Low density thermoset foams having improved properties

Abstract

A method of forming a foam is disclosed that includes: (a) providing a foamable composition comprising an isocyanate, a polyol, and a physical blowing agent comprising at least about 50 wt.% trans-1233zd, wherein the polyol comprises a polyol or mixture of polyols such that trans-1233zd(E) has a solubility in the polyol of 20 pphp or less; and (b) forming a foam from the foamable composition.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) The present invention claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 299,379, filed January 13, 2022, and to U.S. Provisional Patent Application No. 18 / 096,703, filed January 13, 2023, each of which is incorporated by reference in its entirety herein.

[0002] FIELD OF THEINVENTION The present invention relates to thermoset foams, particularly polyurethane foams, polyisocyanurate foams, or mixtures thereof, that achieve improved thermal insulation properties, as well as to foamable compositions and foaming methods for making the foamable compositions. [Background technology]

[0003] The use of foams to provide thermal insulation is well known. For example, insulation boards made from polyisocyanurate (PIR) or polyurethane (PU) foams are used in commercial, residential, and industrial buildings to provide resistance to heat flow into and / or out of buildings. Other forms of PU and PIR foams are also used, at least in part, for their thermal insulation value.

[0004] Polyurethane foams are typically produced by reacting a polyisocyanate (usually a di- or triisocyanate) 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 ingredients. In the case of PIR foams, the foam is formed by reacting the polyisocyanate with itself to form a cyclic trimer structure. In practice, foams commonly described as polyisocyanurate (also referred to as PIR) contain both polyurethane and polyisocyanurate structures, and foams described as polyurethane often incorporate some polyisocyanurate structures. Thus, the present application relates to polyurethane foams, polyisocyanurate foams, and mixtures thereof. The blowing agent may be a physical blowing agent or a chemical blowing agent. A physical blowing agent produces bubbles in a liquid mixture by volatilizing and expanding due to the heat generated when the polyisocyanurate reacts with the polyol to form bubbles therein. In the case of chemical blowing agents, also known as gas generating materials, gaseous 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] The use of certain liquid fluorocarbon blowing agents as blowing agents is common due to their ease of use, among other factors. Not only do the fluorocarbons act as physical blowing agents due to their volatility, but they are also encapsulated or entrained in the closed cell structure of the foam and are generally the primary cause of the foam's poor thermal conductivity properties. After the foam is formed, the k-factor or lambda associated with the foam provides a measure of the foam's ability to resist the transfer of heat through the foam. Foams with lower k-factors are generally better foams for thermal insulation purposes, since they are more resistant to heat transfer. Thus, the production of lower k-factor foams is generally desirable and advantageous.

[0006] In recent years, concerns about climate change have prompted the development of a new generation of blowing agents that can meet the requirements of both ozone depletion and climate change regulations. One particularly interesting hydrohaloolefin is trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)). See, for example, U.S. Patent No. 8,420,706, assigned to the assignee of the present invention. Processes for producing trans-1-chloro-3,3,3-trifluoropropene are disclosed, for example, in U.S. Patent Nos. 6,844,475 and 6,403,847.

[0007] The desirability of an insulating foam generally depends on several properties of the foam when it is formed, including the density of the foam and the insulating ability of the foam. The initial values ​​of these properties are considered when the board is approximately formed, but a more important consideration is often the values ​​of these properties that the foam will have or be expected to have over time thereafter. This is because PIR or PU foam, for example in the form of an insulating board, may remain part of a building structure for an extended period of time, and it is believed to be very important in many applications that the foam is expected to provide the desired insulating and density properties over a substantial period of use.

[0008] An estimate of the average thermal conductivity (lambda value or k-factor) over a 25-year service life under operating conditions can be made using European Standard EN13165:2012+A2:2016 (2010) for factory-made rigid polyurethane and polyisocyanurate foam products used as insulation boards in buildings, and European Standard EN14315 (2013) for in-situ formed sprayed rigid polyurethane and polyisocyanurate foam products, both of which are incorporated by reference. This K-factor value that the foam achieves (sometimes referred to as aged K-factor) is often considered to be an important measure of the foam's performance and value. Blowing agent 1233zd(E) is generally known to provide desirably low aged K-factor values ​​for PU and PIR foams.

[0009] The density of the foam after the aging period is also considered to be important for many applications. In particular, it is known to test the ability of a foam to resist dimensional changes during aging at a given density. According to this test protocol, foam at initial density is subjected to accelerated aging test conditions and the dimensional changes of the foam are measured. One such test is called the "Dim-Vac" test, which is performed as described in the examples of this specification. According to this test, if the change in volume is a large negative number (i.e., a negative number of -5% or more), the test is considered to predict that the foam will fail catastrophically in an unacceptable manner during the foam's expected service life, and the density of the foam that results in this result is considered to be below the minimum useful density.

[0010] Applicants have come to realize that while rigid PU and PIR foams heretofore formed using 1233zd(E) blowing agent have achieved excellent thermal conductivity, they also have undesirably high minimum useful densities, which in turn poses unresolved problems with the use of 1233zd(E) as a blowing agent for rigid PU and PIR insulation foams. Summary of the Invention

[0011] The present invention relates to a method for producing thermoset PU and / or PIR foams having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) a polyol premix composition, comprising a blowing agent comprising at least about 50% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and a foam produced from the premix having a foam yield of 27 kg / m 3 and one or more polyol components, which together have a solubility limit of said 1233zd(E) sufficiently low to enable said polyol premix composition to have a minimum usable density (hereinafter sometimes referred to as "MUD") less than 1233zd(E); (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 1A.

[0012] The terms "1233zd(E) solubility" and minimum usable density (or MUD) are determined when measured according to the procedures specified in the Examples herein or by a procedure that provides essentially the same measurement + / - 2 relative percent.

[0013] As used herein with respect to weight percent of a component, "about" means the specified weight percent + / - 2 relative percent.

[0014] As used herein, the term "pphp" means parts by weight per 100 parts by weight of polyol.

[0015] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) a polyol premix composition, comprising a blowing agent comprising at least about 50% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and a foam produced from the premix having a foam yield of 27 kg / m 3 and one or more polyol components, which together have a solubility limit of said blowing agent low enough to enable said blowing agent to have a MUD of less than 1000 ppm. (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 1B.

[0016] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 50 wt. % of a polyol having a 1233zd(E) solubility of about 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a minimum usable density (hereinafter sometimes referred to as "MUD") less than For convenience, the method according to this paragraph will be referred to herein as Method 1C.

[0017] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 50 wt. % of a polyol(s) having a 1233zd(E) solubility of about 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3producing a foam having a minimum usable density (hereinafter sometimes referred to as "MUD") of less than about 1000 nm, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6; For convenience, the method according to this paragraph will be referred to herein as Method 1D.

[0018] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 50 wt. % of a polyol(s) having a 1233zd(E) solubility of less than about 15 pphp; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a minimum usable density (hereinafter sometimes referred to as "MUD") of less than about 1000 nm, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6; For convenience, the method according to this paragraph will be referred to herein as Method 1E.

[0019] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 75 wt.% of a polyol having a 1233zd(E) solubility of about 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 2A.

[0020] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 75 wt.% of a polyol having a 1233zd(E) solubility of about 15 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 2B.

[0021] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 75 wt. % of a polyol having a 1233zd(E) solubility of less than about 14 pphp; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 3.

[0022] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 80 wt. % of a polyol having a 1233zd(E) solubility of about 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 4A.

[0023] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 80 wt. % of a polyol having a 1233zd(E) solubility of about 15 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 4B.

[0024] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 85 wt. % of a polyol having a 1233zd(E) solubility of less than about 14 pphp; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 5.

[0025] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 90 wt. % of a polyol having a 1233zd(E) solubility of about 20 or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 6A.

[0026] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), the one or more polyols comprising at least about 90 wt. % of a polyol having a 1233zd(E) solubility of about 15 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 6B.

[0027] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), wherein the one or more polyols consist essentially of a polyol(s) having a 1233zd(E) solubility of about 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph will be referred to herein as Method 7A.

[0028] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), wherein the one or more polyols consist essentially of a polyol(s) having a 1233zd(E) solubility of about 15 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than about 1.5, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6; For convenience, the method according to this paragraph will be referred to herein as Method 7B.

[0029] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), wherein the one or more polyols consist essentially of a polyol(s) having a 1233zd(E) solubility of less than about 15 pphp; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than For convenience, the method according to this paragraph is referred to herein as Method 7C.

[0030] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), wherein the one or more polyols consist essentially of a polyol(s) having a 1233zd(E) solubility of less than about 15 pphp; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a density of 27 kg / m 3 producing a foam having a MUD of less than about 1.5, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6; For convenience, the method according to this paragraph will be referred to herein as Method 7D.

[0031] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a physical blowing agent, the physical blowing agent comprising greater than 60 wt.% trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and less than 40 wt.% cyclopentane, based on the total weight of the physical blowing agent, the one or more polyols comprising at least about 50 wt.% polyols having a 1233zd(E) solubility of 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) foaming the foamable composition to form a foam, the foam having a delta lambda of less than 4.5 mW / mK; For convenience, the method according to this paragraph will be referred to herein as Method 8A.

[0032] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a physical blowing agent, the blowing agent comprising at least about 70 wt.% trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and less than about 30 wt.% cyclopentane, based on the total weight of the physical blowing agent, the one or more polyols comprising at least about 50 wt.% of a polyol having a 1233zd(E) solubility of about 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) foaming the foamable composition to form an insulating foam; and For convenience, the method according to this paragraph will be referred to herein as Method 8B.

[0033] The present invention also provides a method for producing a thermoset PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum usable density, comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a physical blowing agent, the blowing agent consisting essentially of about 70 wt.% or more trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and about 30 wt.% or less cyclopentane, based on the total weight of the physical blowing agent, the one or more polyols comprising at least about 50 wt.% of a polyol having a 1233zd(E) solubility of about 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) foaming the foamable composition to produce an insulating foam; and For convenience, the method according to this paragraph will be referred to herein as Method 8C.

[0034] The present invention relates to a thermosetting PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, (a) a plurality of closed cells having cell walls formed of PU and / or PIR; (b) 1233zd(E) contained within the closed bubbles; Including, 27kg / m 3 For convenience, the process according to this paragraph will be referred to herein as Foam 1.

[0035] The present invention relates to a thermosetting PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, (a) cell walls formed of PU and / or PIR forming a plurality of closed cells; (b) 1233zd(E) contained within the cell walls; Including, 27kg / m 3 and an initial K-factor of less than about 18 mW / mK. For convenience, the process according to this paragraph is referred to herein as Foam 2A.

[0036] The present invention relates to a thermosetting PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, (c) cell walls formed of PU and / or PIR forming a plurality of closed cells; (d) 1233zd(E) contained within the cell walls; Including, 27kg / m 3 This includes foams having a MUD of less than about 100 nm, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6. For convenience, the process according to this paragraph is referred to herein as Foam 2B.

[0037] The present invention relates to a thermosetting PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, (a) cell walls formed of PU and / or PIR forming a plurality of closed cells; (b) 1233zd(E) contained within the cell walls; Including, 26kg / m 3 This includes foams having a MUD of less than about 100 nm, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6. For convenience, the process according to this paragraph will be referred to herein as Foam 3.

[0038] The present invention relates to a thermosetting PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, (a) cell walls formed of PU and / or PIR forming a plurality of closed cells; (b) 1233zd(E) contained within the cell walls; Including, Approximately 25kg / m 3 These include foams having the following MUD, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6. For convenience, the process according to this paragraph will be referred to herein as Foam 4.

[0039] The present invention relates to a thermosetting PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and a low minimum usable density, (a) cell walls formed of PU and / or PIR forming a plurality of closed cells; (b) 1233zd(E) contained within the cell walls; Including, 25kg / m 3 This includes foams having a MUD of less than about 100 nm, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6. For convenience, the process according to this paragraph will be referred to herein as Foam 5.

[0040] The present invention relates to a thermosetting PU and / or PIR foam having good thermal insulation properties (preferably including low initial lambda values, low aged lambda values, and / or low delta lambda values) and low minimum density, (a) a plurality of closed cells having cell walls formed of PU and / or PIR; (b) 1233zd(E) contained within the cell walls; Including, Approximately 24kg / m 3This includes foams having the following MUD and having an initial K-factor of less than about 18 mW / mK and a delta lambda of less than 6. For convenience, the process according to this paragraph will be referred to herein as Foam 6. [Brief description of the drawings]

[0041] [Figure 1] 1 is a chart showing the MUD of polyol A determined in Comparative Example 1. [Figure 2A] 1 is a chart showing the MUD of Polyol D using 1233zd(E) as a blowing agent, as determined in Comparative Example 2. [Figure 2B] 1 is a chart showing the MUD of Polyol D using a combination of 1233zd(E) and cyclopentane as a blowing agent, obtained in Comparative Example 2. [Diagram 3] 1 is a chart showing the MUD of Polyol B determined in Example 1. [Figure 4] 1 is a chart showing the MUD of Polyol C determined in Example 2. [Figure 5A] 1 is a chart showing the MUD of Polyol E using 1233zd(E) as a blowing agent, as determined in Example 3. [Figure 5B] 1 is a chart showing the MUD of Polyol E using a combination of 1233zd(E) and cyclopentane as a blowing agent, as determined in Example 4. [Figure 6] 1 is a chart showing results obtained from Example 5.

[0042] definition Trans 1233zd and 1233zd(E) each represent trans 1-chloro-3,3,3-trifluoropropene.

[0043] By closed cell foam it is meant that a substantial volume percentage of the cells in the foam are closed, for example, about 20 volume % or more.

[0044] Initial K-factor (sometimes also referred to as initial lambda) means the initial thermal conductivity measured in accordance with EN 13165:2012+A2:2016 and accordingly measured at a reference mean temperature of 10°C.

[0045] Aged K-factor (sometimes also referred to as aged lambda) means the aged thermal conductivity measured in accordance with EN 13165:2012+A2:2016 and measured accordingly at a reference mean temperature of 10°C.

[0046] Delta lambda refers to the value determined according to the procedure in the Examples herein.

[0047] Density refers to the foam density measured in the examples.

[0048] Minimum usable density and MUD each refer to the minimum usable density measured as in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0049] Foamable Composition As noted above, the foamable composition of the present invention includes as essential components a thermosetting material (preferably a urethane and / or an isocyanurate), a polyol, and a physical blowing agent. Apart from those described as necessary herein, the specific properties and amounts of these components may be provided within broad ranges known to those skilled in the art, and additional optional components, including those described below, may also be included within such broad ranges.

[0050] Foaming Agent For purposes of this invention, the physical blowing agent preferably comprises at least about 50% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)). For convenience, the blowing agent according to this paragraph will be referred to herein as Blowing Agent 1.

[0051] For purposes of the present invention, the physical blowing agent preferably comprises greater than 60% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)). For convenience, the blowing agent according to this paragraph will be referred to herein as Blowing Agent 2.

[0052] For purposes of the present invention, the physical blowing agent preferably comprises at least about 70% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)). For convenience, the blowing agent according to this paragraph will be referred to herein as Blowing Agent 3.

[0053] For purposes of the present invention, the physical blowing agent preferably comprises greater than 60% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and less than 40% by weight of cyclopentane, based on the total weight of the physical blowing agent. For convenience, the blowing agent according to this paragraph will be referred to herein as Blowing Agent 4.

[0054] For purposes of the present invention, the physical blowing agent preferably comprises at least about 70% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and up to about 30% by weight of cyclopentane, based on the total weight of the physical blowing agent. For convenience, the blowing agent according to this paragraph will be referred to herein as Blowing Agent 5.

[0055] A preferred embodiment that achieves excellent insulation results, particularly including initial lambda, aged lambda, and delta lambda, at low cost includes a physical blowing agent of greater than 60% to about 70% by weight trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and about 30% to less than 40% by weight cyclopentane, based on the total weight of the physical blowing agents. For convenience, the blowing agent according to this paragraph will be referred to herein as Blowing Agent 6.

[0056] Optional co-blowing agents include 1,3,3,3-tetrafluoropropene (1234ze) and 1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm). 1,3,3,3-tetrafluoropropene (1234ze) can be provided as a cis isomer, a trans isomer, or a combination thereof. Preferably, 1,3,3,3-tetrafluoropropene is provided as a trans isomer. 1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm) can be provided as a cis isomer, a trans isomer, or a combination thereof. Preferably, 1,1,1,4,4,4-hexafluorobut-2-ene is provided as a cis isomer.

[0057] The physical blowing agent used in accordance with the methods of the present invention, including each of Methods 1-25, may comprise, consist essentially of, or consist of trans-1-chloro-3,3,3-trifluoropropene (1233zd).

[0058] In each of Methods 1-7, the blowing agent may include Blowing Agent 1, or Blowing Agent 2, or Blowing Agent 3, or Blowing Agent 4, or Blowing Agent 5, or Blowing Agent 6.

[0059] Blowing agents include hydrocarbons, fluorocarbons, chlorocarbons, fluorochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, halogenated hydrocarbons, ethers, fluorinated ethers, esters, acetals, alcohols, aldehydes, ketones, organic acids, gas generating materials, water, and carbon dioxide (CO 2), or combinations thereof. Preferred blowing agents have a Global Warming Potential (GWP) of 150 or less, more preferably 100 or less, and even more preferably 75 or less. As used herein, "GWP" is measured relative to the GWP of carbon dioxide and over a 100-year time horizon, as defined in "The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference. Preferred blowing agents have an Ozone Depletion Potential (ODP) of 0.05 or less, more preferably 0.02 or less, and even more preferably about zero. As used herein, "ODP" is as defined in "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference.

[0060] Preferred optional chemical co-blowing agents include water, CO 2 and / or organic acids that produce CO.

[0061] Preferred optional physical co-blowing agents include CO 2, ethers, halogenated ethers; esters, alcohols, aldehydes, ketones; trans-1,2 dichloroethylene; methylal, 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 (236fa); 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); hydrocarbons such as butane; isobutane; normal pentane; isopentane; cyclopentane, or combinations thereof.

[0062] More preferably, the co-blowing agent is water, CO 2 and / or one or more selected from CO-producing organic acids, trans-1,2-dichloroethylene; methylal, methyl formate; 1,1,1,2-tetrafluoroethane (134a); 1,1,1,3,3-pentafluorobutane (365mfc); 1,1,1,2,3,3,3-heptafluoropropane (227ea), 1,1-difluoroethane (152a); 1,1,1,3,3-pentafluoropropane (245fa); butane; isobutane; normal pentane; isopentane; cyclopentane, or combinations thereof.

[0063] The blowing agents of the present invention, including each of Blowing Agents 1-6 which is Trans 1233zd and any optional co-blowing agent, are preferably present in the foamable composition in an amount of from about 1% to about 30% by weight, preferably from about 3% to about 25% by weight, and more preferably from about 5% to about 25% by weight, based on the weight of polyol plus blowing agent in the composition.

[0064] Polyol As mentioned above, applicants have found that careful selection of the polyol used in the current foamable composition can have an unexpected but highly beneficial effect on the heat transfer resistance of foams containing relatively low MUD values. Thus, the polyol according to the present invention should be selected to comply with one of the structural requirements described herein (e.g., solubility of 1233zd(E) of about 20 pphp or less). As long as one of these selections is made in accordance with the teachings of the present specification, the polyol can be any polyol or polyol mixture that reacts with isocyanates in a known manner in the preparation of polyurethane foams, polyisocyanurate foams, or mixtures thereof. The preferred polyols are polyester polyols, and even more preferably, polyester polyols that contain aromatic groups in the polyol. Other useful polyols, in addition to the preferred polyester polyols, can optionally include, for example, sucrose-containing polyols; phenol, phenol formaldehyde-containing polyols; glucose-containing polyols; sorbitol-containing polyols; methyl glucoside-containing polyols.

[0065] The polyol or mixture of polyols may be present in the foamable composition in an amount of, for example, about 20% by weight to about 70% by weight, preferably about 30% by weight to about 60% by weight, and more preferably about 35% by weight to about 55% by weight, based on the total weight of the foamable composition.

[0066] The polyol, preferably a polyester polyol, and even more preferably an aromatic polyester polyol, may preferably have one or more of the following properties within the following broad, medium, and narrow ranges, and any combination of these properties and ranges:

[0067] [Table 1]

[0068] Commercially available low solubility polyols that may be used in connection with the present invention include those available from Stepan, Coim, and Puranova.

[0069] Isocyanates For the purposes of the present invention, the isocyanate can be any organic polyisocyanate that can be used in polyurethane and / or polyisocyanurate foam synthesis, including aliphatic and aromatic polyisocyanates.Suitable organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates that are 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.

[0070] Representative organic polyisocyanates have the formula: R(NCO) z where R is a polyvalent organic group that is either aliphatic, aralkyl, aromatic, or mixtures thereof, and z corresponds to the valence of R and is at least 2. Representative organic polyisocyanates contemplated herein include, for example, aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate; aromatic triisocyanates such as 4,4',4''-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanate; aromatic tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'5,5-'tetraisocyanate; aryl alkyl polyisocyanates such as xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene-1,6-diisocyanate, lysine diisocyanate methyl ester, and mixtures thereof. Other organic polyisocyanates include polymethylene polyphenylisocyanate, hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate.Typical aliphatic polyisocyanates are alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, isophorene diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), and the like.Typical aromatic polyisocyanates include m- and p-phenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 2,4- and 2,6-toluene diisocyanate, dianisidine diisocyanate, bitolene isocyanate, naphthalene 1,4-diisocyanate, bis(4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane, and the like. Preferred polyisocyanates are polymethylene polyphenyl polyisocyanates, particularly mixtures containing about 30 to about 85% by weight of methylene bis(phenylisocyanate), with the remainder of the mixture being polymethylene polyphenyl polyisocyanates of functionality greater than 2. These polyisocyanates are prepared by conventional methods known in the art. In the present invention, the polyisocyanates and polyols are preferably used in amounts that result in an NCO / OH stoichiometric ratio ranging from about 0.9 to about 5.0. In the present invention, the NCO / OH equivalent ratio is preferably from about 1 to about 4, with an ideal range being from about 1.1 to about 3. Particularly suitable organic polyisocyanates include polymethylene polyphenyl polyisocyanate, methylene bis(phenylisocyanate), toluene diisocyanate, or combinations thereof.

[0071] Other components Other components that may be included in the foamable composition include silicone surfactants, non-silicone surfactants, and catalysts, including metal catalysts and amine catalysts and combinations thereof.

[0072] Non-silicone surfactants Non-silicone surfactants, such as non-silicone nonionic surfactants, can include oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oil, castor oil esters, ricinoleic acid esters, turkey red oil, peanut oil, paraffin, and fatty alcohols.Preferred non-silicone nonionic surfactants are LK-443 available from Air Products Corporation or Vorasurf 504 from DOW.

[0073] If a non-silicone nonionic surfactant is used, it is typically present in the composition in an amount of from about 0.25% to about 3.0% by weight, preferably from about 0.5% to about 2.5% by weight, and more preferably from about 0.75% to about 2.0% by weight, based on the weight of the polyol, blowing agent, and silicone in the composition.

[0074] catalyst The catalyst may include an amine catalyst and / or a metal catalyst. The amine catalyst may include, but is not limited to, a primary amine, a secondary amine, or a tertiary amine. Useful tertiary amine catalysts non-exclusively include N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine, dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethyl-ethanolamine, N,N,N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether, tetramethyliminobispropylamine, 2-[[2-[2-(dimethylamino)ethoxy]ethyl]methylamino]ethanol, pentamethyldiethylenetriamine, 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, tetramethyliminobispropylamine, trimethyl-n',2-hydroxyethyl-propylenediamine, bis-(3-aminopropyl)-methylamine, N,N-dimethyl-1,3-propanediamine, 1-(dimethylamino)hexadecane, benzyldimethylamine, 3-dimethylaminopropylurea, dicyclohexylmethylamine; ethyldiisopropylamine; dimethylisopropylamine; methylisopropylbenzylamine; methylcyclopentylbenzylamine; isopropyl-sec-butyl-trifluoroethylamine; diethyl-(α-phenylethyl)amine, tri-n-propylamine, or a combination thereof. Useful secondary amine catalysts non-exclusively include, for example, dicyclohexylamine; t-butylisobutylamine; di-t-butylamine; cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine; di-(α-trifluoromethylethyl)amine; di-(α-phenylethyl)amine; or combinations thereof.

[0075] Other useful amines include morpholine, imidazole, and ether-containing compounds. These include: Dimorpholinodiethyl ether N-Ethylmorpholine N-Methylmorpholine Bis(dimethylaminoethyl) ether Imidizole n-Methylimidazole 1,2-Dimethylimidazole Dimorpholinodimethylether 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 is an example.

[0076] Suitable non-amine catalysts may include organometallic compounds containing bismuth, lead, tin, titanium, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, sodium, potassium, lithium, magnesium, barium, calcium, hafnium, lanthanum, niobium, tantalum, tellurium, tungsten, cesium, or combinations thereof. Preferably, the non-amine catalyst includes an organometallic compound containing bismuth, lead, tin, zinc, sodium, potassium, or combinations thereof.

[0077] Non-amine catalysts include bismuth 2-ethylhexonate, lead 2-ethylhexonate, 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 diisooctylmaleate, 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.

[0078] A trimerization catalyst may be used to convert the blend together with excess isocyanate to a polyisocyanurate-polyurethane foam. The trimerization catalyst used may be any catalyst known to those skilled in the art, including, but not limited to, glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates, and alkali metal carboxylates, as well as mixtures of various types of catalysts. Trimerization catalysts are potassium acetate, potassium octanoate, and N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

[0079] Flame retardants Flame retardants are added to foam insulation boards to inhibit or slow the spread of fire by suppressing the chemical reaction of the flame or by forming a protective char layer on the surface of the material. Generally, the flame retardant is added to the polyol premix or foamable composition as a liquid or solid. Alternatively, the flame retardant may be added with the isocyanurate or as a separate stream before forming the foam. Generally, the flame retardant may be mineral-based, organohalogen, or organophosphorus. Conventional flame retardants used in foam insulation boards include tris(2-chloroethyl)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, tri(1,3-dichloropropyl)phosphate, and tetrakis-(2-chloroethyl)ethylene diphosphate, triethyl phosphate, ammonium phosphate, various halogenated aromatic compounds, aluminum trihydrate, diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol 6), and melamine.

[0080] For the purposes of the present invention, the phosphate-based flame retardant is preferably selected from the group consisting of tris(2-chloroethyl)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, tri(1,3-dichloroisopropyl)phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol 6), 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 (Fyrol 6).

[0081] The amount of phosphate flame retardant in the polyol premix composition is preferably 25 phpp or less, preferably 20 phpp or less, preferably 15 pphp or less, preferably 10 pphp or less, preferably 5 pphp or less. Preferably, the foamable composition does not contain a phosphate flame retardant.

[0082] The flame retardant can be blended with the polyol and thus provided in a polyol premix composition with the polyol or mixture of polyols prior to the formation of the foamable composition. Alternatively, the flame retardant can be added as a separate stream during the formation of the foamable composition. For purposes of the present invention, the amount of phosphate-based flame retardant includes the amount of all phosphate-based flame retardants, i.e., the amount of phosphate-based flame retardants present in the polyol premix composition or added as a separate stream during the formation of the foamable composition.

[0083] others The polyol premix composition may also include other ingredients such as dyes, fillers, pigments, etc. Dispersants and cell stabilizers may be used. Conventional fillers for use herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fiber, carbon black, and silica. Fillers, when used, are typically present in an amount ranging from about 5 parts to 100 parts per 100 parts polyol by weight. Pigments that may be used herein may be any conventional pigment, such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, iron blue sienna, molybdenum orange, as well as organic pigments, such as para red, benzidine yellow, toluidine red, toner, and phthalocyanine.

[0084] Foaming Method The preparation of polyurethane and / or polyisocyanurate foams using blowing agent, polyol, optional other components, and isocyanate can follow any method known in the art for foam formation, see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and Technology, 1962, John Wiley and Sons, New York, NY, or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, NY, or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, OH. In general, polyurethane and / or polyisocyanurate foams are prepared by combining, among other things, isocyanate and polyol premix compositions. The foam produced is preferably a closed-cell foam, which can be rigid or semi-rigid. Preferably, the foam produced is a rigid foam.

[0085] For the purposes of the present invention, the isocyanate may be provided in combination with other components, such as certain silicone surfactants. The isocyanate may be combined with a blowing agent, but it is assumed herein that the blowing agent comprises 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.

[0086] Polyurethane foams, polyisocyanurate foams or mixtures thereof are prepared by combining isocyanates and polyol premix compositions by hand mixing for small batch preparations, preferably by continuous or discontinuous production techniques to form boards, blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, scum, etc. Optionally, other ingredients such as colorants, auxiliary blowing agents, water, catalysts, and even other polyols may be added as streams to the mix head or reaction site. Most conveniently, however, they are all incorporated into the polyol premix as described above.

[0087] For purposes of this invention, the polyurethane foam, polyisocyanurate foam, or mixtures thereof may be produced as continuous or discontinuous pour-in-place panels, boards, or spray applied foams.

[0088] Specifically, when the foam is provided as a board or panel, the foamable mixture can be poured between two decorative surfaces of the panel and the foam allowed to rise to produce a "foam sandwich" that is cut to the desired length. The decorative surfaces of the panel can be aluminum foil, roofing paper, metal, wood, etc. The resulting board or panel can then be applied to the exterior of an existing structure or used to form the exterior of a structure. These panels can be manufactured by a continuous process, or by a discontinuous process, or by a combination thereof.

[0089] use Among many applications, the foams of the present invention may be used to insulate buildings (e.g., the exterior of a building) or any structure where energy management and / or insulation from temperature fluctuations outside thereof is desirable, including, but not limited to, homes, office buildings, or other structures residential, commercial, industrial, agricultural, or otherwise where energy efficiency and insulation may be desirable, made from clay, wood, stone, metal, plastic, concrete, etc.

[0090] Thus, an aspect of the invention relates to a board foam, foam core panel, or spray foam produced by the method of the first aspect of the invention.

[0091] Experimental procedure Polyol Blends: Blends were prepared by mixing materials based on the following formulation:

[0092] Foaming: Foams were made by hand mixing based on the formula listed below: A mould (30cm x 30cm x 10cm) was used.

[0093] Lambda values: Lambda values ​​were recorded using a Laser Comp FOX50 with a sample size of 20cm x 20cm x 2cm.

[0094] For the examples herein, the four polyols tested are designated Polyol A, Polyol B, Polyol C, Polyol D, and Polyol E. These polyols have the following properties:

[0095] [Table 2] ND - Not tested

[0096] Example #1 - 1233zd(E) Solubility in Polyols The five polyols identified above were tested for their ability to solvate 1233zd(E) at various concentrations including one or more of 10, 15, and 20 parts by weight per 100 parts polyol (pphp). Testing was performed by forming a mixture containing the specified amount of 1233zd(E) blowing agent and the balance polyol in a calibrated miscible tube. After the mixture was thoroughly mixed at room temperature, the tube was placed in a room temperature thermostat for approximately 24 hours. If only a single phase was observed after this period, it indicates that the solubility limit of the blowing agent is greater than the amount tested. If two phases are clearly observed, it indicates that the solubility limit of the blowing agent is less than the amount tested. The results are shown in the table below:

[0097] [Table 3] * -FS indicates complete solvation, TPF indicates that two phases were formed, and NSL means that a single phase cloudy mixture was observed, indicating that the concentration is at or essentially at the solubility limit for purposes of the present invention.

[0098] Testing showed that Polyol A fully solvated 15 pphp of 1233zd(E) and therefore had a 1233zd(E) solubility limit greater than 15 pphp and likely greater than 20 pphp, while for Polyol B, Polyol C, and Polyol D, the solubility limit was reached at or below 20 pphp, and especially below 15 pphp for Polyols B and C. For Polyol D, 1233zd(E) was fully solvated at all concentrations tested, so the solubility limit for this polyol is greater than 20 pphp.

[0099] Comparative Examples 1-2: MUD for High Solubility Polyols in PIR Foams A series of foams were prepared using two high solubility polyols (Polyol A and Polyol D) as the polyol component of the foamable composition, as described in Table C1 below.

[0100] [Table 4]

[0101] Five foamable compositions were made according to Table C1 above using combinations of 1233zd(E) and 1233ad(E) with cyclopentane in the amounts specified in Table C1B below.

[0102] [Table 5]

[0103] For each of the foamable compositions ExC1A-ExC2F, foams were produced by hand mixing the polyol premix at a temperature of 50-62.5° F. with MDI at approximately 71.5° F. in either a 12″×12″×5″ open mold or a 14″×14″×4″ open mold.

[0104] The reactivity of each foam and the properties of the foams thus produced are reported in Tables C1C1 and C1C2 below:

[0105] [Table 6]

[0106] [Table 7]

[0107] The Dim-Vac test, which measures the dimensional stability of foam samples over time when exposed to vacuum and aging conditions, was determined using the following procedure. Six samples of each foam were cut to dimensions of 4'' x 4'' x 1'', with three samples used for the test condition designated "hot" and three samples used for the test condition designated "cold". The edges of the samples should be smooth, uniform, and crack-free. The samples should not have layers. The samples were conditioned to constant mass in an environment of 23±2°C and 50±10% relative humidity before being exposed to vacuum and the specified aging conditions. After the foams were made, conditioned for the appropriate time, and the samples were cut, each sample was placed in an appropriate apparatus to accurately measure the sample dimensions before performing the test condition parameters. The three test conditions used were as follows:

[0108] [Table 8]

[0109] The vacuum oven process was equilibrated to the conditions specified above at 7 millitorr absolute pressure. After 48 hours + / - 1 hour at 70°C and 7 millitorr vacuum, the vacuum and heat are stopped and the samples are removed and then tested at room temperature and pressure for weight and dimensional conditions using the same procedures used before conditioning in the oven. For the "cold" test, three of the samples are then placed in a freezer maintained at the temperature specified in the table above for 24 hours. For the "hot" test, three of the samples are then placed in an oven maintained at the temperature and humidity specified in the table above for 24 hours. All six samples are then removed from their respective chambers and allowed to equilibrate for two hours, and the weights and dimensions are measured again. The following calculations are then used to determine the volume change:

[0110]

number

[0111] The initial volume is calculated using the following formula: V i =L i ×W i ×H i (In the formula, L i = Initial length W i = initial width H i = initial average height)

[0112] The conditioned volume is calculated using the following formula: V f =L f ×W f ×H f (In the formula, L f = Length after conditioning W f = Width after conditioning H f = average height after conditioning)

[0113] The Dim-Vac (low temperature) results determined by this technique are shown in Figures 1, 2A, and 2B herein, respectively.

[0114] As can be seen from the data above, and as shown in Figures 1, 2A, and 2B, using polyols with 1233zd(E) solubility greater than 20 pphp to make PIR foams can produce foams with good thermal insulation properties, but with a minimum usable density of about 27.5 kg / m 3 and similar results are obtained when the blowing agent comprises a 50:50 molar ratio of 1233zd(E) and cyclopentane. These are undesirable results for many applications. In comparison, when a mixture of cyclopentane and isopentane is used in this formulation, the MUD is approximately 25 kg / m 3This difference precludes the use of the more environmentally friendly and non-flammable 1233zd(E) as a blowing agent in such applications and / or creates an undesirable weight or cost penalty if 1233zd(E) is used in such applications.

[0115] Examples 1-4: Foams made with polyols having low 1233zd(E) solubility in the polyol The materials and procedures described in Comparative Example 1 were repeated, except that the low solubility polyols Polyol B, Polyol C, and Polyol E were used instead of the high solubility polyols in the Comparative Example, and as shown in Tables E1 / 2 and E3 / 4 below. 1 The results for Polyol B and Polyol C are provided below in Table E1 / 2, and the results for Polyol E are provided in Table E2 / 3. 1 In order to make the reactivity of the foaming procedure comparable to the results of Comparative Example 1, the catalyst and MDI were changed.

[0116] [Table 9] NC - No change

[0117] [Table 10] * Considered acceptable but not quantified

[0118] The Dim-Vac results for Examples 1-4 are shown in Figures 3-5B herein. In this regard, it should be noted that a 50:50 molar blend of 1233zd(E) and cyclopentane is the same as a 70:30 weight blend, and thus the results for Comparative Examples ExC2D, ExC2F use the same blowing agent as Examples Ex4A-Ex4C.

[0119] As can be seen from the data reported above, and as shown in the figures herein, the selection of a polyol component having a 1233zd(E) solubility of about 20 pphp or less results in a dramatic and unexpected improvement in the key foam property of minimum usable density (MUD) when the blowing agent includes 1233zd(E). For example, low solubility polyols A and D have a MUD of about 27.5, as shown in Figures 3 and 4, while polyols B and C have MUDs of approximately 25 and about 25.5, respectively. This is a surprising and highly advantageous result. The results for polyol E, which includes 1233zd(E), are even more dramatically unexpected. In particular, as shown in Figure 5A, the foam has a volume change that has not begun to decrease even at the lowest tested density of 24.5, thus establishing that the MUD of the foam is less than 24.5.

[0120] Example 5 - Foams made with polyols having low 1233zd(E) solubility in the polyol and blowing agents containing 1233zd(E) and cyclopentane The materials and procedures described in Example 1 were repeated for Polyol B, except that the physical blowing agent tested included a blend of 1233zd(E) and cyclopentane. Additionally, foams were made using the same procedures using 100% 1233zd(E) as the physical blowing agent, and for comparison, a blend of cyclopentane and isopentane was also tested. The results are reported in Table E5 below. 2 : 2 In order to make the reactivity of the foaming procedure comparable to the results of Comparative Example 1, the catalyst and MDI were changed.

[0121] [Table 11] NC - No change

[0122] For convenience, these results are presented in the graph of FIG.

[0123] As can be seen from the results reported in this example, delta lambda is unexpectedly low when the physical blowing agent comprises more than about 60 wt% 1233zd(E) and less than about 40 wt% cyclopentane. Specifically, applicants have found that using about a 60 / 40 blend of 1233zd(E) / cyclopentane results in less than a 5% relative improvement in delta lambda, but increasing the relative amount to above about 60% results in a dramatically larger and unexpected improvement in delta lambda. Furthermore, this improvement levels off at amounts of 1233zd(E) greater than about 70% of 1233zd(E). Thus, the preferred blowing agent blends of the present invention, particularly those including blowing agents 5 and 6, can realize unexpected advantages in both performance and cost.

Claims

1. 1. A method for producing a thermoset PU and / or PIR foam comprising the steps of: (a) a polyol premix composition comprising a blowing agent comprising at least about 50% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)); and a foam produced from said premix having a foam viscosity of 27 kg / m ３ and one or more polyol components, which together have a solubility limit of said 1233zd(E) sufficiently low to enable said 1233zd(E) to have a minimum usable density ("MUD") less than 0.01; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a pressure of 27 kg / m ３ producing a foam having a MUD of less than A method comprising:

2. The method of claim 1 , wherein the one or more polyols comprise at least about 50% by weight of a polyester polyol.

3. The method of claim 1 , wherein the one or more polyols comprise at least about 75% by weight of a polyester polyol.

4. The foam has a viscosity of 25 kg / m ３ The method of claim 1 , having a MUD of less than 100 μm.

5. 1. A method for producing a thermoset PU and / or PIR foam having good thermal insulation properties and low minimum usable density (MUD), comprising the steps of: (a) providing a polyol premix composition comprising one or more polyols and a blowing agent comprising trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), wherein the one or more polyols comprise at least about 50 wt. % of a polyol having a 1233zd(E) solubility of about 20 pphp or less; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a pressure of 27 kg / m ３ producing a foam having a minimum usable density ("MUD") less than A method comprising:

6. 6. The method of claim 5, wherein the one or more polyols comprise at least about 75 wt.% of a polyol having a 1233zd(E) solubility of less than about 15 pphp.

7. 1. A thermosetting PU and / or PIR foam having good thermal insulation properties and low minimum density, (a) cell walls formed of PU and / or PIR forming a plurality of closed cells; (b) 1233zd(E) contained within the cell walls; and Including, 27kg / m ３ a MUD of less than about 1.5, an initial K-factor of less than about 18 mW / mK, and a delta lambda of less than 6.

8. 8. The foam of claim 7 which is a PU foam or a PIR foam.

9. 8. A board or slab or poured-in-place panel or building structure comprising the foam of claim 7.

10. 1. A method for producing a thermoset PU and / or PIR foam comprising the steps of: (a) a polyol premix composition comprising a blowing agent comprising at least about 50% by weight of trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)); and a foam produced from said premix having a foam viscosity of 27 kg / m ３ and one or more polyol components, which together have a solubility limit of said blowing agent low enough to enable said blowing agent to have a MUD of less than 0.05; (b) combining the polyol premix composition with a polyisocyanate to form a foamable composition; (c) The foamable composition is foamed to a pressure of 27 kg / m ３ producing a foam having a MUD of less than A method comprising:

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