2 Below, flexural failure load is greater than 25 N and less than or equal to 100 N, and compressive strength is greater than 15 and less than or equal to 25 N / cm 2 A method for manufacturing a polyurethane foam characterized by the following.

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