Thermosetting foam having improved thermal insulating value

Abstract

To provide a polyurethane foam which achieves improved thermal insulating properties.SOLUTION: Disclosed is a method of forming a foam, comprising: (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent comprising at least about 50 wt.% of hydrohaloolefin including trans-1233zd, wherein the polyol comprises a polyol or a mixture of polyols such that the hydrohaloolefin including trans-1233zd has a solubility of less than about 30% in the polyol; and (b) forming a foam from the foamable composition.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 800022, and hereby claims the same.

[0002] (Field of the Invention) The present invention relates to thermosetting foams, particularly polyurethane foams, polyisocyanurate foams, or mixtures thereof, that achieve improved thermal insulation properties, as well as to foaming compositions and foaming methods for producing such foaming compositions.

Background Art

[0003] The use of foams for providing thermal insulation is well - known. For example, thermal insulation boards made from polyisocyanurate (PIR) or polyurethane (PU) foams are used in commercial, residential, and industrial buildings to provide resistance to the flow of heat into and / or out of the building. Other forms of PU and PIR foams are also used at least in part for their thermal insulation values. Such foams can also have low density, excellent fire resistance, and / or a high strength - to - weight ratio, depending on the needs of a particular application.

[0004] Polyurethane foams are typically produced by reacting a polyisocyanate with one or more polyols in the presence of one or more blowing agents, one or more catalysts, one or more surfactants, and optionally other components. In the case of PIR foams, the foam is formed by reacting the polyisocyanate itself to form a cyclic trimer structure. In practice, foams generally described as polyisocyanurate are poly ​Contains both urethane and polyisocyanurate structures and is described as polyurethane The foams, which often incorporate some polyisocyanurate structures. Thus this application relates to polyurethane foams, polyisocyanurate foams, and mixtures thereof The blowing agent may be a physical blowing agent or a chemical blowing agent. Physical blowing agents are volatilized and expanded by the heat generated when the polyisocyanate reacts with the polyol to form bubbles inside it, thereby generating bubbles in the liquid mixture In the case of chemical blowing agents, also known as gas-generating materials, the gas species are generated by thermal decomposition or reaction with one or more of the components used to produce the polyurethane and / or polyisocyanurate foam As the polymerization reaction proceeds, the liquid mixture becomes a cellular solid, encapsulating the blowing agent within the cells of the foam

[0005] Certain liquid fluorocarbon blowing agents are commonly used among other factors because of their ease of use Fluorocarbons act not only as physical blowing agents due to their volatility, but are also encapsulated or entrained in the closed-cell structure of the foam and are generally the main cause of the low thermal conductivity properties of the foam After the foam is formed, the k-factor or lambda associated with the resulting foam provides a measure of the foam's ability to resist heat transfer through the foam Foams with lower k-factors are more resistant to heat transfer and are thus generally better foams for insulation purposes Therefore, the production of lower k-factor foams is generally desirable and advantageous

[0006] ​​​​​In recent years, concerns about climate change have grown to the point where they are no longer sufficient to meet the requirements of both ozone depletion and climate change regulations. The development of new generation blowing agents that can meet the requirements of the 1,3,3, 3-Tetrafluoropropene (1234ze) and 1,1,1,4,4,4-Hexafluoropropene Of particular interest is orobut-2-ene (1336mzzm). Of particular importance are 1-chloro-3,3,3-trifluoropropene (1233zd). There are certain hydrohaloolefins, including certain hydrochlorofluoroolefins. The process for the preparation of acetonitrile-1,3,3,3-tetrafluoropropene is described in U.S. Pat. Trans-1- Process for the production of chloro-3,3,3-trifluoropropene (trans 1233zd) The process is disclosed in U.S. Patent Nos. 6,844,475 and 6,403,847. There are. Summary of the Invention [Problem to be solved by the invention]

[0007] PIR or PU foam insulation boards may remain part of a building for a long period of time. Average thermal conductivity (lambda value or k-factor) over a 25-year service life under operating conditions ) estimates are based on factory-made rigid polyurethane and building insulation boards. European Standard EN13165 (2010) for polyisocyanurate foam products, and , sprayed in situ formed rigid polyurethane and polyisocyanurate foams European Standard EN 14315 (2013) for products (both of which are incorporated by reference) ) can be used.

[0008] The K-factor (or lambda) of the foam has hitherto been generally related to the thermal insulation properties of the blowing agent used to form the foam. However, the applicants have found that, particularly for certain blowing agents including trans-1,2,3,3,3-pentafluoropropene (HFO-1233zd), the interaction between the blowing agent and the polyol used in the production of the foam can have a significant impact not only on the initial K-factor of the foam but also on the K-factor of the foam after aging. The present invention is based, at least in part, on the unexpected discovery of the inventors that a synergistic relationship between a physical blowing agent, particularly a chlorotrifluoropropene blowing agent, such as in particular, preferably trans-1,2,3,3,3-pentafluoropropene (HFO-1233zd), and a certain polyol used in the formation of the foam results in a foam having improved thermal insulation properties, such as in particular, the ability to maintain the thermal insulation properties of the foam after aging is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0009]

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Figure 7

DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (e.g., preferably, a low initial lambda value, a low aging lambda value, and / or a low delta lambda value), and this method comprises: (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent, wherein such polyol comprises at least about 50% by weight (based on the total polyol in the foamable composition) of a low solubility polyol with respect to such physical blowing agent, and such physical blowing agent comprises at least about 50% by weight (based on the total weight of the physical blowing agent used in the formation of the foam) of a hydrohaloolefin blowing agent, and (b) forming a foam from such foamable composition. For convenience, herein the method according to this paragraph is referred to as Method 1.

[0011] As used herein, the term "low solubility polyol" means that a hydrofluoroolefin physical blowing agent has a solubility of 30% or less in such polyol.

[0012] As used herein, the term "solubility in the polyol" means the solubility when measured according to the procedure specified in the examples herein or by a procedure that provides essentially the same measured value + / - 2%. When used herein with respect to the weight percentage of a component, "about" means the indicated weight percentage + / - 2%.

[0013]

[0014] The present invention also provides excellent insulating properties (e.g., preferably low initial lambda values, low aged lambda values). and / or a low delta lambda value, The method is (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent; and wherein the polyol is at least about 50% by weight relative to the physical blowing agent. % (based on the total polyols in the foamable composition) of low solubility polyol, The physical blowing agent is at least about 50% by weight (the total weight of the physical blowing agent used to form the foam). Based on trans-1-chloro-3,3,3-trifluoropropene (trans 12 33zd), (b) forming a foam from the foamable composition. Hereinafter, the method according to this paragraph will be referred to as Method 2.

[0015] The present invention provides a method for producing a thermal insulating material having excellent thermal insulation properties (preferably low initial lambda value and low aged lambda value). The present invention also includes a method of producing a thermoset foam comprising the steps of: (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent; and wherein the polyol comprises at least about 75% by weight of the polyol in the foamable composition. The physical blowing agent comprises at least About 50% by weight (based on the total weight of the physical blowing agents used to form the foam) of hydrohalogen containing a olefin blowing agent; (b) forming a foam from the foamable composition. Hereinafter, the method according to this paragraph will be referred to as Method 3.

[0016] The present invention relates to a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value and a low aging lambda value), and the method includes: providing a foaming composition including an isocyanate, a polyol, and a physical blowing agent, wherein the polyol includes at least about 75% by weight (based on the total amount of polyols in the foaming composition) of a low solubility polyol, and the physical blowing agent includes at least about 50% by weight (based on the total weight of the physical blowing agent used for forming the foam) of trans-1,2,3,3,3-pentafluoropropene (HFO-1233zd), and forming a foam from the foaming composition. For convenience, the method according to this paragraph is referred to as Method 4 in this specification.

[0017] The present invention relates to a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aging lambda value, and / or a low delta lambda value), and the method includes: providing a foaming composition including an isocyanate, a polyol, and a physical blowing agent, wherein the polyol includes at least about 90% by weight (based on the total amount of polyols in the foaming composition) of a low solubility polyol, and the physical blowing agent includes at least about 50% by weight (based on the total weight of the physical blowing agent used for forming the foam) of a hydrofluoroolefin blowing agent, and forming a foam from the foaming composition. For convenience, the method according to this paragraph is referred to as Method 5 in this specification.

[0018] The present invention relates to a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aging lambda value, and / or a low delta lambda value), and the method includes: (a) To provide a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent, wherein such polyol comprises at least about 90 wt% (based on the total polyol in the foamable composition) of a low solubility polyol, and such physical blowing agent comprises at least about 50 wt% (based on the total weight of the physical blowing agent used in the formation of the foam) of trans-1,2,3,3,3-pentafluoropropene, and (b) forming a foam from such foamable composition. For convenience, herein the method according to this paragraph is referred to as Method 6.

[0019] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aging lambda value, and / or a low delta lambda value), and this method includes (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent, wherein such polyol comprises at least about 50 wt% (based on the total polyol in the foamable composition) of a low solubility polyol, and such physical blowing agent comprises at least about 75 wt% (based on the total weight of the physical blowing agent used in the formation of the foam) of a hydrohaloolefin blowing agent, and (b) forming a foam from such foamable composition. For convenience, herein the method according to this paragraph is referred to as Method 7.

[0020] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aging lambda value, and / or a low delta lambda value), and this method includes (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent, wherein such polyol comprises at least about 50 wt% (based on the total polyol in the foamable composition) of a polyol, including a polyester polyol (based on the total of all), and such a physical blowing agent is at least about 75% by weight (based on the total weight of the physical blowing agent used in the formation of the foam) of trans 1233zd, and (b) forming a foam from such a foamable composition. For convenience, herein the method according to this paragraph is referred to as method 8.

[0021] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aged lambda value, and / or or, a low delta lambda value), and this method is (a) providing a foamable composition including an isocyanate, a polyol, and a physical blowing agent wherein such a polyol includes at least about 50% by weight (based on the total of the polyols in the foamable composition) of a low solubility polyol, and such a physical blowing agent is at least about 95% by weight (based on the total weight of the physical blowing agent used in the formation of the foam) of a hydrohalo refin blowing agent, and (b) forming a foam from such a foamable composition. For convenience, herein the method according to this paragraph is referred to as method 9.

[0022] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aged lambda value, and / or or, a low delta lambda value), and this method is (a) providing a foamable composition including an isocyanate, a polyol, and a physical blowing agent wherein such a polyol includes at least about 50% by weight (based on the total of the polyols in the foamable composition) of a polyester polyol, and such a physical blowing agent is at least ​​At least about 95 wt% (based on the total weight of the physical blowing agent used to form the foam) of trans 1233zd, and (b) forming a foam from such a foamable composition. For convenience, the method according to this paragraph is referred to as Method 10 in this specification .

[0023] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aged lambda value, and / or or a low delta lambda value), the method comprising (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent , wherein the polyol comprises at least about 75 wt% (based on the total of the polyols in the foamable composition) of a low solubility polyol, and the physical blowing agent comprises at least about 75 wt% (based on the total weight of the physical blowing agent used to form the foam) of a hydrohaloolefin blowing agent , and (b) forming a foam from such a foamable composition. For convenience, the method according to this paragraph is referred to as Method 11 in this specification .

[0024] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aged lambda value, and / or or a low delta lambda value), the method comprising (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent , wherein the polyol comprises at least about 75 wt% (based on the total of the polyols in the foamable composition) of a low solubility polyol, and the physical blowing agent comprises at least about 75 wt% (based on the total weight of the physical blowing agent used to form the foam) of a hydrohaloolefin blowing agent , and (b) forming a foam from such a foamable composition. For convenience, the method according to this paragraph is referred to as Method 11 in this specification ​(b) forming a foam from such a foaming composition, and the like. For convenience, in this specification the method according to this paragraph is referred to as method 12.

[0025] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aging lambda value, and / or a low delta lambda value), and this method includes (a) providing a foaming composition containing an isocyanate, a polyol, and a physical blowing agent, wherein such a polyol contains at least about 95% by weight (based on the total amount of polyols in the foaming composition) of a low-solubility polyol, and such a physical blowing agent contains at least about 75% by weight (based on the total weight of the physical blowing agent used in the formation of the foam) of a hydrohaloolefin blowing agent, and the like, about 75% by weight (based on the total weight of the physical blowing agent used in the formation of the foam) of a hydrohaloolefin blowing agent, including, (b) forming a foam from such a foaming composition, and the like. For convenience, in this specification the method according to this paragraph is referred to as method 13.

[0026] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aging lambda value, and / or a low delta lambda value), and this method includes (a) providing a foaming composition containing an isocyanate, a polyol, and a physical blowing agent, wherein such a polyol contains at least about 95% by weight (based on the total amount of polyols in the foaming composition) of a low-solubility polyol, and such a physical blowing agent contains at least about 75% by weight (based on the total weight of the physical blowing agent used in the formation of the foam) of a low-solubility polyol, and such a physical blowing agent contains at least about 75% by weight (based on the total weight of the physical blowing agent used in the formation of the foam) of trans-1,2,3,3,3-pentafluoropropene (HFO-1233zd), including, (b) forming a foam from such a foaming composition, and the like. For convenience, in this specification the method according to this paragraph is referred to as method 14.

[0027] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aged lambda value, and / or or a low delta lambda value), the method comprising: (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent, wherein the polyol comprises at least about 95 wt% (based on the total polyol in the foamable composition) of a low solubility polyol, and the physical blowing agent comprises at least about 95 wt% (based on the total weight of the physical blowing agent used in the formation of the foam) of a hydrohaloolefin, and (b) forming a foam from the foamable composition. For convenience, herein the method according to this paragraph is referred to as method 15.

[0028] The present invention includes a method for producing a thermosetting foam having excellent heat insulation properties (preferably, a low initial lambda value, a low aged lambda value, and / or or a low delta lambda value), the method comprising: (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent, wherein the polyol comprises at least about 95 wt% (based on the total polyol in the foamable composition) of a low solubility polyol, and the physical blowing agent comprises at least about 95 wt% (based on the total weight of the physical blowing agent used in the formation of the foam) of trans-1,2,3,3,3-pentafluoropropene (HFO-1233zd), and (b) forming a foam from the foamable composition. For convenience, herein the method according to this paragraph is referred to as method 16.

[0029] The present invention also includes a thermosetting foam comprising each of methods 1, 3, 5, 7, 9, 11, 13, and 15, Also included is a method for producing a rigid foam, and such a low solubility polyol includes a polyol or a mixture of polyols, and such a hydrohaloolefin blowing agent has a solubility in such a polyol of less than about 25% (a solubility is said polyol). For convenience, in this specification, the method according to this paragraph is referred to as Method 17. Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 25%. For convenience, in this specification, the method according to this paragraph is referred to as Method 18. Also included is a method for producing a thermosetting foam including each of Methods 1, 3, 5, 7, 9, 11, 13, and 15, and such a low solubility polyol includes a polyol or a mixture of polyols, and such a hydrohaloolefin blowing agent has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 19. Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 20.

[0030] Also included is a method for producing a thermosetting foam including each of Methods 1 to 20. Also included is a method for producing a rigid foam, and such a low solubility polyol includes a polyol or a mixture of polyols, and such a hydrohaloolefin blowing agent has a solubility in such a polyol of less than about 25% (a solubility is said polyol). For convenience, in this specification, the method according to this paragraph is referred to as Method 17. Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 25%. For convenience, in this specification, the method according to this paragraph is referred to as Method 18. Also included is a method for producing a thermosetting foam including each of Methods 1, 3, 5, 7, 9, 11, 13, and 15, and such a low solubility polyol includes a polyol or a mixture of polyols, and such a hydrohaloolefin blowing agent has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 19.

[0031] Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 20. Also included is a method for producing a rigid foam, and such a low solubility polyol includes a polyol or a mixture of polyols, and such a hydrohaloolefin blowing agent has a solubility in such a polyol of less than about 25% (a solubility is said polyol). For convenience, in this specification, the method according to this paragraph is referred to as Method 17. Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 25%. For convenience, in this specification, the method according to this paragraph is referred to as Method 18. Also included is a method for producing a thermosetting foam including each of Methods 1, 3, 5, 7, 9, 11, 13, and 15, and such a low solubility polyol includes a polyol or a mixture of polyols, and such a hydrohaloolefin blowing agent has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 19.

[0032] Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 20. Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 20. Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 20. Also included is a method for producing a thermosetting foam including each of Methods 2, 4, 6, 8, 10, 12, 14, and 16, and such a low solubility polyol includes a polyol or a mixture of polyols, and such trans-1,2,3,3-ZD has a solubility in such a polyol of less than about 20%. For convenience, in this specification, the method according to this paragraph is referred to as Method 20.

[0033] Also included is a method for producing a thermosetting foam including each of Methods 1 to 20. ​See, such low solubility polyols include polyester polyols. For convenience, in this specification , the method according to this paragraph is referred to as method 21.

[0034] The present invention also includes a method for producing a thermosetting foam, each of which includes methods 1 to 20 See, such low solubility polyols contain at least about 50% by weight of polyester polyols . For convenience, in this specification, the method according to this paragraph is referred to as method 22.

[0035] The present invention also includes a method for producing a thermosetting foam, each of which includes methods 1 to 20 See, such low solubility polyols contain at least about 75% by weight of polyester polyols . For convenience, in this specification, the method according to this paragraph is referred to as method 23.

[0036] The present invention also includes a method for producing a thermosetting foam, each of which includes methods 1 to 20 See, such low solubility polyols consist essentially of polyester polyols. For convenience, in this specification, the method according to this paragraph is referred to as method 24.

[0037] The present invention also includes a method for producing a thermosetting foam, each of which includes methods 1 to 20 See, such low solubility polyols consist of polyester polyols. For convenience, in this specification it is, the method according to this paragraph is referred to as method 25.

[0038] The present invention also provides a foam produced by any of the methods described herein, each of which includes methods 1 to 25 .

[0039] The present invention includes a spray foam produced according to any of the methods described herein, each of which includes methods 1 to 25 .

[0040] The present invention includes a sandwich panel foam produced according to any of the methods described herein, each including Methods 1 to 25.

[0041] The present invention includes a sandwich panel foam produced according to any of the methods described herein, each including Methods 1 to 25.

[0042] The present invention includes a foam for electrical appliances, such as refrigerators, freezers, and water heaters, produced according to any of the methods described herein, each including Methods 1 to 25.

[0043] The present invention includes a board stock produced according to any of the methods described herein, each including Methods 1 to 25.

[0044] The present invention includes a block foam produced according to any of the methods described herein, each including Methods 1 to 25.

[0045] The present invention includes a pipe foam produced according to any of the methods described herein, each including Methods 1 to 25.

[0046] The present invention includes a pipe foam produced according to any of the methods described herein, each including Methods 1 to 25.

[0047] The present invention includes a container insulation foam produced according to any of the methods described herein, each including Methods 1 to 25.

[0048] The present invention includes a in-place foam produced according to any of the methods described herein, each including Methods 1 to 25. The present invention includes each of Methods 1 to 25. 、including a PIR foam produced according to any of the methods described herein.

[0049] The present invention includes a PIR foam produced according to any of the methods described herein, each of which includes Methods 1 to 25. including a PIR foam produced according to any of the methods described herein.

[0050] Each and any of the foams of the present invention described above, including each of Methods 1 to 25, may be polyurethane, polyisocyanurate, or a combination of the two.

[0051] Detailed Description Foam The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, having a delta lambda of 7 mW / mK (10 °C) or less, produced by any of the methods described herein, each of which includes Methods 1 to 25. including a PIR foam produced according to any of the methods described herein. including a PIR foam produced according to any of the methods described herein. . As used herein, the term "delta lambda" refers to the delta lambda measured at 10 °C according to the examples herein.

[0052] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, having a delta lambda of 7 mW / mK (10 °C) or less, produced by any of the methods described herein, each of which includes Methods 1 to 25. including a PIR foam produced according to any of the methods described herein. including a PIR foam produced according to any of the methods described herein. . As used herein, the term "delta lambda" refers to the delta lambda measured at 10 °C according to the examples herein.

[0053] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, having a delta lambda of about 6 mW / mK (10 °C) or less, produced by any of the methods described herein, each of which includes Methods 1 to 25. including a PIR foam produced according to any of the methods described herein. ​​or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided When used herein, the term as used herein in connection with the delta lambda value "about" means the indicated value + / - 0.5

[0054] The present invention provides a thermosetting foam having a delta lambda of about 5 mW / mK (10 °C) or less, prepared by any of the methods herein, each of Methods 1-25, preferably or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided The present invention provides a thermosetting foam having a delta lambda of 5.5 mW / mK (10 °C) or less, prepared by any of the methods herein, each of Methods 1-25 preferably or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided preferably or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided

[0055] The present invention provides a thermosetting foam having an initial lambda value of 20 mW / mK (10 °C) or less, prepared by any of the methods herein, each of Methods 1-25, preferably or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided When used herein, the term "initial lambda" refers to the lambda measured at 10 °C according to the examples herein

[0056] The present invention provides a thermosetting foam having an initial lambda value of about 17 mW / mK (10 °C) or less, prepared by any of the methods herein, each of Methods 1-25 preferably or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided preferably or a polyurethane foam, a polyisocyanurate foam, or a mixture thereof is provided The term "about" as used herein in connection with the lambda value means the indicated value + / - 0 ​​means 0.1.

[0057] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an aged lambda of about 27 mW / mK or less. When used herein, the term "aged lambda" refers to the lambda measured after aging at 70 °C for 21 days according to the procedure described in the examples herein. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an aged lambda of about 26 mW / mK or less. When used herein, the term "aged lambda" refers to the lambda measured after aging at 70 °C for 21 days according to the procedure described in the examples herein. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an aged lambda of about 25 mW / mK or less.

[0058] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an aged lambda of about 24 mW / mK or less. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less.

[0059] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less.

[0060] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less.

[0061] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less. The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, produced by any of the methods herein, each of Methods 1 to 25 having an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less. A thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced as follows. is provided.

[0062] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced by any of the methods herein and has an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 25 mW / mK or less. A thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced as follows. is provided.

[0063] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced by any of the methods herein and has an initial lambda value of 20 mW / mK (10 °C) or less and an aged lambda of about 24 mW / mK or less. A thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced as follows. is provided.

[0064] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced by any of the methods herein and has an initial lambda value of 17 mW / mK (10 °C) or less and an aged lambda of about 27 mW / mK or less. A thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced as follows. is provided.

[0065] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced by any of the methods herein and has an initial lambda value of 17 mW / mK (10 °C) or less and an aged lambda of about 25 mW / mK or less. A thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, which is produced as follows. is provided.

[0066] The present invention provides a thermosetting foam, preferably a polyurethane foam, a polyisocyanurate foam, or a mixture thereof, having an initial lambda value of 17 mW / mK (10 °C) or less and an aged lambda of about 24 mW / mK or less, produced by any of the methods herein including each of Methods 1 to 25. As described above, the foaming composition of the present invention includes a thermosetting material (preferably urethane and / or isocyanurate) as an essential component, a polyol, and a physical blowing agent. Separate from what is required herein, the specific properties and amounts of these components may be provided over a wide range known to those skilled in the art and may also include any additional optional constituents such as those described below within such a wide range.

[0067] Foaming composition As described above, the foaming composition of the present invention includes a thermosetting material (preferably urethane and / or isocyanurate) as an essential component, a polyol, and a physical blowing agent. Separate from what is required herein, the specific properties and amounts of these components may be provided over a wide range known to those skilled in the art and may also include any additional optional constituents such as those described below within such a wide range. For the purposes of the present invention, the physical blowing agent preferably includes at least about 50 wt% of trans-1-chloro-3,3,3-trifluoropropene (1233zd). Any co-blowing agents include 1,3,3,3-tetrafluoropropene (1234ze), 1,1,1,4,4,4-hexafluorobuta-2-ene (1336mzzm).

[0068] Blowing agent For the purposes of the present invention, the physical blowing agent preferably includes at least about 50 wt% of trans-1-chloro-3,3,3-trifluoropropene (1233zd). Any co-blowing agents include 1,3,3,3-tetrafluoropropene (1234ze), 1,1,1,4,4,4-hexafluorobuta-2-ene (1336mzzm).

[0069] 1,3,3,3-tetrafluoropropene (1234ze) can be provided as the cis isomer, the trans isomer, or a combination thereof. Preferably, 1,3,3,3-tetrafluoropropene is provided as the trans isomer. 1,1,1,4,4,4-hexafluorobuta-2-ene (1336mzzm) can be provided as the cis isomer, the trans isomer, or a combination thereof. Preferably, 1,3,3,3-tetrafluoropropene is provided as the trans isomer. 1,3,3,3-tetrafluoropropene is provided as the trans isomer. 1,1,1,4,4,4-hexafluorobuta-2-ene (1336mzzm) can be provided as the cis isomer, the trans isomer, or a combination thereof. Preferably, 1,1,1,4,4,4-hexafluorobuta-2-ene is provided as the cis isomer. It can be provided as a trans isomer, or a combination thereof. Preferably, 1 ,1,1,4,4,4-hexafluorobut-2-ene is provided as the cis isomer .

[0070] The physical blowing agent used according to the method of the present invention, including each of Methods 1 to 25, may contain trans-1-chloro-3,3,3-trifluoropropene (1233zd), may consist essentially of it, or may consist of it .

[0071] The blowing agent may further contain one or more additional co-blowing agents such as hydrocarbons, fluorocarbons, chlorocarbons, fluorochlorocarbons , hydrochlorofluorocarbons, hydrofluorocarbons, halogenated hydrocarbons , ethers, fluorinated ethers, esters, acetals, alcohols, aldehydes, ketones , organic acids, gas generating materials, water, carbon dioxide (CO2), or combinations thereof. Preferred blowing agents have a global warming potential (GWP) of 150 or less, preferably 100 or less, more preferably 75 or less. As used herein, "GWP" is incorporated herein by reference to "The Sci entific Assessment of Ozone Depletion, 20 02, a report of the World Meteorological Association’s Global Ozone Research and Monitoring Project", and is measured relative to the GWP of carbon dioxide and over a 100-year planning horizon. Preferred "blowing agents" are 0.05 or less, preferably 0.02 or less, more preferably approximately zero ozone depletion potential . . . has an ODP). As used herein, "ODP" is incorporated herein by reference to "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Me teorological Association’s Global Ozone Research and Monitoring Project" as defined therein.

[0072] Any preferred chemical co-blowing agent includes water, CO2 and / or an organic acid that generates CO is mentioned.

[0073] Any preferred physical co-blowing agent includes CO2, ether, halogenated ether; e ster, alcohol, aldehyde, ketone; trans 1,2 dichloroethylene; methylene chloride, methyl formate; hydrofluorocarbons such as 1,1,1,2-tetrafluoroethane (134a); 1,1,2,2-tetrafluoroethane (134); 1,1,1,3, 3-pentafluorobutane (365mfc); 1,1,1,2,3,3,3-heptafluoropropane (227ea), 1,1,1,3,3,3-hexafluoropropane (23 6fa); 1,1,1,2,3,3-hexafluoropropane (236ea); 1,1, 1,2,3,3,3-heptafluoropropane (227ea), 1,1-difluoroethane (152a); 1,1,1,3,3-pentafluoropropane (245fa); butane hydrocarbons such as; isobutane; normal pentane; isopentane; cyclopentane, or a combination thereof is mentioned.

[0074] More preferably, the co - blowing agent is water, CO2 and / or an organic acid that generates CO, tran s - 1,2 - dichloroethylene; methylal, methyl formate; 1,1,1,2 - tetraflu oroethane (134a); 1,1,1,3,3 - pentafluorobutane (365mfc) ; 1,1,1,2,3,3,3 - heptafluoropropane (227ea), 1,1 - dif luoroethane (152a); 1,1,1,3,3 - pentafluoropropane (245fa ); butane; isobutane; normal pentane; isopentane; cyclopentane, or a combination thereof .

[0075] The blowing agent that is trans - 1,2,3,4 - zd and the optional co - blowing agent are preferably present in the foaming composition in an amount of about 1 wt% to about 30 wt%, preferably about 3 wt% % to about 25 wt%, more preferably about 5 wt% to about 25 wt%, by weight of the polyol and the blowing agent in the composition .

[0076] Polyol As described above, the applicants have found that when the polyol used in the foaming composition of the present invention is carefully selected, it can have an unexpected but very beneficial effect on the heat transfer resistance of the foam, including the decrease in the heat transfer resistance over time when the foam ages . Therefore, the polyol according to the present invention should be selected according to one of the structural requirements described herein (for example, in accordance with at least 50% of the polyol ester), and / or according to one of the solubility requirements described herein (for example, a solubility of 25% or less with respect to trans - 1,2,3,3 - zd) . When one of these selections is made in accordance with the teachings of this specification, the polyol is a polyurethane foam, a polyisocyanurate foam or a mixture thereof ​​​​​​ Any polyol or polyol mixture that reacts with an isocyanate in a method known in the preparation of an article can be. Useful polyols include, in addition to preferred polyester polyols, optionally, for example, sucrose-containing polyols; phenol, phenol formaldehyde dehydrated-containing polyols; glucose-containing polyols; sorbitol-containing polyols; methyl glucoside-containing polyols may be mentioned.

[0077] The polyol or polyol mixture may be present in the foaming composition, for example, in an amount of about 20% to about 70% by weight, preferably about 30% to about 60% by weight, more preferably about 35% to about 55% by weight, based on the total weight of the foaming composition.

[0078] Isocyanate For the purposes of the present invention, the isocyanate can be any organic polyisocyanate that can be used in the synthesis of polyurethane and / or polyisocyanurate foams containing aliphatic and aromatic polyisocyanates . Suitable organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates well known in the field of polyurethane chemistry. These are described, for example, in U.S. Patent Nos. 4,868,224, 3,401,190, 3,454,606, 3,277,138, 3,492,330, 3,001,973, 3,394,164, 3,124,605, and 3,201,372, all of which are incorporated herein by reference . Aromatic polyisocyanates are preferred as a class.

[0079]

[0079] Representative organic polyisocyanates have the formula: R(NCO) z corresponds to, where R is a polyvalent organic group that is aliphatic, aralkyl, aromatic, or a mixture thereof, and z corresponds to the valence of R and is an integer of at least 2. Representative organic polyisocyanates contemplated herein include, for example, aromatic diisocyanates , such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2, 4- and 2,6-toluene diisocyanate mixture, crude toluene diisocyanate, me thylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate; aromatic to lylene diisocyanate, such as 4,4’,4’’-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanate; aromatic tetraisocyanate, such as 4,4 ’-dimethyl diphenylmethane-2,2’5,5-’tetraisocyanate; aryl a lkyl polyisocyanate, such as xylene diisocyanate; hexamethylene-1,6 -diisocyanate, aliphatic polyisocyanates such as lysine diisocyanate methyl ester, and mixtures thereof. Other organic polyisocyanates include poly methylene polyphenyl isocyanate, hydrogenated methylene diphenyl isocyanate, m- phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyp henylene-2,4-diisocyanate, 4,4’-biphenylene diisocyanate, 3, 3’-dimethoxy-4,4’-biphenyl diisocyanate, 3,3’-dimethyl-4, 4’-biphenyl diisocyanate, and 3,3’-dimethyl diphenylmethane-4,4 ’-diisocyanate. Typical aliphatic polyisocyanates are alkylene ​​Diisocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), etc. Typical aromatic polyisocyanates include m- and p-phenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 2,4- and 2,6-toluene diisocyanate, di anisidine diisocyanate, bitolylene isocyanate, 1,4-diisocyanate, bis(4-isocyanatophenyl)methane, bis(2-methyl-4-isocyanatophenyl l)methane, etc. Preferred polyisocyanates are polymethylene polyphenyl l polyisocyanates, especially those containing about 30 to about 85% by weight of methylene bis(phenyl isocyanate ), and the remainder of the mixture being a polymethylene polyphenyl l polyisocyanate of functionality higher than 2. These polyisocyanates are prepared by conventional methods known in the art. In the present invention, the polyisocyanate and the po lyol are preferably used in amounts that provide an NCO / OH stoichiometric ratio in the range of about 0.9 to about 5.0. In the present invention, the NCO / OH equivalent ratio is preferably about 1 or more and about 4 or less, and the ideal range is about 1.1 to about 3. Particularly suitable organic polyisocyanates include polymethylene polyphenyl polyisocyanate, methylene bis(phenyl isocyanate ), toluene diisocyanate, or combinations thereof.

[0080] Other components Other components that may be included in the foaming composition include silicone surfactants, non-silicone - A surfactant and a catalyst (including metal catalysts, amine catalysts, and combinations thereof (in cludind) are mentioned.

[0081] Non-Silicon surfactant As non-silicon surfactants, for example, as non-silicon non-ionic surfactants, oxy ethylated alkylphenols, oxyethylated aliphatic alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, Turkey red oil, peanut oil, paraffin, and aliphatic alcohols may be mentioned. Preferred non-silicon non-ionic surfactants are Ai r Products Corporation's LK-443 or Vorasurf 504 from Dow.

[0082] When a non-silicon non-ionic surfactant is used, based on the weight of the polyol, foaming agent, and silicon in the composition, it is usually present in the composition in an amount of about 0.25 wt% to about 3.0 wt%, preferably about 0.5 wt% to about 2.5 wt%, more preferably about 0.75 wt% to about 2. 0 wt%.

[0083] Catalyst Examples of catalysts include amine catalysts and / or metal catalysts. Amine catalysts may include, but are not limited to, primary amines, secondary amines, or tertiary amines. Useful tertiary amine catalysts include, non-exclusively, N,N-dimethylcyclohexylamine , N,N-dimethylethanolamine, dimethylaminoethoxyethanol, N,N,N '-trimethylaminoethylethanolamine, N,N,N'-trimethyl-N'-hyd roxyethylpiperazine, and N,N,N'-trimethyl-N'-hydroxypropylpiperazine. Roxyethylbisaminoethyl ether, tetramethyliminobispropylamine, 2- [[2-[2-(dimethylamino)ethoxy]ethyl]methylamino]ethanol, pen tamethyldiethylenetriamine, pentamethyldipropylenetriamine, N,N,N’, N’’,N’’-pentamethyl-dipropylenetriamine, 1,1,4,7,10,10 -hexamethyltriethylenetetramine, N,N-bis(3-dimethylaminopropyl) -N-isopropanolamine, N’-(3-(dimethylamino)propyl)-N,N- dimethyl-1,3-propanediamine, bis(3-dimethylaminopropyl)-n,n- dimethylpropanediamine, bis-(2-dimethylaminoethyl)ether, N,N’, N’’-dimethylaminopropylhexahydrotriazine, tetramethyliminobispro pylamine, trimethyl-n’, 2-hydroxyethyl-propylenediamine, bis-( 3-aminopropyl)-methylamine, N,N-dimethyl-1,3-propanediamine, 1-(dimethylamino)hexadecane, benzyldimethylamine, 3-dimethylaminop ropylurea, dicyclohexylmethylamine; ethyldiisopropylamine; dimethyli sopropylamine; methylisopropylbenzylamine; methylcyclopentylbenzyl amine; isopropyl-sec-butyl-trifluoroethylamine; diethyl-(α- phenylethyl)amine, tri-n-propylamine, or a combination thereof may be mentioned Useful secondary amine catalysts include, but are not limited to, dicyclohexylamine; t-butyl-i sobutylamine, di-t-butylamine; cyclohexyl-t-butylamine; di-se c-butylamine, dicyclopentylamine; di-(α-trifluoromethylethyl)a Minn; di-(α-phenylethyl)amine; or a combination thereof.

[0084] Other useful amines include morpholine, imidazole, and ether-containing compounds including. These include dimorpholinodiethyl ether N-ethylmorpholine N-methylmorpholine bis(dimethylaminoethyl) ether imidazole n-methylimidazole 1,2-dimethylimidazole dimorpholinodimethyl ether N,N,N’,N’,N’’,N’’-pentamethyldiethylenetriamine N,N,N’,N’,N’’,N’’-pentaethyldiethylenetriamine N,N,N’,N’,N’’,N’’-pentamethyldipropylenetriamine bis(diethylaminoethyl) ether bis(dimethylaminopropyl) ether.

[0085] Suitable non-amine catalysts include organometallic compounds containing bismuth, lead, tin, titanium, antimony, uranium, cadmium ium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum denum, vanadium, copper, manganese, zirconium, sodium, potassium, lithium, magnesium nesium, barium, calcium, hafnium, lanthanum, niobium, tantalum, tellurium r, tungsten, cesium, or a combination thereof. Preferably, the non-amine catalyst includes an organometallic compound containing bismuth, lead, tin, zinc, sodium, potassium ium, or a combination thereof. including.

[0086] As non-amine catalysts, bismuth 2-ethylhexanoate, lead 2-ethylhexanoate, lead benzoate, stannous salts of carboxylic acids, zinc salts of carboxylic acids, dialkyltin salts of carboxylic acids (e.g., dibutyltin dilaurate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dibutyltin dilauryl mercaptide dibutyltin diisooctyl maleate dimethyltin dilauryl mercaptide dioctyltin dilauryl mercaptide , dibutyltin dithioglycolate, dioctyltin dithioglycolate), potassium acetate , potassium octanoate, potassium 2-ethylhexanoate, glycine salts, quaternary ammonium carboxylates, alkali metal carboxylates and tin(II) 2-ethylhexanoate or combinations thereof are included.

[0087] The trimerization catalyst can be used for the purpose of converting the blend together with excess isocyanate into a polyisocyanurate-polyurethane foam. The trimerization catalysts used include glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates, and alkali metal carboxylates, as well as mixtures of various types of catalysts, but are not limited thereto , and can be any catalyst known to those skilled in the art. The trimerization catalysts are potassium acetate, potassium octanoate , and N-(2-hydroxy-5-nonylphenyl)methyl-N-methylglycine ate.

[0088] Flame Retardant The flame retardant is added to the foamed insulation board to suppress the chemical reaction of the flame or form a protective char layer on the surface of the material, thereby suppressing or delaying the spread of fire. Generally, the flame retardant is , added to the polyol premix or the foaming composition as a liquid or a solid. Alternatively , a flame retardant may be added with isocyanurate, or added as a separate stream before forming the foam. Generally, the flame retardant can be a mineral-based, organic halogen compound or an organic phosphorus compound. Conventional flame retardants used in foamed insulation boards include tris(2-chloro ethyl) phosphate, tris(2-chloropropyl) phosphate, tris(1,3 -dichloropropyl) phosphate, tri(2-chloroisopropyl) phosphate, tricresyl phosphate, tri(2,2-dichloroisopropyl) phosphate, N,N-bis (2-hydroxyethyl)aminomethylphosphonic acid diethyl, dimethyl methylphosphonate , tris(1,3-dichloropropyl) phosphate, and tetrakis-(2-chloroethyl )ethylene diphosphate, triethyl phosphate, ammonium phosphate, various halogen ated aromatic compounds, aluminum trihydrate, diethyl-N,N-bis(2-hydroxyethyl )aminomethylphosphonate (Fyrol6) and melamine.

[0089] For the purposes of the present invention, phosphate-based flame retardants are preferably tris(2-chloro ethyl) phosphate, tris(2-chloropropyl) phosphate, tris(1,3- dichloropropyl) phosphate, tri(2-chloroisopropyl) phosphate, tricresyl phosphate, tri(2,2-dichloroisopropyl) phosphate, diethyl N,N -bis(2-hydroxyethyl)aminomethylphosphonate, dimethyl methylphosphonate , tris(1,3-dichloroisopropyl) phosphate, diethyl-N,N-bis(2- (Hydroxyethyl)aminomethylphosphonate (Fyrol6), tetrakis-(2-chloroethyl) ethylene diphosphate, triethyl phosphate and ammonium phosphate, more preferably, tris(1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate (TEP) and diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol6). It is selected from the group consisting of ethyl ethylene diphosphate, triethyl phosphate and ammonium phosphate. Preferably, it is selected from the group consisting of tris(1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate (TEP) and diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol6). It is selected from the group consisting of ethyl ethylene diphosphate, triethyl phosphate and ammonium phosphate, more preferably, tris(1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate (TEP) and diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol6). It is selected from the group consisting of ethyl ethylene diphosphate, triethyl phosphate and ammonium phosphate, more preferably, tris(1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate (TEP) and diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol6).

[0090] The amount of the phosphate flame retardant in the polyol premix composition is preferably 25 phpp or less, preferably 20 phpp or less, preferably 15 phpp or less, preferably 10 phpp or less, preferably 5 phpp or less. Preferably, the foaming composition does not contain a phosphate flame retardant. The amount of the phosphate flame retardant in the polyol premix composition is preferably 25 phpp or less, preferably 20 phpp or less, preferably 15 phpp or less, preferably 10 phpp or less, preferably 5 phpp or less. Preferably, the foaming composition does not contain a phosphate flame retardant. The amount of the phosphate flame retardant in the polyol premix composition is preferably 25 phpp or less, preferably 20 phpp or less, preferably 15 phpp or less, preferably 10 phpp or less, preferably 5 phpp or less. Preferably, the foaming composition does not contain a phosphate flame retardant. The amount of the phosphate flame retardant in the polyol premix composition is preferably 25 phpp or less, preferably 20 phpp or less, preferably 15 phpp or less, preferably 10 phpp or less, preferably 5 phpp or less. Preferably, the foaming composition does not contain a phosphate flame retardant.

[0091] The flame retardant can be blended with the polyol and thus can be provided as a polyol premix composition with a polyol or a mixture of polyols before the formation of the foaming composition. Alternatively, the flame retardant can be added as a separate stream during the formation of the foaming composition. For the purposes of the present invention, the amount of the phosphate flame retardant includes all phosphate flame retardants, i.e., the amount of the phosphate flame retardant present in the polyol premix composition or added as a separate stream during the formation of the foaming composition. The flame retardant can be blended with the polyol and thus can be provided as a polyol premix composition with a polyol or a mixture of polyols before the formation of the foaming composition. Alternatively, the flame retardant can be added as a separate stream during the formation of the foaming composition. For the purposes of the present invention, the amount of the phosphate flame retardant includes all phosphate flame retardants, i.e., the amount of the phosphate flame retardant present in the polyol premix composition or added as a separate stream during the formation of the foaming composition. The flame retardant can be blended with the polyol and thus can be provided as a polyol premix composition with a polyol or a mixture of polyols before the formation of the foaming composition. Alternatively, the flame retardant can be added as a separate stream during the formation of the foaming composition. For the purposes of the present invention, the amount of the phosphate flame retardant includes all phosphate flame retardants, i.e., the amount of the phosphate flame retardant present in the polyol premix composition or added as a separate stream during the formation of the foaming composition. The flame retardant can be blended with the polyol and thus can be provided as a polyol premix composition with a polyol or a mixture of polyols before the formation of the foaming composition. Alternatively, the flame retardant can be added as a separate stream during the formation of the foaming composition. For the purposes of the present invention, the amount of the phosphate flame retardant includes all phosphate flame retardants, i.e., the amount of the phosphate flame retardant present in the polyol premix composition or added as a separate stream during the formation of the foaming composition. The flame retardant can be blended with the polyol and thus can be provided as a polyol premix composition with a polyol or a mixture of polyols before the formation of the foaming composition. Alternatively, the flame retardant can be added as a separate stream during the formation of the foaming composition. For the purposes of the present invention, the amount of the phosphate flame retardant includes all phosphate flame retardants, i.e., the amount of the phosphate flame retardant present in the polyol premix composition or added as a separate stream during the formation of the foaming composition. The flame retardant can be blended with the polyol and thus can be provided as a polyol premix composition with a polyol or a mixture of polyols before the formation of the foaming composition. Alternatively, the flame retardant can be added as a separate stream during the formation of the foaming composition. For the purposes of the present invention, the amount of the phosphate flame retardant includes all phosphate flame retardants, i.e., the amount of the phosphate flame retardant present in the polyol premix composition or added as a separate stream during the formation of the foaming composition.

[0092] The inventors have limited the amount of the phosphate flame retardant in the polyol premix composition to 25 phpp or less, and after aging at 70°C for 21 days, the polyurethane foam, polyisocyanurate foam, or their mixture generated from the polyol premix composition The inventors have limited the amount of the phosphate flame retardant in the polyol premix composition to 25 phpp or less, and after aging at 70°C for 21 days, the polyurethane foam, polyisocyanurate foam, or their mixture generated from the polyol premix composition The inventors have limited the amount of the phosphate flame retardant in the polyol premix composition to 25 phpp or less, and after aging at 70°C for 21 days, the polyurethane foam, polyisocyanurate foam, or their mixture generated from the polyol premix composition It has also been found that the lambda aging of these mixtures can be reduced.

[0093] Others In addition, the polyol premix composition may contain other components such as dyes, fillers, pigments, etc. Dispersants and cell stabilizers can be used. Conventional fillers used herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fiber, carbon black, and silica. When used, the filler is usually present in an amount in the range of about 5 parts to 100 parts per 100 parts by weight of the polyol. Pigments that can be used herein include any conventional pigment, such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chromium green, chromium yellow, iron blue prussian, molybdenum orange, and organic pigments, such as para red, benzidine yellow, toluidine red, toner, and phthalocyanine.

[0094] Foaming method The preparation of polyurethane and / or polyisocyanurate foams using a blowing agent, polyol, any other constituent components, and isocyanate can be carried out according to any method known in the art relating to foam formation, Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and technology, 1962, John Wiley and Sons, New York, N.Y. or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New ​​​​New York, N.Y. or Klempner and Sendijarevic, P Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, O See H. Generally, polyurethane and / or polyisocyanurate foams are made by combining, among other things, an isocyanate and a polyol premix composition. The resulting foam is preferably a closed-cell foam that can be rigid or semi-rigid and is preferably a rigid foam. For purposes of the present invention, the isocyanate can be provided in combination with other components such as certain silicone surfactants. The isocyanate can be combined with a blowing agent, although the blowing agent is herein assumed to comprise at least primarily the polyol premix composition of the first aspect. However, the present invention encompasses the option that at least a portion of the blowing agent is combined with the isocyanate.

[0095] For purposes of the present invention, the isocyanate can be provided in combination with other components such as certain silicone surfactants. The isocyanate can be combined with a blowing agent, although the blowing agent is herein assumed to comprise at least primarily the polyol premix composition of the first aspect. However, the present invention encompasses the option that at least a portion of the blowing agent is combined with the isocyanate. For purposes of the present invention, the isocyanate can be provided in combination with other components such as certain silicone surfactants. The isocyanate can be combined with a blowing agent, although the blowing agent is herein assumed to comprise at least primarily the polyol premix composition of the first aspect. However, the present invention encompasses the option that at least a portion of the blowing agent is combined with the isocyanate. For purposes of the present invention, the isocyanate can be provided in combination with other components such as certain silicone surfactants. The isocyanate can be combined with a blowing agent, although the blowing agent is herein assumed to comprise at least primarily the polyol premix composition of the first aspect. However, the present invention encompasses the option that at least a portion of the blowing agent is combined with the isocyanate. For purposes of the present invention, the isocyanate can be provided in combination with other components such as certain silicone surfactants. The isocyanate can be combined with a blowing agent, although the blowing agent is herein assumed to comprise at least primarily the polyol premix composition of the first aspect. However, the present invention encompasses the option that at least a portion of the blowing agent is combined with the isocyanate. For purposes of the present invention, the isocyanate can be provided in combination with other components such as certain silicone surfactants. The isocyanate can be combined with a blowing agent, although the blowing agent is herein assumed to comprise at least primarily the polyol premix composition of the first aspect. However, the present invention encompasses the option that at least a portion of the blowing agent is combined with the isocyanate.

[0096] Polyurethane foams, polyisocyanurate foams or mixtures thereof are prepared by hand mixing for small scale production, preferably by continuous or discontinuous production techniques for forming boards, blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, skims, etc., by bringing together the isocyanate and the polyol premix composition. Optionally, other components such as colorants, auxiliary blowing agents, water, catalysts, and still other polyols can be added as a stream to the mixing head or reaction site. However, Polyurethane foams, polyisocyanurate foams or mixtures thereof are prepared by hand mixing for small scale production, preferably by continuous or discontinuous production techniques for forming boards, blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, skims, etc., by bringing together the isocyanate and the polyol premix composition. Optionally, other components such as colorants, auxiliary blowing agents, water, catalysts, and still other polyols can be added as a stream to the mixing head or reaction site. However, Polyurethane foams, polyisocyanurate foams or mixtures thereof are prepared by hand mixing for small scale production, preferably by continuous or discontinuous production techniques for forming boards, blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, skims, etc., by bringing together the isocyanate and the polyol premix composition. Optionally, other components such as colorants, auxiliary blowing agents, water, catalysts, and still other polyols can be added as a stream to the mixing head or reaction site. However, Polyurethane foams, polyisocyanurate foams or mixtures thereof are prepared by hand mixing for small scale production, preferably by continuous or discontinuous production techniques for forming boards, blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, skims, etc., by bringing together the isocyanate and the polyol premix composition. Optionally, other components such as colorants, auxiliary blowing agents, water, catalysts, and still other polyols can be added as a stream to the mixing head or reaction site. However, Polyurethane foams, polyisocyanurate foams or mixtures thereof are prepared by hand mixing for small scale production, preferably by continuous or discontinuous production techniques for forming boards, blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, skims, etc., by bringing together the isocyanate and the polyol premix composition. Optionally, other components such as colorants, auxiliary blowing agents, water, catalysts, and still other polyols can be added as a stream to the mixing head or reaction site. However, Polyurethane foams, polyisocyanurate foams or mixtures thereof are prepared by hand mixing for small scale production, preferably by continuous or discontinuous production techniques for forming boards, blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, skims, etc., by bringing together the isocyanate and the polyol premix composition. Optionally, other components such as colorants, auxiliary blowing agents, water, catalysts, and still other polyols can be added as a stream to the mixing head or reaction site. However, However, most conveniently, they are all incorporated into the polyol premix as described above. are incorporated.

[0097] For the purposes of the present invention, the polyurethane foam, polyisocyanurate foam, or a mixture thereof is produced as a continuous or discontinuous pore-in-place panel, board, or spray-applied foam. are produced as a continuous or discontinuous pore-in-place panel, board, or spray-applied foam. is produced.

[0098] Specifically, when the foam is provided as a board or panel, the foam can be produced by pouring a foaming mixture between two facings of the panel, raising the foam, and cutting it to the desired length to produce a "foam sandwich". The decorative surface of the panel can be aluminum foil, roofing paper, metal, wood, etc. The resulting board or panel can then be applied to an existing building enclosure or used to form the building enclosure. is poured between two facings of the panel, the foam is raised, and cut to the desired length to produce a "foam sandwich". The decorative surface of the panel can be aluminum foil, roofing paper, metal, wood, etc. The resulting board or panel can then be applied to an existing building enclosure or used to form the building enclosure. The decorative surface of the panel can be aluminum foil, roofing paper, metal, wood, etc. The resulting board or panel can then be applied to an existing building enclosure or used to form the building enclosure. These panels can be produced by both continuous and discontinuous processes. These panels can be produced by both continuous and discontinuous processes. .

[0099] The polyurethane foam, polyisocyanurate foam, or a mixture thereof produced has a density that can vary from about 0.5 pounds per cubic foot to about 60 pounds per cubic foot, preferably from about 1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to 6.0 pounds per cubic foot. The resulting density is a function of the amount of blowing agent or blowing agent mixture, and additionally water or co-blowing agents such as co-blowing agents used to prepare the foam. has a density that can vary from about 0.5 pounds per cubic foot to about 60 pounds per cubic foot, preferably from about 1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to 6.0 pounds per cubic foot. .0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to 6.0 pounds per cubic foot. The resulting density is a function of the amount of blowing agent or blowing agent mixture, and additionally water or co-blowing agents such as co-blowing agents used to prepare the foam. The resulting density is a function of the amount of blowing agent or blowing agent mixture, and additionally water or co-blowing agents such as co-blowing agents used to prepare the foam. .

[0100] Uses Among many uses, the foam of the present invention is suitable for buildings (e.g., building envelopes) or Insulate any structure where energy management and / or insulation from external temperature fluctuations is desirable may be used for. Such structures include, but are not limited to, houses, office buildings, or other structures made from clay, wood, stone metal, plastic, concrete, etc., including locations where residential, commercial, industrial, agricultural, or energy efficiency and insulation may be desirable but are not limited to these.

[0101] Accordingly, aspects of the present invention relate to a board foam, foam core panel, or spray foam produced by the method of the first aspect of the present invention.

[0102] Experimental procedures Polyol blend: The blend was prepared by mixing materials based on the following formulation.

[0103] Foaming: The foam was made by hand mixing based on the formulation listed below. A mold (30 cm × 30 cm × 10 cm) was used.

[0104] Lambda value: The lambda value was recorded using a LaserComp FOX50 with a sample size of 20 cm × 20 cm × 2 cm.

[0105] 1233zd(E) gas solubility: The solubility of 1233zd(E) in the polyol / flame retardant is measured using a gravimetric method utilizing a microbalance. The microbalance is made by a VTI model GHP (High Pressure Gravimetric Analyzer). The sample is placed in an environment filled with pure gas, and the weight gain of the sample is measured over time at a constant temperature and pressure. From the time-dependent data, the solubility can be determined from the initial and equilibrium weights.

[0106] ​​​​Example #1 - 1233zd(E) Gas Solubility in Different Polyols Various polyols, including polyester polyols with different functionalities, Polyether polyols with different initiators were polymerized on a microbalance at 30°C. was selected for testing 1233zd(E) gas solubility by measuring mass increase. Table 1 summarizes the solubility of 1233zd(E) gas in various polyols.

[0107] [Table 1]

[0108] Among the polyols tested, Isoexter 4404-US was the 1233zd( E) It has the lowest solubility for gases, and Voranol 270 has the highest. Applicants believe that, in general, polyester polyols are more effective than polyether polyols. It was found that 1233zd(E) tends to have low solubility.

[0109] Example 2 Initial Lambda of PIR Foams Based on Different Polyols Table 2 shows the composition of the polyol preblends. These preblends were mixed at 250 PIR foam by reacting with isocyanate M20 with the same index was used in the preparation of

[0110] [Table 2]

[0111] The freshly made foam was allowed to cure for 24 hours and then placed in a mold measuring 20cm x 20cm x 2cm. of core foam was cut out and an initial lambda measurement was taken.

[0112] The initial lambda of each PIR foam changed significantly as shown in Fig. 1. Terate The foam using the polyester polyol of HT 5510 had the best initial lambda of 17.62 mW / mK( at 10 °C), while the foam using the polyether polyol Vora nol 270 had the worst initial lambda of 23.8 mW / mK .

[0113] Example 3 Aging Lambda of PIR Foams Based on Different Polyols After recording the initial lambda, the exact same foams were placed in an oven and aged at 70 °C for 21 days based on the requirements of the EN 13165 normative test. The lambda value (aging lambda) was measured again from such aged foam samples . The aging lambda of the PIR foam changed significantly depending on the polyol used in the preparation of the foam, as shown in Fig. 2. The foam with the best aging lambda was the one using Terate HT 5510 , while the foam prepared from Voranol 270 had the worst aging lambda . .

[0114] Example 4 Aging Performance of PIR Foams Based on Different Polyols The aging performance of the foam can be judged by the delta lambda value obtained based on the difference between the aging lambda and the initial lambda . Delta lambda = aging lambda - initial lambda

[0115] Fig. 3 shows the aging performance (delta lambda) of each foam depending on the polyol used in the foam. The foam using Terate HT 5510 had the best aging performance with the lowest delta lambda of 4.53 mW / mK, while Voranol 270 ​​​The foam using it has the worst aging performance with a delta lambda of 11.72 mW / mK. Such a tendency is consistent with the observation about the influence of the polyol on the initial lambda of each foam.

[0116] Example 5 Correlation between the gas solubility and the initial lambda of each foam, and the aging lambda and delta lambda relationship As shown in Figure 4, the results of Example 4 show that there is a correlation between the solubility of 1233zd(E) in each polyol (the value on the right y-axis indicated by the line in the figure) and the initial lambda of the PIR foam (the value on the left y-axis indicated by the bar in the figure). The foam with the best initial lambda contained the polyol with the lowest solubility for 1233zd(E) gas.

[0117] There was a similar correlation between the aging lambda of the foam and the gas solubility of 1233zd(E) used in the preparation of the foam (see Figure 5, where the solubility in each polyol is indicated by the line in the figure, and the value is on the right y-axis, and the aging lambda of the PIR foam is indicated by the bar in the figure, and the value is on the left y-axis).

[0118] A similar conclusion can be drawn between the gas solubility of 1233zd(E) in each polyol and the aging performance of the foam using the polyol (Figure 6).

[0119]

Table 3

[0120] Example 6 Influence of the gas solubility of 1233zd(E) on the lambda of the spray foam The influence of the gas solubility of 1233zd(E) in the polyol on the lambda value is for spraying ​​​​​​​Observed in the foam and shown in Figure 7. The formulations of the spray foams tested are listed in Table 3. are shown.

[0121]

Table 4

[0122] The polyol Terol 649 has a higher gas solubility of 233zd(E) than the polyol Terate HT5350. When Terol 649 in the spray foam was replaced with Terate HT 5350, all lambda values were improved. The gas solubility of 233zd(E) is high. When Terol 649 in the spray foam was replaced with Terate HT 5350, all lambda values were improved. are improved.

Claims

1. 1. A method for making a thermosetting insulating foam comprising the steps of: (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent; The polyol is at least about 50% by weight of the physical blowing agent. The physical blowing agent comprises a low solubility polyol, and the physical blowing agent is at least about 50% by weight of a trans-1 -chloro-3,3,3-trifluoropropene (trans 1233zd); 、 (b) forming a foam from said foamable composition.

2. 10. The method of claim 1, wherein the foam has a delta lambda of less than about 7 mW / mK. 。

3. 5. The method of claim 4, wherein the polyol comprises at least about 75% by weight of a low solubility polyol. The method according to

4. The polyol comprises at least about 75% by weight of a polyester polyol. Item 5. The method according to item 4.

5. The physical blowing agent comprises at least about 75% by weight of the trans 1233zd. The method according to claim 6.

6. The physical blowing agent comprises at least about 75% by weight of the trans 1233zd. The method according to claim 5.

7. The low solubility polyol comprises a polyol or a mixture of polyols, 1233zd has a solubility in said polyol of less than about 25%, and said foam has a solubility of about 6 mW 2. The method of claim 1 , having a delta lambda of less than 1 / mK.

8. 1. A method for making a thermosetting insulating foam comprising the steps of: (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent; wherein the physical blowing agent is at least about 50% by weight of trans-1-chloro- 3,3,3-trifluoropropene (trans 1233zd), said polyol so that the trans-1233zd has a solubility in the polyol of less than about 25%. , a polyol or a mixture of polyols; (b) forming a foam from said foamable composition.

9. The polyol has a trans-1233zd content of about 20% or less. The foam contains a polyol or a mixture of polyols so as to have a solubility of 20 ml.

9. The method of claim 8 having an initial lambda of less than or equal to W / mK.

10. 10. The method of claim 9, wherein the foam has a delta lambda of less than about 7 mW / mK. 。

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