Polyurethane blowing agent composition, and method for preparing polyurethane blowing agent by using same

Abstract

A polyurethane blowing agent composition according to the present invention comprises glycerol carbonate, which has a certain ratio of a physical blowing agent and a chemical blowing agent. Polyurethane foam produced using same has a very low global warming potential and ozone depletion potential and, simultaneously, has improved physical properties of thermal conductivity, absorption amount, flexural strength and compressive strength that satisfy the standards for a rigid urethane foam insulation material.

Description

Polyurethane foaming agent composition and method for producing polyurethane foam using the same

[0001] The present invention relates to a polyurethane foaming agent composition and a method for producing a polyurethane foam using the same, and more particularly, to a polyurethane foaming agent composition having a very low global warming potential and ozone depletion potential while simultaneously having improved properties of thermal conductivity, water absorption, flexural strength and compressive strength that meet the standards for rigid polyurethane foam insulation, by including a certain ratio of a physical foaming agent and a chemical foaming agent, glycerol carbonate, in the polyurethane foaming agent composition, and a method for producing a polyurethane foam using the same.

[0002] Low-density rigid polyurethane foams are used in a variety of applications, including bedding such as mattresses and pillows, cushioning such as household chairs and car seats, roofing systems, and insulation in buildings such as building panels. A key factor in the large-scale commercial use of rigid polyurethane foams is their ability to provide excellent balance properties. Rigid polyurethane foams are known for their excellent insulation properties, excellent heat resistance, and excellent structural properties due to their relatively low density. The foam industry has traditionally used liquid fluorocarbon blowing agents due to their ease of processing.

[0003] In the art, 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 due to their excellent physical properties, such as low thermal conductivity and high dimensional stability. However, the use of these fluorine-containing olefin compounds has been decreasing in recent years as environmental issues have become more important due to the high cost of the blowing agents and the very high global warming potential (GWP).

[0004] To compensate for the shortcomings of these fluorinated olefin compounds, hydrocarbon blowing agents such as iso-pentane, n-pentane, and cyclopentane can be used. Hydrocarbon blowing agents have an ozone depletion potential (ODP) of zero and a very low global warming potential, making them environmentally friendly. However, foams manufactured from these agents have lower thermal insulation efficiency than foams manufactured using fluorinated olefin compounds as blowing agents. In addition, hydrocarbon blowing agents are not sufficiently compatible with materials and additives essential for the manufacture of polyurethane foams, such as polyols, making the process and equipment complex and uneconomical. In addition, when additives are additionally included in the composition to improve various properties of the polyurethane foam, the mechanical properties of the final polyurethane foam are deteriorated. Moreover, cyclopentane itself is highly flammable, making it difficult to handle in actual processes.

[0005] Also, trans-1,2-dichloroethylene, which is another compound that can complement the shortcomings of fluorine-containing olefin compounds, is a non-toxic substance that is liquid at room temperature because it has a boiling point of 48. It does not destroy the ozone layer and has a very short atmospheric lifetime, so it has a very low ozone depletion potential. U.S. Patent No. 7,144,926 discloses a composition comprising trans-1,2-dichloroethylene and a hydrofluorocarbon compound, and Korean Patent No. 10-1532221 discloses a polyol premix composition comprising a mixture of a hydrohaloolefin blowing agent including trans-1,2-dichloroethylene and the like, a polyol, a surfactant that is a non-silicone surfactant but is substantially free of a silicone surfactant, and a tertiary amine catalyst. However, the above patents have the problem that they contain hydrofluorocarbons (HFCs) with high GWP and hydrohaloolefins (HFOs) that have few environmental problems but are very expensive and difficult to access economically.

[0006] Meanwhile, methyl formate can also be used as a blowing agent. Patent Publication No. 2016-0023050 discloses a composition for forming rigid polyurethane foam comprising polyester polyol and / or polyether polyol and a methyl formate blowing agent. When methyl formate is used to produce polyurethane foam, the foam experiences significant shrinkage, resulting in poor dimensional stability. Furthermore, it has the disadvantage of poor compatibility with polyols and other essential materials for the production of polyurethane foam, as well as poor storage stability.

[0007] In addition, research has been conducted on 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 Publication No. 0 419 114 A2). However, when glycerol carbonate, a chemical blowing agent, is used alone, there is a problem that the foam becomes instable (splitting) and reactivity increases due to the generation of internal heat.

[0008] Accordingly, there is a need for a novel foaming agent that minimizes the disadvantages of the foaming agent used in the production of conventional polyurethane foam while providing excellent physical properties to the polyurethane foam produced using the foaming agent, and a composition for producing polyurethane foam containing the foaming agent.

[0009] Accordingly, the inventors of the present invention have made extensive efforts to solve the above problems, and as a result, 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 urethane foam insulation, and at the same time, the global warming potential and ozone depletion potential are very low, thereby enabling the manufacture of an environmentally friendly polyurethane foam, thereby completing the present invention.

[0010]

[0011] [Prior Art Literature]

[0012] [Patent Document]

[0013] U.S. Patent No. 5,703,136

[0014] European Patent Publication No. 0 419 114 A2

[0015]

[0016] [Non-patent literature]

[0017] 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

[0018] The purpose 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 improved performance such as thermal conductivity, water absorption, flexural strength and compressive strength to meet the standards for rigid polyurethane foam insulation, and a method for producing a polyurethane foam using the same.

[0019] To achieve the above purpose,

[0020] The present invention provides a polyurethane foaming agent composition comprising glycerol carbonate and a physical foaming agent.

[0021] 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, It is preferable that at least one is selected from the group consisting of 1,1-dichloro-1-fluoroethane, trans-1,2-dichloroethylene, chloropropane, methylal, c-pentane, n-pentane, and i-pentane.

[0022] It is preferable to include the physical foaming agent in an amount of 20 to 40 parts by weight based on 100 parts by weight of the composition.

[0023] Based on 100 parts by weight of the above glycerol carbonate, 0 to 10 parts by weight of methyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate or 0 to 5 parts by weight of bis ((2-oxo-1,3-dioxolan-4-yl)methyl) carbonate may be additionally included.

[0024] 0.01 to 30 parts by weight of glycerol may be additionally included for 100 parts by weight of the above glycerol carbonate.

[0025] The above physical blowing agent is methyl formate,

[0026] It is preferable that the above methyl formate is included in an amount of 20 to 30 parts by weight per 100 parts by weight of the above composition.

[0027] The above physical blowing agent is chloropropene,

[0028] It is preferable that the above chloropropene be included in an amount of 20 to 40 parts by weight based on 100 parts by weight of the composition.

[0029] The above physical blowing agent is 1-chloro-3,3,3-trifluoropropene (HFO-1233zd),

[0030] It is preferable that the above 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) is included in an amount of 20 to 40 parts by weight based on 100 parts by weight of the composition.

[0031] The above physical blowing agents are chloropropene and 1-chloro-3,3,3-trifluoropropene (HFO-1233zd),

[0032] It is preferable that the chloropropene is included in an amount of 15 to 20 parts by weight based on 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 based on 100 parts by weight of the composition.

[0033] In addition, the present invention

[0034] (a) a step of preparing a first liquid comprising a polyol, a surfactant, water, a catalyst, trichloropropyl phosphate, and a polyurethane foaming agent composition of the present invention;

[0035] (b) a step of mixing 100 parts by weight of the first liquid and 100 to 150 parts by weight of the second liquid containing polyisocyanate relative to 100 parts by weight of the first liquid; and

[0036] (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.

[0037] The thermal conductivity of the above polyurethane foam is greater than 0.018 and less than 0.023 W / m·K, and the absorption is greater than 0 and less than 3.0 g / 100cm. 2 Below, the flexural breaking load is more than 25 N and less than 100 N, and the compressive strength is more than 15 and 25 N / cm. 2 Below is the text.

[0038] A polyurethane foam manufactured using a polyurethane foaming agent composition according to the present invention has an effect of having very low global warming potential and ozone depletion potential, while at the same time having improved properties of thermal conductivity, water absorption, flexural strength, and compressive strength that meet the standards for rigid urethane foam insulation.

[0039] Additionally, its rapid post-curing process is particularly advantageous for spray applications, and its compatibility with ester polyols enhances flame retardancy and reduces costs. While used to prevent shrinkage in foams, this product can achieve shrinkage prevention without the use of sorbitol-based ether polyols, which are problematic due to their high viscosity.

[0040] In addition, it is an environmentally friendly foaming agent that has excellent storage stability after system manufacturing and commercial effectiveness during system manufacturing.

[0041] Figure 1 is a photograph of the cell size during foaming according to Comparative Example 2 of the present invention.

[0042] Figure 2 is a photograph of the cell size during foaming according to Example 8 of the present invention.

[0043] Figure 3 is a graph comparing the thermal conductivity of Examples 1 to 15 of the present invention.

[0044] Hereinafter, the present invention will be described in detail. In describing the present invention, detailed descriptions of related known structures or functions may be omitted.

[0045] Terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted with meanings and concepts that are consistent with the technical aspects of the present invention.

[0046] 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 of the technical ideas of the present invention, so there may be various equivalents and modified examples that can replace them at the time of filing this application.

[0047]

[0048] Hereinafter, the present invention will be described in more detail through examples. These examples are intended solely to illustrate the present invention more specifically, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples, in accordance with the gist of the present invention.

[0049]

[0050] In the present invention, when a polyurethane foaming agent composition containing a certain ratio of glycerol carbonate, a chemical blowing agent, and methyl formate, a physical blowing agent, is used in a process for manufacturing polyurethane foam, it was confirmed that the physical properties such as thermal conductivity, water absorption, flexural strength, and compressive strength are improved to a level that satisfies the standards for rigid urethane foam insulation, and at the same time, the storage stability and compatibility are excellent, and the global warming potential and ozone depletion potential are very low, so that an environmentally friendly polyurethane foam can be manufactured.

[0051] Accordingly, the present invention relates, in one aspect, to a polyurethane blowing agent composition comprising glycerol carbonate and a physical blowing agent.

[0052] In another aspect, the present invention also relates to a method for producing a polyurethane foam, comprising the steps of: (a) 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.

[0053]

[0054] Hereinafter, a polyurethane foaming agent composition according to the present invention and a method for producing a polyurethane foam using the same will be described in detail.

[0055]

[0056] The present invention relates to a foaming agent composition comprising glycerol carbonate, a chemical foaming agent for producing polyurethane foam, and comprising an appropriate and ideal ratio of glycerol carbonate, a chemical foaming agent for polyurethane foam, and a physical foaming agent such as methyl formate, thereby optimizing the function as a composite foaming agent by controlling the phenomenon of foam instability (splitting) and rapid reactivity due to internal heat that occurs when glycerol carbonate, a chemical foaming agent, is used alone, with methyl formate, a physical foaming agent.

[0057] That is, the chemical blowing agent glycerol carbonate exhibits a mechanism in which foaming occurs simultaneously with polyurethane bonding due to the release of carbon dioxide through a rapid reaction between the cyclic carbonate contained in the structure and the NCO of the isocyanate, thereby creating internal cells. The polyurethane foam produced by the generation of carbon dioxide through this chemical change increases the formation of urethane cross links due to the NCO bonds, thereby increasing the strength of the foam surface and the interior. However, this reaction is considered to have major problems in that it reduces the initial foaming power and causes foam splitting due to the internal exothermic reaction. Therefore, the mixed use of a physical blowing agent with a fast foaming power by taking advantage of the low boiling point property can be said to be the discovery of a stable mixed blowing agent (Physico-chemical Blowing Agent) that utilizes the advantages of each other.

[0058] The formation of foam using a mixed blowing agent demonstrates the formation of very small, uniform cells, which significantly influences thermal conductivity and predicts excellent properties as an insulating material. Furthermore, the rapid completion of the crosslinking reaction can be a significant advantage for foams used in polyurethane boards and spray foams.

[0059]

[0060] The present invention provides a foaming agent composition that simultaneously satisfies the criteria of very low global warming potential and ozone depletion potential.

[0061] ODP (Ozone Depletion Potential) is a numerical representation of the ozone-depleting potential of a chemical substance that directly or indirectly contributes to ozone destruction. ODP is expressed as a ratio of the ozone-depleting potential of other chemicals, with the ozone-depleting potential of 1 kg of trichlorofluorocarbon (CFC-11), a type of chlorofluorocarbon, as the standard. In other words, it is calculated as (the amount of ozone destroyed by 1 kg of a chemical substance / the amount of ozone destroyed by 1 kg of CFC-11), and the higher the ODP number, the greater the degree of ozone destruction.

[0062] Each greenhouse gas contributes to global warming to a different degree, and the contribution of each gas is generally specified based on carbon dioxide, called the global warming potential (GWP). When calculating greenhouse gas emissions, each country calculates emissions in units of CO2 tons, taking into account the global warming potential of each gas.

[0063] "GWP" is measured 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."

[0064] 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 an ozone depletion potential of 0 (zero). The mixed physical blowing agent has very low values, meaning it is an environmentally friendly blowing agent with a GWP and ODP value close to "0."

[0065]

[0066] The polyurethane foaming agent composition of the present invention comprises glycerol carbonate and a physical foaming agent.

[0067] In the present invention, the physical foaming 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, At least one 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 (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1-dichloro-1-fluoroethane (HCFC-141b) can be used, but are not limited thereto.In particular, methyl formate is preferred because it has the advantages of being inexpensive and environmentally friendly, and similar functions can be achieved by applying other types of physical foaming agents.

[0068] In the present invention, glycerol carbonate is called glycerine carbonate or 4-(hydroxymethyl)-1,3-dioxolan-2-one and has a structure represented by chemical formula 1. Methyl formate has a structure represented by chemical formula 2.

[0069]

[0070] [Chemical Formula 1]

[0071]

[0072]

[0073] [Chemical Formula 2]

[0074]

[0075]

[0076] 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 based on 100 parts by weight of the composition.

[0077] As the content of the physical blowing agent in the polyurethane foam composition according to the present invention decreases, the degree of urethane crosslinking increases, resulting in higher values ​​in density and compressive strength.

[0078] If the content of the above physical foaming agent is less than 20 parts by weight, there is a problem that the foam splits due to internal heat and that it is difficult to control the reaction speed, and if it exceeds 40 parts by weight, there are problems such as the storage stability of the system and shrinkage of the foam.

[0079] When the physical foaming agent is methyl formate, it is preferable to include 20 to 30 parts by weight of methyl formate per 100 parts by weight of the composition.

[0080] When the physical foaming agent is chloropropene, it is preferable to include 20 to 40 parts by weight of chloropropene based on 100 parts by weight of the composition.

[0081] When the physical foaming agent is 1-chloro-3.3.3-trifluoropropene (HFO-1233zd), it is preferable that the 1-chloro-3.3.3-trifluoropropene (HFO-1233zd) is included in an amount of 20 to 40 parts by weight based on 100 parts by weight of the composition.

[0082] The above physical blowing agents are chloropropene and 1-chloro-3,3,3-trifluoropropene (HFO-1233zd),

[0083] It is preferable that the chloropropene is included in an amount of 15 to 20 parts by weight based on 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 based on 100 parts by weight of the composition.

[0084] In the polyurethane foaming agent composition of the present invention, methyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate of chemical formula 3 may be additionally included in an amount of 0 to 10 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of glycerol carbonate, or bis ((2-oxo-1,3-dioxolan-4-yl)methyl) carbonate of chemical formula 4 may be additionally included in an amount of 0 to 5 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of glycerol carbonate. The above components are components included as by-products during manufacturing, and serve as separate cross-links by stably supplying CO2 and combining with NCO of MDI.

[0085]

[0086] [Chemical Formula 3]

[0087]

[0088]

[0089] [Chemical Formula 4]

[0090]

[0091]

[0092] In the polyurethane foaming agent composition of the present invention, a large amount of glycerol carbonate, which is the main foaming agent, is required, whereas there is no problem at all with adding a very small amount of methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate or bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate as a by-product, and when the amount of methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate added exceeds 10 parts by weight or the amount of bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate added exceeds 5 parts by weight, there is a problem of interfering with the function of the foaming agent due to excessive crosslinking.

[0093] Based on 100 parts by weight of the above glycerol carbonate, 0.01 to 30 parts by weight of glycerol may be additionally included. Glycerol is also called propane-1,2,3-triol, has a structure of chemical formula 5, and acts as a cross link for polyurethane foam.

[0094]

[0095] [Chemical Formula 5]

[0096]

[0097]

[0098] 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, there is a problem that the functionality of the polyol is lowered, thereby lowering the strength of the foam and causing shrinkage. In addition, if it exceeds 30 parts by weight, a large amount of MDI is required, and there is a problem that the surface of the foam becomes rough.

[0099] 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 absorption amount is 3.0 g / 100cm 2 Below, the flexural breaking load is 25 N or more, and the compressive strength is 15 N / cm. 2 It could be strange.

[0100] The standard for rigid polyurethane foam insulation (according to KS M 3809) requires that the thermal conductivity, which is one of the most important properties in insulation type 2, number 2 (density 35 or more), be 0.023 or less, and the polyurethane foam composition according to the present invention has the effect of satisfying this requirement.

[0101]

[0102] In addition, the present invention

[0103] (a) a step of preparing a first liquid comprising a polyol, a surfactant, water, a catalyst, trichloropropyl phosphate, and a polyurethane foaming agent composition of the present invention;

[0104] (b) a step of mixing 100 parts by weight of the first liquid and 100 to 150 parts by weight of the second liquid containing polyisocyanate relative to 100 parts by weight of the first liquid; and

[0105] (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.

[0106] In the present invention, the polyol may be a mixture of one or more polyol components, and may be any polyol component containing two or more reactive groups, preferably OH groups, particularly polyether alcohols and / or polyester alcohols having a hydroxyl value in the range of 200 to 600 mg KOH / g. Specific examples include a polyol mixture comprising 25 wt% to 35 wt% of a polyol having a hydroxyl value of 450 to 500 mg KOH / g obtained by adding glycerin and propylene glycol to sucrose, 15 wt% to 25 wt% of a sucrose polyol having a hydroxyl value of 360 to 400 mg KOH / g obtained by adding glycerin and propylene glycol to sucrose, 15 wt% to 25 wt% of a sorbitol polyol having a hydroxyl value of 460 to 520 mg KOH / g obtained by adding propylene glycol to sorbitol, and 25 wt% to 35 wt% of a polyether polyol having 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 wt% of a polyol having a hydroxyl value of 450 to 500 mg KOH / g obtained by adding glycerin and propylene glycol to sucrose, 20 wt% of a sucrose polyol having a hydroxyl value of 360 to 400 mg KOH / g obtained by adding glycerin and propylene glycol to sucrose, 20 wt% of a sorbitol polyol having a hydroxyl value of 460 to 520 mg KOH / g obtained by adding propylene glycol to sorbitol, and 30 wt% of a polyether polyol having a hydroxyl value of 300 to 350 mg KOH / g obtained by adding ethylene oxide and propylene oxide to bromine-substituted glycerin.

[0107] 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 mixing amount of these reaction catalysts is an amount usually used to promote the reaction. In addition, the catalysts may be used alone or in any desired 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 are each included in an amount of 0.5 to 2 parts by weight based on 100 parts by weight of the polyol. If it is included in an amount less than 0.5 parts by weight, the reaction promotion effect is insufficient, and if it is included in an amount exceeding 2 parts by weight, there is a disadvantage that the catalytic efficiency is reduced.

[0108] In the present invention, the surfactant is preferably a silicone-based surfactant, a specific example of which is L-6900. Commercially available products can be used. The silicone-based surfactant is preferably 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 minimal, and if it exceeds 5 parts by weight, it only results in waste of raw materials without any additional surfactant effect.

[0109]

[0110] Hereinafter, the present invention will be described in more detail through examples. These examples are intended solely to illustrate the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

[0111]

[0112] [Example]

[0113]

[0114] Examples 1 to 5 and Comparative Example 1: Production of polyurethane foam (spray foam)

[0115] As described in Table 1, 75 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (Seho Co., Ltd. product), 10 parts by weight of polyester polyol (Polyester polyol, OHV=400, RA-4001, SKC product), 15 parts by weight of polyester polyol (Polyester polyol, OHV=360, NT-360, KPC product), 10 parts by weight of silicone 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 (Diethanol amine, crosslinking agent), 1.5 parts by weight of CAT 1 (DC-2), 1.5 parts by weight of CAT 2 (PC-5), CAT 3(DMEA(Dimethylethanolamine)) 2 parts by weight was added. Nexgener and methyl formate were added in the amounts shown in Table 1 to manufacture a polyurethane foam.

[0116] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate (B) + glycerol.

[0117]

[0118] Examples 6 to 10 and Comparative Example 2: Production of polyurethane foam (spray foam)

[0119] As described in Table 2, 75 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (Seho Co., Ltd. product), 10 parts by weight of polyester polyol (Polyester polyol, OHV=400, RA-4001, SKC product), 15 parts by weight of polyester polyol (Polyester polyol, OHV=360, NT-360, KPC product), 10 parts by weight of silicone 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 (Diethanol amine, crosslinking agent), 1.5 parts by weight of CAT 1 (DC-2), 1.5 parts by weight of CAT 2 (PC-5), CAT 3(DMEA(Dimethylethanolamine)) 2 parts by weight was added. Nexgener and chloropropene were added in the amounts shown in Table 2 to manufacture a polyurethane foam.

[0120] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate (B) + glycerol.

[0121]

[0122] Examples 11 to 15 and Comparative Example 3: Production of polyurethane foam (spray foam)

[0123] As described in Table 3, 75 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (Seho Co., Ltd. product), 10 parts by weight of polyester polyol (Polyester polyol, OHV=400, RA-4001, SKC product), 15 parts by weight of polyester polyol (Polyester polyol, OHV=360, NT-360, KPC product), 10 parts by weight of silicone 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 (Diethanol amine, crosslinking agent), 1.5 parts by weight of CAT 1 (DC-2), 1.5 parts by weight of CAT 2 (PC-5), CAT 3(DMEA(Dimethylethanolamine)) 2 parts by weight was added. To this, Nexgener, HFO-1233zd (Honeywell product, LBA) was added in the amount shown in Table 3 to manufacture polyurethane foam.

[0124] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate (B) + glycerol.

[0125]

[0126] Examples 16 to 20 and Comparative Example 4: Production of polyurethane foam (discontinuous foam)

[0127] As described in Table 4, 100 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (Seho Co., Ltd. product), 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 (Diethanol amine, crosslinking agent), and 0.3 parts by weight of CAT (PC-3) were added. Nexgener and methyl formate were added in the amounts described in Table 4 to manufacture a polyurethane foam.

[0128] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate (B) + glycerol.

[0129]

[0130] Examples 21 to 25 and Comparative Example 5: Production of polyurethane foam (discontinuous foam)

[0131] As described in Table 5, 100 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (Seho Co., Ltd. product), 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 (Diethanol amine, crosslinking agent), and 0.3 parts by weight of CAT (PC-3) were added. To this, Nexgener and chloropropene were added in the amounts described in Table 5 to manufacture a polyurethane foam.

[0132] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate (B) + glycerol.

[0133]

[0134] Examples 26 to 30 and Comparative Example 6: Production of polyurethane foam (discontinuous foam)

[0135] As described in Table 6, 100 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (Seho Co., Ltd. product), 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 (Diethanol amine, crosslinking agent), and 0.3 parts by weight of CAT (PC-3) were added. To this, Nexgener, HFO-1233zd (Honeywell product, LBA) was added in the amount described in Table 6 to manufacture a polyurethane foam.

[0136] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate (B) + glycerol.

[0137]

[0138] Example 31 and Comparative Example 7: Preparation of polyurethane foam (spray foam, using two physical blowing agents)

[0139] As described in Table 7, 75 parts by weight of polyester polyol (Polyester polyol, OHV=320, SP-320G (Seho Co., Ltd. product), 10 parts by weight of polyester polyol (Polyester polyol, OHV=400, RA-4001, SKC product), 15 parts by weight of polyester polyol (Polyester polyol, OHV=360, NT-360, KPC product), 10 parts by weight of silicone 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 (Diethanol amine, crosslinking agent), 1.5 parts by weight of CAT 1 (DC-2), 1.5 parts by weight of CAT 2 (PC-5), CAT 3 (DMEA (Dimethylethanolamine)) 2 parts by weight was added. Nexgener, chloropropene, and HFO-1233zd were added thereto in the amounts shown in Table 7 to manufacture a polyurethane foam.

[0140] Here, NexGener is glycerol carbonate + methyl(2-oxo-1,3-dioxolan-4-yl)methyl carbonate (A) + bis((2-oxo-1,3-dioxolan-4-yl)methyl)carbonate (B) + glycerol.

[0141]

[0142] [Example Exam]

[0143] Test Example 1: Measurement of apparent density of polyurethane foam

[0144] The measurement of apparent density is in accordance with KS M ISO 845 and the following. The insulation board is made to have the same thickness as the sample, and three test pieces of approximately 100 mm x 100 mm are cut from the sample.

[0145] Density (kg / m) 3 ) = m / V

[0146]

[0147] Test Example 2: Measurement of shrinkage rate of polyurethane foam

[0148] To measure shrinkage, three test pieces were cut into cubes measuring exactly 50*50*50 from the foam sample. The volume change of the foam was measured by leaving it at approximately -30 degrees Celsius (refrigerator freezer) for 48 hours.

[0149] Volume change rate (shrinkage, %) = (V1-V2) / V1 * 100

[0150] The volume was measured using the floating method in water.

[0151]

[0152] Test Example 3: Measurement of thermal conductivity of polyurethane foam

[0153] Thermal conductivity of the polyurethane foams manufactured in the above examples and comparative examples was measured according to KS L 9016 using a thermal conductivity measuring device (model number: MA01906) from Laser Comp.

[0154]

[0155] Test Example 4: Measurement of compressive strength of polyurethane foam

[0156] The compressive strength of the polyurethane foam manufactured in the above example was measured using a universal testing machine according to KS M ISO 844.

[0157]

[0158] Test Example 5: Measurement of absorption capacity of polyurethane foam

[0159] 1) Remove the epidermis from the sample, make three test pieces of 100mm*100mm*25mm, and measure the dimensions.

[0160] 2) Immerse the test piece 50 mm below the surface of a container containing clear water at approximately 25°C. After 10 seconds, remove the test piece, allow it to stand for 30 seconds, and measure its weight. This is the reference weight (C). Then, immerse it again in clear water, allow it to absorb for 24 hours, and measure its weight (B). The amount of absorption is calculated using the following equation:

[0161] Absorption (g / 100cm) 2 ) = (BC) / surface area * 100

[0162]

[0163] Test Example 6: Measurement of flexural failure load of polyurethane foam

[0164] The compressive strength of the polyurethane foam manufactured in the above example was measured using a universal testing machine according to KS M ISO 1209-1, 1209-2.

[0165]

[0166] The properties of the polyurethane foams of Examples 1 to 5 and Comparative Example 1 are shown in Table 1.

[0167]

[0168]

[0169] The properties of the polyurethane foams of Examples 6 to 10 and Comparative Example 2 are shown in Table 2.

[0170]

[0171]

[0172] The properties of the polyurethane foams of Examples 11 to 15 and Comparative Example 3 are shown in Table 3.

[0173]

[0174]

[0175] The properties of the polyurethane foams of Examples 16 to 20 and Comparative Example 4 are shown in Table 4.

[0176]

[0177]

[0178] The properties of the polyurethane foams of Examples 21 to 25 and Comparative Example 5 are shown in Table 5.

[0179]

[0180]

[0181] The properties of the polyurethane foams of Examples 26 to 30 and Comparative Example 6 are shown in Table 6.

[0182]

[0183]

[0184] Polyurethane foams foamed without a physical blowing agent increase internal strength by increasing the formation of urethane crosslinks through NCO bonds. However, significant problems currently include a decrease in initial foaming power, foam cracking due to internal exothermic reactions, and poor long-term storage stability.

[0185] Accordingly, the present invention aims to produce a stable foaming agent by using a mixture of a physical foaming agent having a rapid foaming ability and a low boiling point property.

[0186] The thermal conductivity of the 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 absorption amount is 3.0 g / 100cm 2 Below, the flexural breaking load is 25 N or more, and the compressive strength is 15 N / cm. 2 The effect is such that it satisfies the rigid urethane foam insulation standard (KS M 3809).

[0187] 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. This shows a similar trend even when the content of the physical foaming agent is 37.5 parts by weight.

[0188] However, in the case of methyl formate, unlike other physical blowing agents, the effect of reducing thermal conductivity according to content is low. This is because methyl formate has a relatively high boiling point and does not affect the cell size within the polyurethane foam.

[0189] In addition, when the content of the physical foaming agent is 50 parts by weight, the cell size becomes non-uniform, and the synergy effect is offset due to the difficulty in controlling the reactivity due to the extreme difference in properties according to the chemical reaction and boiling point.

[0190] Therefore, it can be seen that the storage stability of physical blowing agents (chloropropene, HFO-1233zd) other than methyl formate, which has low storage stability on its own, improves as the content increases when mixed with glycerol carbonate.

[0191]

[0192] The properties of the polyurethane foam of Example 31 and Comparative Example 7 are shown in Table 7.

[0193]

[0194]

[0195] When foaming was performed solely using chloropropene as shown in Table 2 or Table 5 above, the foaming speed was so fast that there was a risk of bursting during foam curing. Therefore, by controlling the foaming speed of chloropropene with the slow foaming speed of NeXgener, a more stable polyurethane foam can be produced than when foaming chloropropene alone.

[0196] In addition, when HFO-1233zd is foamed alone as shown in Table 3 or Table 6, there are no disadvantages in terms of shrinkage, storage stability, and thermal conductivity, but there is a problem of relatively low compressive strength. Therefore, by foaming together with NeXgener to increase the degree of cross-linking, the problem of HFO-1233zd foaming alone can be supplemented.

[0197] In addition, when NeXgener is added while using both physical blowing agents, chloropropene and HFO-1233zd, as shown in Table 7 above, it can have the effect of compensating for the difference in the foaming power of the blowing agents as described above and further increasing the compressive strength. In particular, it was confirmed that the adhesive strength was excellent during spray foaming and that there were no problems with post-foaming or shrinkage.

[0198]

[0199] In general, the content of the physical foaming agent is suitable for achieving a synergistic effect at 20 to 40 parts by weight based on 100 parts by weight of the total composition, and more preferably, it is suitable for containing 25 to 30 parts by weight.

Claims

1. A polyurethane blowing agent composition containing glycerol carbonate and a physical blowing agent.

2. In paragraph 1, 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, A polyurethane foaming agent composition characterized in that at least one member is selected from the group consisting of 1,1-dichloro-1-fluoroethane, trans-1,2-dichloroethylene, chloropropane, methylal, c-pentane, n-pentane, and i-pentane.

3. In paragraph 1, A polyurethane foaming agent composition characterized in that the physical foaming agent is contained in an amount of 20 to 40 parts by weight based on 100 parts by weight of the composition.

4. In paragraph 1, A polyurethane foaming agent composition further comprising 0 to 10 parts by weight of methyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate or 0 to 5 parts by weight of bis ((2-oxo-1,3-dioxolan-4-yl)methyl) carbonate, based on 100 parts by weight of the above glycerol carbonate.

5. In paragraph 1, A polyurethane foaming agent composition further comprising 0.01 to 30 parts by weight of glycerol per 100 parts by weight of the above glycerol carbonate.

6. In paragraph 1, The above physical blowing agent is methyl formate, A polyurethane foaming agent composition characterized in that the methyl formate is contained in an amount of 20 to 30 parts by weight based on 100 parts by weight of the composition.

7. In paragraph 1, The above physical blowing agent is chloropropene, A polyurethane foaming agent composition characterized in that the chloropropene is contained in an amount of 20 to 40 parts by weight based on 100 parts by weight of the composition.

8. In paragraph 1, The above physical blowing agent is 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), A polyurethane foaming agent composition characterized in that the 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) is contained in an amount of 20 to 40 parts by weight based on 100 parts by weight of the composition.

9. In paragraph 1, The above physical blowing agents are chloropropene and 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), A polyurethane foaming agent composition characterized in that the chloropropene is contained in an amount of 15 to 20 parts by weight based on 100 parts by weight of the composition, and the 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) is contained in an amount of 15 to 20 parts by weight based on 100 parts by weight of the composition. 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 of any one of claims 1 to 9; (b) a step of mixing 100 parts by weight of the first liquid and 100 to 150 parts by weight of the second liquid containing polyisocyanate relative to 100 parts by weight of the first liquid; and (c) A method for producing a polyurethane foam, comprising: a step of producing a polyurethane foam by reacting a mixture of the first liquid and the second liquid.

11. In paragraph 10, The thermal conductivity of the above polyurethane foam is greater than 0.018 and less than 0.023 W / m·K, and the absorption is greater than 0 and less than 3.0 g / 100cm. 2 Below, the flexural breaking load is more than 25 N and less than 100 N, and the compressive strength is more than 15 and 25 N / cm. 2 A method for producing a polyurethane foam, characterized by the following:

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