Method for forming a polyol premix, foaming composition and foam formed therefrom

Abstract

To provide a polyol premix having improved resistance to frothing.SOLUTION: A polyol premix comprises: one or more polyols; and a blowing agent, comprising a significant proportion of transHFCO-1233zd or cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm) as a main blowing agent, and a physical co-blowing agent in an effective amount to reduce the de-frothing time to achieve a substantially froth-free state.SELECTED DRAWING: None

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of priority of U.S. Provisional Application No. 62 / 560,596, filed Sep. 19, 2017, and U.S. Provisional Application No. 62 / 563,393, filed Sep. 26, 2017, each of which is incorporated herein by reference.

[0002] (Field of the Invention) The present invention relates to a method for forming a polyol premix, a method for forming a foamable composition and a foam, and a foamable composition and a foam formed therefrom.

Background Art

[0003] Polyurethane (PU) and polyisocyanurate (PIR) foams generally have many wide - ranging applications and can be formed from a wide variety of materials suitable for this purpose. For example, one such application is to provide insulation.

[0004] Polyurethane foams are 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 polyisocyanurate foams, the foam is formed by reacting the polyisocyanate itself to form a cyclic trimer structure. In practice, foams generally described as polyisocyanurates contain both polyurethane and polyisocyanurate structures, and foams described as polyurethanes often incorporate some polyisocyanurate structures. Thus, this application relates to polyurethane foams, polyisocyanurate foams, and mixtures thereof. For convenience, the notation "PU / PIR" is intended to indicate a material suitable for forming PU foams, PIR foams, and any foam combining PU and PIR foam structures.

[0005] In most manufacturing processes of PU / PIR foams, a cellular structure is imparted by incorporating a chemical blowing agent and / or a physical blowing agent into the foamable formulation. Chemical blowing agents react under the conditions of the curing reaction to produce gas. One of the most commonly used chemical blowing agents is water, which reacts with isocyanate groups to form urea bonds that extend the polymer chains, and carbon dioxide gas is produced as a byproduct of this reaction, which then acts as a blowing agent. Physical blowing agents are low-boiling liquids that volatilize under curing conditions to form a blowing gas. Various types of hydrocarbons, fluorocarbons, hydrofluorocarbons, and other halogenated compounds are used as physical blowing agents.

[0006] As is known to those skilled in the art, in many applications, it is desirable and convenient to provide the components for forming the PU / PIR foam in a pre-blended formulation. Typically, the foam formulation is pre-blended into two separate mixtures or blends. The polyisocyanate and any isocyanate-compatible raw materials are included in a first mixture or blend, generally referred to as the "A" side or blend. A second separate blend, generally referred to as the "B" side, is also formed, and this blend includes a polyol or a mixture of polyols that react with the polyisocyanate in the A side. It is often desirable to include in the B side one or more of a surfactant, a catalyst, a blowing agent, and other isocyanate-reactive and non-reactive components. In practice, the components of the A side and the B side are prepared and packaged in separate containers, usually drums, etc., and can then be stored and / or transported to the intended place of use. At the time of foam formation, the drum or other container of the B side is opened or tapped, and then the contents are removed and combined with the A side under conditions known in the art suitable for initiating the foaming reaction. Since the B side is blended at a point prior to the intended use, it is sometimes referred to in the industry as a polyol premix. and can then be stored and / or transported to the intended place of use. At the time of foam formation, the drum or other container of the B side is opened or tapped, and then the contents are removed and combined with the A side under conditions known in the art suitable for initiating the foaming reaction. Since the B side is blended at a point prior to the intended use, it is sometimes referred to in the industry as a polyol premix.

[0007] During both the formation of the polyol premix and the opening or tapping of the drum or container, stirring of the polyol and the blowing agent occurs, and / or the temperature relatively increases when the drum or container is opened or tapped, which is common and possible. The applicants have come to understand that one of the difficulties that can occur with some combinations of polyols and certain blowing agents is the problem of foaming. This problem can manifest in one or more different ways. For example, this problem may unnecessarily increase the time required to produce a homogeneous and stable premix that can be packaged and stored for later use. This problem can also manifest when the stored polyol premix is opened or tapped. In such cases, the drum or container in which the polyol was stored may be subjected to a level of stirring that generates undesirable foaming, and / or the temperature relatively increases when the drum or container is opened or tapped, and then either a defective foam will be formed or a very disadvantageous delay will be added before use to terminate the foaming. Another drawback of such possible foaming is that the polyol premix can flow out of the container into the environment due to foaming, which may potentially cause the outflow of expensive and potentially dangerous chemicals in the use area.

[0008] As used herein, the term "foaming" generally refers to the formation of a layer or region of a polyol premix on a surface where bubbles are formed by a blowing agent flowing out of the liquid polyol of the polyol premix. This foaming is generally a dynamic phenomenon that tends to dissipate and cease in most cases over time. As described above, foaming can occur during the formation process of the polyol premix and can also occur as part of the process of bringing the polyol premix together with side A during use or immediately prior thereto. Foaming in both of these contexts is generally considered disadvantageous because formulators and / or users need to include defoaming time in the process. Further, foaming can be disadvantageous as it makes it difficult to obtain proper flow of the dispensed polyol premix and can degrade the quality of the foam if foaming is present when sides A and B are brought together.

[0009] Potential difficulties associated with foaming are recognized, for example, in U.S. Patent No. 9,228,071. This '071 patent discloses the use of several blowing agents included in a pre-blended side B cylinder. This patent describes the degree of foaming associated with several blowing agents tested in Example 5. Although there is no disclosure of a method for testing or measuring foaming, this patent shows that for two blowing agents mainly containing (by weight) HFO-1233zd, the "degree of foaming" is "none" when combined with a specific combination of polyols. It is shown that the other blowing agents tested had either a "high" or "very high" degree of foaming when using the same combination of polyols.

[0010] As will be described in detail below, Applicants have come to understand that, notwithstanding the disclosure of Patent No. 9,228,071, the foaming problem associated with the use of blowing agents containing a high concentration of HFCO-1233zd can be particularly severe and disadvantageous and / or unacceptable when such blowing agents are used with a particular type of polyol, especially when the polyol contains a particular type of polyol. SUMMARY OF THE INVENTION

[0011] Without the present invention, the Applicants have found that there are foaming problems associated with the formation and / or use of polyol premixes containing blowing agents using trans-HFCO-1233zd and blowing agents using cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm), and if these foaming problems are left unresolved, it may be possible to determine the economic viability of such polyol premixes for many applications. The present invention provides a polyol premix having unexpectedly and significantly improved foam resistance, and in a preferred embodiment,

[0012] (a) one or more polyols, preferably polyester polyols, and (b) a blowing agent containing at least about 50% by weight of trans-HFCO-1233zd, and (c) an antifoaming component, comprising (1) a physically co-blowing agent having antifoaming properties selected from the group consisting of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm), methylal, methyl formate, glycerin, trans-dichloroethylene (tDCE), and mixtures of two or more thereof, or (2) a surfactant having antifoaming properties, preferably a surfactant combined with a glycol ether, or (3) any combination of (1) and (2), wherein the amount of the aforementioned antifoaming component is effective to shorten the defoaming time of the polyol premix, and is preferably at least about 30%, more preferably at least about 50%, and even more preferably at least about 80% shorter compared to the defoaming time of the same polyol premix without the antifoaming component.

[0013] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, and (b) A blowing agent containing at least about 50% by weight of trans HFCO-1233zd, and (c) An antifoaming component containing, consisting essentially of, or consisting of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm), and The amount of the aforementioned antifoaming component is effective to reduce the antifoaming time of the polyol premix by at least about 30%.

[0014] As used herein, references to a reduction in foaming in terms of percentage amounts refer to the relative proportion in the antifoaming time of the same polyol premix without the antifoaming component.

[0015] The term "blowing agent 1", as used herein, refers to each of a blowing agent containing at least about 50% by weight of trans HFCO-1233zd and an antifoaming component containing, consisting essentially of, or consisting of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm).

[0016] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) One or more polyester polyols, and (b) Blowing agent 1, and the amount of the aforementioned antifoaming component is effective to reduce the antifoaming time of the polyol premix by at least about 50%.

[0017] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) One or more polyester polyols, and (b) Blowing agent 1, and the amount of the aforementioned antifoaming component is effective to reduce the antifoaming time of the polyol premix by at least about 80%.

[0018] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) One or more polyester polyols, and (b) a blowing agent comprising at least about 50 wt% trans - HFCO - 1233zd, and (c) an anti - foaming component comprising, consisting essentially of, or consisting of methylal, wherein the amount of the foregoing anti - foaming component is effective to reduce the defoaming time of the polyol premix by at least about 30%.

[0019] The term "blowing agent 2", as used herein, refers to each of a blowing agent comprising at least about 50 wt% trans - HFCO - 1233zd, and an anti - foaming component comprising, consisting essentially of, or consisting of methylal.

[0020] The present invention provides a polyol premix having significantly improved anti - foaming properties. In a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 2, wherein the amount of the foregoing anti - foaming component is effective to reduce the defoaming time of the polyol premix by at least about 50%.

[0021] The present invention provides a polyol premix having significantly improved anti - foaming properties. In a preferred embodiment, (a) one or more polyester polyols, and (b) a blowing agent comprising at least about 50 wt% trans - HFCO - 1233zd, and (c) an anti - foaming component comprising, consisting essentially of, or consisting of methyl formate, wherein the amount of the foregoing anti - foaming component is effective to reduce the defoaming time of the polyol premix by at least about 30%.

[0022] The term "blowing agent 3", as used herein, refers to each of a blowing agent comprising at least about 50 wt% trans - HFCO - 1233zd, and an anti - foaming component comprising, consisting essentially of, or consisting of methyl formate.

[0023] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 3, wherein the amount of the defoaming component described above is effective to shorten the defoaming time of the polyol premix by at least about 50%.

[0024] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 3, wherein the amount of the defoaming component described above is effective to shorten the defoaming time of the polyol premix by at least about 80%.

[0025] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) a blowing agent containing at least about 50 wt% of trans-HFCO-1233zd, and (c) a defoaming component containing glycerin, consisting essentially of, or consisting of glycerin, wherein the amount of the defoaming component described above is effective to shorten the defoaming time of the polyol premix by at least about 30%.

[0026] The term "blowing agent 4" as used herein refers to each of a blowing agent containing at least about 50 wt% of trans-HFCO-1233zd and a defoaming component containing glycerin, consisting essentially of, or consisting of glycerin.

[0027] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 4, wherein the amount of the defoaming component described above is effective to shorten the defoaming time of the polyol premix by at least about 50%.

[0028] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) a blowing agent 4, wherein the amount of the defoaming component described above is effective to reduce the defoaming time of the polyol premix by at least about 80%.

[0029] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) a blowing agent containing at least about 50% by weight of trans-HFCO-1233zd, and (c) a defoaming component containing, consisting essentially of, or consisting of glycerin, wherein the amount of the defoaming component described above is effective to reduce the defoaming time of the polyol premix by at least about 30%.

[0030] The term "blowing agent 4", as used herein, refers to each of a blowing agent containing at least about 50% by weight of trans-HFCO-1233zd and a defoaming component containing, consisting essentially of, or consisting of glycerin.

[0031] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) a blowing agent 4, wherein the amount of the defoaming component described above is effective to reduce the defoaming time of the polyol premix by at least about 50%.

[0032] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) a blowing agent 4, wherein the amount of the defoaming component described above is effective to reduce the defoaming time of the polyol premix by at least about 80%.

[0033] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, (b) a blowing agent comprising at least about 50 wt% of trans-HFCO-1233zd, and (c) an anti-foaming component comprising, consisting essentially of, or consisting of trans-dichloroethylene (tDCE), wherein the amount of the anti-foaming component is effective to reduce the anti-foaming time of the polyol premix by at least about 30%.

[0034] The term "blowing agent 5", as used herein, refers to each of a blowing agent comprising at least about 50 wt% of trans-H FCO-1233zd and an anti-foaming component comprising, consisting essentially of, or consisting of trans-dichloroethylene (tDCE).

[0035] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 5, wherein the amount of the anti-foaming component is effective to reduce the anti-foaming time of the polyol premix by at least about 50%.

[0036] The present invention provides a polyol premix having significantly improved anti-foaming properties, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 5, wherein the amount of the anti-foaming component is effective to reduce the anti-foaming time of the polyol premix by at least about 80%.

[0037] The term "blowing agent 6", as used herein, refers to each of a blowing agent comprising at least about 20 wt% of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm) and an anti-foaming component comprising, consisting essentially of, or consisting of trans-HFCO-1233zd.

[0038] The present invention provides a polyol premix having significantly improved anti-foaming properties. In a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 6, wherein the amount of the aforementioned defoaming component is effective to reduce the defoaming time of the polyol premix by at least about 50%.

[0039] The present invention provides a polyol premix having significantly improved anti-foaming properties. In a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 6, wherein the amount of the aforementioned defoaming component is effective to reduce the defoaming time of the polyol premix by at least about 80%.

[0040] The present invention provides a polyol premix having unexpectedly and significantly improved anti-foaming properties. In a preferred embodiment, (a) one or more polyols, preferably polyester polyols, and (b) a blowing agent containing at least about 50% by weight of trans-HFCO-1233zd, and (c) a surfactant having defoaming properties, preferably a surfactant combined with a glycol ether, wherein the amount of the aforementioned surfactant is effective to shorten the defoaming time of the polyol premix, and is preferably effective to shorten it by at least about 30%, more preferably at least about 50%, and even more preferably at least about 80% compared to the defoaming time of the same polyol premix without the defoaming component.

[0041] The defoaming time, as used herein, means the time to defoam a combination of a polyol and a blowing agent, measured according to the examples herein.

[0042] In a preferred embodiment, the present invention provides a polyol premix having unexpectedly and significantly improved anti-foaming properties. (a) One or more polyols, preferably polyester polyols, and (b) A blowing agent comprising at least about 50 wt% trans - HFCO - 1233zd, and (c) An anti - foaming component comprising a physical co - blowing agent having anti - foaming properties selected from the group consisting of cis - 1,1,1,4,4,4 - hexafluoro - 2 - butene (HFO - 1336mzzm(Z) or cis - 1336mzzm), methylal, methyl formate, glycerin, trans - dichloroethylene (tDCE), and mixtures of two or more thereof, and optionally, a silicone surfactant in combination with an anti - foaming surfactant, preferably a glycol ether, The amount of the aforementioned anti - foaming component is effective to provide a polyol premix with an anti - foaming time of about 30 minutes or less, more preferably about 20 minutes or less, even more preferably about 15 minutes or less, and most preferably 10 minutes or less of the polyol premix, and the aforementioned anti - foaming time is measured as described in the examples herein.

[0043] As used herein, the anti - foaming time means the time to defoam a combination of a polyol and a blowing agent, measured according to the examples herein.

[0044] The present invention provides a polyol premix having significantly improved anti - foaming resistance. In a preferred embodiment, (a) One or more polyester polyols, and (b) A blowing agent 1, and the amount of the aforementioned anti - foaming component is Effective to provide a polyol premix with an anti - foaming time of about 40 minutes or less of the polyol premix.

[0045] As used herein, the anti - foaming time refers to the measured value described in the examples herein.

[0046] The present invention provides a polyol premix having significantly improved anti - foaming resistance. In a preferred embodiment, (a) One or more polyester polyols, and (b) It contains blowing agent 1, and the amount of the aforementioned defoaming component is effective to provide a defoaming time of the polyol premix of about 30 minutes or less for the polyol premix.

[0047] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 1, and the amount of the aforementioned defoaming component is effective to provide a defoaming time of the polyol premix of about 20 minutes or less for the polyol premix.

[0048] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 2, and the amount of the aforementioned defoaming component is effective to provide a defoaming time of the polyol premix of about 40 minutes or less for the polyol premix.

[0049] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 2, and the amount of the aforementioned defoaming component is effective to provide a defoaming time of the polyol premix of about 30 minutes or less for the polyol premix.

[0050] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, and (b) blowing agent 2, and the amount of the aforementioned defoaming component is effective to provide a defoaming time of the polyol premix of about 20 minutes or less for the polyol premix.

[0051] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) One or more polyester polyols, and (b) Foaming agent 3, and the amount of the defoaming component described above is effective for providing a defoaming time of the polyol premix of about 40 minutes or less for the polyol premix.

[0052] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) One or more polyester polyols, and (b) Foaming agent 3, and the amount of the defoaming component described above is effective for providing a defoaming time of the polyol premix of about 30 minutes or less for the polyol premix.

[0053] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) One or more polyester polyols, and (b) Foaming agent 3, and the amount of the defoaming component described above is effective for providing a defoaming time of the polyol premix of about 20 minutes or less for the polyol premix.

[0054] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) One or more polyester polyols, and (b) Foaming agent 4, and the amount of the defoaming component described above is effective for providing a defoaming time of the polyol premix of about 40 minutes or less for the polyol premix.

[0055] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) One or more polyester polyols, and (b) Foaming agent 4, and the amount of the defoaming component described above is effective for providing a defoaming time of the polyol premix of about 30 minutes or less for the polyol premix.

[0056] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, (b) a blowing agent 4, and the amount of the defoaming component described above is effective to provide a defoaming time of the polyol premix of about 20 minutes or less for the polyol premix.

[0057] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, (b) a blowing agent 5, and the amount of the defoaming component described above is effective to provide a defoaming time of the polyol premix of about 40 minutes or less for the polyol premix.

[0058] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, (b) a blowing agent 5, and the amount of the defoaming component described above is effective to provide a defoaming time of the polyol premix of about 30 minutes or less for the polyol premix.

[0059] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, (b) a blowing agent 5, and the amount of the defoaming component described above is effective to provide a defoaming time of the polyol premix of about 20 minutes or less for the polyol premix.

[0060] The present invention provides a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) one or more polyester polyols, (b) a blowing agent 6, and the amount of the defoaming component described above is effective to provide a defoaming time of the polyol premix of about 40 minutes or less for the polyol premix.

[0061] The present invention provides a polyol premix having significantly improved foam resistance. In a preferred embodiment, (a) one or more polyester polyols, and (b) a blowing agent 6, wherein the amount of the defoaming component described above is effective to provide a defoaming time of the polyol premix of about 30 minutes or less for the polyol premix.

[0062] The present invention provides a polyol premix having significantly improved foam resistance. In a preferred embodiment, (a) one or more polyester polyols, and (b) a blowing agent 6, wherein the amount of the defoaming component described above is effective to provide a defoaming time of the polyol premix of about 20 minutes or less for the polyol premix.

[0063] In a preferred embodiment, the present invention provides a polyol premix having unexpectedly and significantly improved foam resistance, (a) one or more polyols, preferably polyester polyols, and (b) a blowing agent containing at least about 50% by weight of trans-HFCO-1233zd or at least 20% by weight of HFO-1333mzzm(Z), and (c) a surfactant having defoaming properties, preferably a silicone surfactant combined with a glycol ether, wherein the amount of the defoaming component described above is effective to provide a defoaming time of the polyol premix of about 30 minutes or less, more preferably about 20 minutes or less, still more preferably about 15 minutes or less, and most preferably 10 minutes or less for the polyol premix, and the defoaming time described above is measured as described in the examples herein.

[0064] In embodiments where a surfactant is present, the surfactant is a silicone surfactant and is preferably present in combination with a glycol ether.

[0065] In embodiments where a surfactant is present, the surfactant is a non-silicone surfactant and is preferably present in combination with a glycol ether.

[0066] The present invention also provides an improved method for forming a polyol premix having unexpectedly and significantly improved anti-foaming properties. In preferred embodiments, (a) combining one or more polyols, preferably a polyester polyol, with a blowing agent, wherein the blowing agent described above comprises at least about 70% by weight, more preferably at least about 80% by weight of trans HFCO-1233zd, and cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm), methylal, methyl formate, glycerin, trans dichloroethylene (tDC E), and a physical co-blowing agent having anti-foaming properties selected from the group consisting of mixtures of two or more of these, and (b) forming a polyol premix that does not substantially foam from the above combination, wherein the amount of the co-blowing agent described above is such that the time from the completion of the above combination step to the formation of the polyol premix that does not substantially foam is about 30 minutes or less, more preferably about 20 minutes or less, more preferably about 10 minutes or less, more preferably about 5 minutes or less, and even more preferably about 1 minute or less. The process includes a step that is effective to ensure this.

[0067] The present invention also provides an improved method for forming a polyol premix having significantly improved anti-foaming properties. In preferred embodiments, (a) combining one or more polyols, preferably a polyester polyol, with a blowing agent, wherein the blowing agent described above comprises at least about 20% by weight, more preferably at least about 30% by weight of cis-1336mzzm, and a physical co-blowing agent having anti-foaming properties containing trans 1233zd, and (b) A step of forming a polyol premix that substantially does not cause foaming from the aforementioned combination, wherein the amount of the aforementioned co-foaming agent is such that the time from the completion of the aforementioned combination step to the formation of the aforementioned polyol premix that substantially does not cause foaming is about 30 minutes or less, more preferably about 20 minutes or less, more preferably about 10 minutes or less, more preferably about 5 minutes or less, and even more preferably about 1 minute or less, which is effective for ensuring this, and the step, are included.

[0068] The present invention also provides an improved method for forming a polyol premix having significantly improved foam resistance, and in a preferred embodiment, (a) A step of combining one or more polyester polyols and a foaming agent, wherein the aforementioned foaming agent includes at least about 20% by weight of cis-1336mzzm and a physical co-foaming agent having defoaming properties including trans 1233zd, and the step, (b) A step of forming a polyol premix that substantially does not cause foaming from the aforementioned combination, wherein the amount of the aforementioned co-foaming agent is effective for ensuring that the time from the completion of the aforementioned combination step to the formation of the aforementioned polyol premix that substantially does not cause foaming is about 30 minutes or less, and the step, are included. More preferably about 20 minutes or less, more preferably about 10 minutes or less, more preferably about 5 minutes or less, and even more preferably about 1 minute or less.

[0069] The present invention also provides an improved method for forming a foam, and in a preferred embodiment, (a) A step of opening and / or tapping a container containing a polyol premix comprising one or more polyols, preferably at least one polyester polyol, and a blowing agent, wherein the blowing agent is at least about 70% by weight, more preferably at least about 80% by weight of trans HFCO-1233zd, and a physically co-blowing agent having defoaming properties selected from the group consisting of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm), methylal, methyl formate, glycerin, trans-dichloroethylene (tDCE), and mixtures of two or more thereof, and the polyol premix substantially ceases to foam within about 30 minutes, more preferably within about 20 minutes, more preferably within about 10 minutes, more preferably within about 5 minutes, even more preferably within about 1 minute after the opening and / or tapping step, (b) A step of forming a foam from the polyol premix that substantially ceases to foam by combining the polyol premix that substantially ceases to foam with a thermosetting component.

[0070] The present invention also provides an improved method for forming a polyol premix having unexpectedly and significantly improved anti-foaming properties, and in a preferred embodiment, (a) A step of combining one or more polyols, preferably a polyester polyol, and a blowing agent, wherein the blowing agent is at least about 20% by weight, more preferably at least about 30% by weight of cis-1336mzzm, and a physically co-blowing agent having defoaming properties selected from the group consisting of trans 1233zd, methylal, methyl formate, glycerin, trans-dichloroethylene (tDCE), and mixtures of two or more thereof, with trans 1233zd being particularly preferred, (b) A step of forming a polyol premix that does not substantially cause foaming from the aforementioned combination, wherein the amount of the aforementioned co-foaming agent is such that the time from the completion of the aforementioned combination step to the formation of the aforementioned polyol premix that does not substantially cause foaming is about 30 minutes or less, more preferably about 20 minutes or less, more preferably about 10 minutes or less, more preferably about 5 minutes or less, and even more preferably about 1 minute or less, which is effective to ensure this, and the step is included.

[0071] As used herein, the term "polyol premix that does not substantially cause foaming" means a polyol premix that is determined not to substantially cause foaming according to the procedures described in the examples herein.

Mode for Carrying Out the Invention

[0072] Method One aspect of the present invention relates to an improved method for forming a polyol premix composition that is substantially non-foaming, and in particular, requires a substantially shorter time at initial formation and / or use than has been possible heretofore with the use of blowing agents that include a substantial proportion of trans-HFO-1233zd blowing agent or a substantial proportion of cis-1336mzzm blowing agent, to form a polyol premix composition that is substantially non-foaming. The method includes providing a mixture that includes a polyol, preferably a polyol that includes at least 50 weight percent polyol ester, and a blowing agent, where the polyol and the blowing agent composition are each selected in accordance with the teachings herein, and unexpectedly shortens the time required to reach a substantially non-foaming state. Applicants have unexpectedly found that foaming problems can occur in connection with the formation and / or use of certain polyol premixes, such that the degree of foaming upon mixing and / or upon opening and / or tapping of a container holding the polyol premix results in a highly undesirable foaming effect, thereby causing a delay in the formation time of a substantially non-foaming polyol premix and potentially other drawbacks described herein. Applicants have found that a careful selection of a co-blowing agent for use with the trans-HFCO-1233zd primary blowing agent can serve to dramatically shorten the time to achieve a substantially non-foaming state. Applicants have also found that a careful selection of a co-blowing agent for use with the cis-HFO-1336mzzm primary blowing agent can also serve to dramatically shorten the time to achieve a substantially non-foaming state.

[0073] The step of combining the polyol of the present invention with a blowing agent, and the step of opening and / or tapping a container containing the polyol premix of the present invention do not require any special technology, and any conventional known technology can be used to combine these two components with any optional component and / or to open and / or tap the container, which is advantageous. The forming step also generally requires only placing the container containing the combined components in a stationary state after the mixing step or after the opening / tapping step, i.e., preferably, not adding any substantial additional amount of kinetic energy to the container after the completion of the combining step and / or the opening / tapping step, which is very advantageous. As described above, the present invention preferably includes a careful selection of a blowing agent for use with a polyol, preferably a polyol containing a polyester polyol, and more preferably a polyol containing at least about 40% by weight of polyester polyol based on the total of the polyols, when preparing the polyol premix. Preferred blowing agents and polyols, as well as any additional components, are described below in this specification.

[0074] Blowing agent Trans HFCO-1233zd and cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z)) One preferred blowing agent composition, which is preferred for use with the method, the polyol premix of the present invention, and the foam, comprises from about 25 wt% to about 80 wt% trans HFO-1233zd and, in an amount effective to ensure that the time from the completion of the aforementioned combination step of the method and / or from the completion of the opening and / or tapping step of the method to the formation of the aforementioned substantially non-foaming polyol premix is about 30 minutes or less, more preferably about 20 minutes or less, even more preferably about 10 minutes or less, a co-blowing agent comprising at least HFO-1336mzzm(Z). Preferably, in such embodiments, HFO-1336mzzm(Z) is present in the blowing agent in an amount of about 20 wt% or more based on the total weight of the blowing agent components. Applicants have surprisingly found that use in amounts of less than about 20 wt% of HFO-1336mzzm(Z) is not effective in substantially shortening the defoaming time, and have surprisingly found that when HFO-1336mzzm(Z) is present in an amount of 20% to about 75%, a shortening of the defoaming time of at least about 30 relative percent can be achieved. Applicants have also surprisingly found that use in amounts of less than about 20 wt% of HFO-1336mzzm(Z) is not effective in shortening the defoaming time to about 30 minutes or less in the preferred embodiments, and have surprisingly found that when HFO-1336mzzm(Z) is present in an amount of 20% to about 75%, a defoaming time of about 30 minutes or less can be achieved.

[0075] In a preferred embodiment, the blowing agent comprises from about 50 wt% to about 80 wt% trans HFO-1233zd and from about 20 wt% to about 50 wt% HFO-1336mzzm(Z).

[0076] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of from about 50 wt% to about 80 wt% trans HFO-1233zd and from about 20 wt% to about 50 wt% HFO-1336mzzm(Z).

[0077] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of from about 50 wt% to about 80 wt% trans HFO-1233zd and from about 20 wt% to about 50 wt% HFO-1336mzzm(Z).

[0078] In a preferred embodiment, the blowing agent comprises from about 70 wt% to about 80 wt% trans HFO-1233zd and from about 20 wt% to about 30 wt% HFO-1336mzzm(Z).

[0079] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of from about 70 wt% to about 80 wt% trans HFO-1233zd and from about 20 wt% to about 30 wt% HFO-1336mzzm(Z).

[0080] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of from about 70 wt% to about 80 wt% trans HFO-1233zd and from about 20 wt% to about 30 wt% HFO-1336mzzm(Z).

[0081] Each of the blowing agents described in this section is useful according to any of the methods described herein.

[0082] Each of the blowing agents described in this section is useful for forming any of the premix compositions described herein.

[0083] Each of the blowing agents described in this section is useful for making any of the foams described herein.

[0084] trans HFCO-1233zd and methylal One preferred blowing agent composition, which is preferred for use by this method, the polyol premix of the present invention, and the foam, comprises at least about 70 wt% trans HFO-1233zd and, in an amount effective to ensure that the time from the completion of the aforementioned combination step of the method and / or from the completion of the opening and / or tapping step of the method to the formation of the aforementioned substantially non-foaming polyol premix is about 30 minutes or less, more preferably about 20 minutes or less, more preferably about 15 minutes or less, a co-blowing agent comprising at least dimethoxymethane (CH3-O-CH2-O-CH3, also known as methylal). Preferably, in such an embodiment, methylal is present in the blowing agent in an amount of at least about 0.5 wt% based on the total weight of the blowing agent components. Applicants have found that use in an amount of less than about 0.50 wt% of methylal is not effective in substantially shortening the defoaming time, and surprisingly, that when methylal is present in an amount of about 0.5% to about 3%, a shortening of at least about 50 relative percent of the defoaming time can be achieved. Further, applicants have also surprisingly found that use in an amount of more than 3% to about 25% of methylal has the effect of shortening the defoaming time, but this shortening is actually less than when the amount is about 0.5% to about 3%, preferably about 1%. Applicants have further surprisingly found that the greatest shortening of the defoaming time occurs with a blowing agent consisting essentially of, preferably consisting of, about 70 wt% trans HFO-1233zd and about 30 wt% methylal. In particular, in such a preferred embodiment, where the blowing agent consists essentially of, preferably consists of, about 70 wt% trans HFO-1233zd and about 30 wt% methylal, a shortening of at least about 75 relative percent, even more preferably about 85 relative percent of the defoaming time can be achieved, and / or a defoaming time of less than 20 minutes, more preferably less than about 15 minutes can be achieved.

[0085] In a preferred embodiment, the blowing agent comprises from about 70 wt% to about 99 wt% trans HFO-1233zd and from about 1 wt% to about 30 wt% methylal.

[0086] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of about 70 wt% to about 99 wt% of trans HFO-1233zd and about 1 wt% to about 30 wt% of methylal.

[0087] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 70 wt% to about 99 wt% of trans HFO-1233zd and about 1 wt% to about 30 wt% of methylal.

[0088] In a preferred embodiment, the blowing agent comprises about 97 wt% to about 99.5 wt% of trans HFO-1233zd and more than 0.5 wt% to less than 3 wt% of methylal.

[0089] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of about 97 wt% to about 99.5 wt% of trans HFO-1233zd and more than 0.5 wt% to less than 3 wt% of methylal.

[0090] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 97 wt% to about 99.5 wt% of trans HFO-1233zd and more than 0.5 wt% to less than 3 wt% of methylal.

[0091] In a preferred embodiment, the blowing agent comprises about 70 wt% of trans HFO-1233zd and about 30 wt% of methylal.

[0092] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of about 70 wt% of trans HFO-1233zd and about 30 wt% of methylal.

[0093] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 70 wt% of trans HFO-1233zd and about 30 wt% of methylal.

[0094] Each of the blowing agents described in this section is useful according to any of the methods described herein.

[0095] Each of the blowing agents described in this section is useful for forming any of the premix compositions described herein.

[0096] Each of the blowing agents described in this section is useful for making any of the foams described herein.

[0097] trans-HFCO-1233zd and methyl formate One preferred blowing agent composition according to the present invention is at least about 70 wt% trans-HFO-1233zd and an effective amount to ensure that the time from the completion of the foregoing combination step to the formation of the polyol premix that does not substantially foam as described above is about 30 minutes or less, more preferably about 20 minutes or less, and more preferably about 15 minutes or less, and a co-blowing agent comprising at least methyl formate (HCO2CH3). Preferably, in such an embodiment, methyl formate is present in the blowing agent in an amount of at least about 0.5 wt% based on the total weight of the blowing agent components. The applicants have surprisingly found that the use of an amount of less than about 0.50 wt% of methyl formate is not effective in substantially shortening the defoaming time, and surprisingly, when methyl formate is present in an amount of about 0.5% to about 2%, at least about 50 relative percent shortening of the defoaming time can be achieved. Further, the applicants have also surprisingly found that the use of an amount of more than 2% to about 25% of methyl formate has the effect of shortening the defoaming time, but this shortening is actually less than when the amount is about 0.5% to about 2%, preferably about 1%. The applicants have further surprisingly found that the greatest shortening of the defoaming time occurs with a blowing agent consisting essentially of, preferably consisting of, about 70 wt% trans-HFO-1233zd and about 30 wt% methyl formate. In particular, in such a preferred embodiment where the blowing agent consists essentially of, preferably consists of, about 70 wt% trans-HFO-1233zd and about 30 wt% methyl formate, at least about 75 relative percent, even more preferably about 85 relative percent shortening of the defoaming time can be achieved, and / or a defoaming time of less than 20 minutes, more preferably less than about 15 minutes can be achieved.

[0098] In a preferred embodiment, the blowing agent comprises from about 70% to about 99% by weight of trans-HFO-1233zd and from about 1% to about 30% by weight of methyl formate.

[0099] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of from about 70% to about 99% by weight of trans-HFO-1233zd and from about 1% to about 30% by weight of methyl formate.

[0100] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of from about 70% to about 99% by weight of trans-HFO-1233zd and from about 1% to about 30% by weight of methyl formate.

[0101] In a preferred embodiment, the blowing agent comprises from about 90% to about 97% by weight of trans-HFO-1233zd and more than 3% to less than 10% by weight of methyl formate.

[0102] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of from about 90% to about 97% by weight of trans-HFO-1233zd and more than 3% to less than 10% by weight of methyl formate.

[0103] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of from about 90% to about 97% by weight of trans-HFO-1233zd and more than 3% to less than 10% by weight of methyl formate.

[0104] In a preferred embodiment, the blowing agent comprises about 70% by weight of trans-HFO-1233zd and about 30% by weight of methyl formate.

[0105] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of about 70% by weight of trans-HFO-1233zd and about 30% by weight of methyl formate.

[0106] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 70% by weight of trans-HFO-1233zd and about 30% by weight of methyl formate.

[0107] In a preferred embodiment, the blowing agent comprises about 99% by weight of trans HFO-1233zd and about 1% by weight of methyl formate.

[0108] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of about 99% by weight of trans HFO-1233zd and about 1% by weight of methyl formate.

[0109] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 99% by weight of trans HFO-1233zd and about 1% by weight of methyl formate.

[0110] Each of the blowing agents described in this section is useful according to any of the methods described herein.

[0111] Each of the blowing agents described in this section is useful for forming any of the premix compositions described herein.

[0112] Each of the blowing agents described in this section is useful for making any of the foams described herein.

[0113] trans HFCO-1233zd and trans dichloroethylene One preferred blowing agent composition according to the present invention comprises at least about 70 wt% of trans HFO-1233zd and a co-blowing agent comprising at least trans-1,2-dichloroethylene (ClHC=CHCl) (also referred to herein as "tDCE") in an amount effective to ensure that the time from the completion of the foregoing combination step to the formation of the foregoing substantially non-foaming polyol premix is about 30 minutes or less, more preferably about 20 minutes or less, even more preferably about 15 minutes or less. Preferably, in such embodiments, tDCE is present in the blowing agent in an amount of at least about 2 wt% based on the total weight of the blowing agent components. Applicants have surprisingly found that use in amounts of about 1 wt% or less of tDCE is not effective in substantially shortening the defoaming time, and surprisingly, that when tDCE is present in amounts of about 2% to about 10%, at least about 30 relative percent shortening of the defoaming time can be achieved. Further, applicants have also surprisingly found that use in amounts greater than 2% to about 5% of tDCE has the effect of shortening the defoaming time, but this shortening is further improved in a blowing agent composition in which tDCE is present in an amount of about 10%. In particular, in such preferred embodiments, the blowing agent consists essentially of, and preferably consists of, about 90 wt% of trans HFO-1233zd and about 10 wt% of tDCE, and at least about 75 relative percent, even more preferably about 85 relative percent shortening of the defoaming time can be achieved, and / or a defoaming time of less than 20 minutes, more preferably less than about 15 minutes can be achieved.

[0114] In a preferred embodiment, the blowing agent comprises from about 90 wt% to about 97 wt% of trans HFO-1233zd and from about 3 wt% to about 10 wt% of tDCE.

[0115] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of from about 90 wt% to about 97 wt% of trans HFO-1233zd and from about 3 wt% to about 10 wt% of tDCE.

[0116] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 90 wt% to about 97 wt% of trans HFO-1233zd and about 3 wt% to about 10 wt% of tDCE.

[0117] In a preferred embodiment, the blowing agent comprises about 90 wt% to about 95 wt% of trans HFO-1233zd and more than 5 wt% to about 10 wt% of tDCE.

[0118] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of about 90 wt% to about 95 wt% of trans HFO-1233zd and more than 5 wt% to about 10 wt% of tDCE.

[0119] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 90 wt% to about 95 wt% of trans HFO-1233zd and more than 5 wt% to about 10 wt% of tDCE.

[0120] In a preferred embodiment, the blowing agent comprises about 90 wt% of trans HFO-1233zd and about 10 wt% of tDCE.

[0121] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of about 90 wt% of trans HFO-1233zd and about 10 wt% of tDCE.

[0122] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 90 wt% of trans HFO-1233zd and about 10 wt% of tDCE.

[0123] Each of the blowing agents described in this section is useful according to any of the methods described herein.

[0124] Each of the blowing agents described in this section is useful for forming any of the premix compositions described herein.

[0125] Each of the blowing agents described in this section is useful for making any of the foams described herein.

[0126] One preferred blowing agent composition, which is preferred for use by this method, the polyol premix of the present invention, and the foam, comprises from about 25 wt% to about 80 wt% of HFO-1336mzzm(Z) and, from the completion of the foregoing combining step of the method, and / or from the completion of the opening and / or tapping step of the method, in an amount effective to ensure that the time to the formation of the foregoing substantially non-foaming polyol premix is about 40 minutes or less, more preferably about 30 minutes or less, even more preferably about 20 minutes or less, a co-blowing agent comprising trans HFO-1233zd. Preferably, in such an embodiment, trans 1233zd is present in the blowing agent in an amount of about 25 wt% or more and about 75 wt% or less based on the total weight of the blowing agent components. Applicants have surprisingly found that use in amounts of less than about 25 wt% and more than 80 wt% of trans 1233zd is not effective to substantially shorten the defoaming time, and surprisingly, when trans 1233zd is present in an amount of from 25 wt% to about 80 wt%, a shortening of the defoaming time of at least about 20 relative percent, more preferably at least about 30 relative percent, can be achieved. Applicants have also surprisingly found that use in amounts of less than about 25 wt% of trans 1233zd is not effective to shorten the defoaming time to about 30 minutes or less in a preferred embodiment, and surprisingly, when HFO-1336mzzm(Z) is present in an amount of from 25 wt% to about 80 wt%, a substantial and unexpected shortening of the defoaming time can be achieved, preferably to a time of about 30 minutes or less. In a preferred embodiment, the blowing agent comprises from about 20 wt% to about 75 wt% of HFO-1336mzzm(Z) and from about 25 wt% to about 80 wt% of trans HFO-1233zd.

[0127] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of from about 20 wt% to about 75 wt% of HFO-1336mzzm(Z) and from about 25 wt% to about 80 wt% of trans HFO-1233zd.

[0128]

[0129] ​In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 20 wt% to about 75 wt% of HFO-1336mzzm(Z) and about 25 wt% to about 80 wt% of trans-HFO-1233zd.

[0130] In a preferred embodiment, the blowing agent comprises about 20 wt% to about 30 wt% of HFO-1336mzzm(Z) and about 70 wt% to about 80 wt% of trans-HFO-1233zd.

[0131] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting essentially of about 20 wt% to about 30 wt% of HFO-1336mzzm(Z) and about 70 wt% to about 80 wt% of trans-HFO-1233zd.

[0132] In a preferred embodiment, the blowing agent comprises a physical blowing agent consisting of about 20 wt% to about 30 wt% of HFO-1336mzzm(Z) and about 70 wt% to about 80 wt% of trans-HFO-1233zd.

[0133] Each of the blowing agents described in this section is useful according to any of the methods described herein.

[0134] Each of the blowing agents described in this section is useful for forming any of the premix compositions described herein.

[0135] Each of the blowing agents described in this section is useful for making any of the foams described herein.

[0136] Preferred amount of blowing agent in the polyol premix Regarding the amount of the blowing agent (trans-1,2,3,3,3-pentafluoropropene and an antifoaming co-blowing agent, or cis-1,3,3,3,6,6,6-heptafluoropropene and its antifoaming co-blowing agent) of the present invention used in the polyol premix composition of the present invention, this amount can vary greatly, and it is contemplated that the advantageous properties described herein with respect to the method, foam, and polyol premix can be achieved. In a preferred embodiment, the blowing agent is about 2 wt% to about 40 wt%, or about 2 wt% to about 30 wt%, or about 5 wt% to about 30 wt%, or about 10 wt% to about 30 wt%, or about 2 wt% to about 25 wt%, or about 5 wt% to about 25 wt% %, or about 10 wt% to about 25 wt% by weight, based on the total weight of the components in the premix composition, and can be present in the polyol premix.

[0137] Those skilled in the art will be able to select the amount of the blowing agent used for the type of foam to be produced based on the teachings contained herein. For example, flexible foams preferably use a relatively low concentration of the blowing agent according to any embodiment of the blowing agents disclosed herein, preferably in an amount of about 0.25 wt% to about 10 wt%, or 0.5 wt% to about 8 wt%, or about 0.5 wt% to about 6 wt%, or about 0.5 wt% to about 5 wt%, or 0.5 wt% to about 4 wt%. Spray foams preferably contain the blowing agent according to any embodiment of the blowing agents disclosed herein, preferably in an amount of about 4 wt% to about 25 wt%, or about 4 wt% to about 20 wt%, or about 4 wt% to about 15 wt%, or about 6 wt% to about 12 wt%. Foams for electrical appliances, PIR panel foams, and PUR panel foams preferably contain the blowing agent according to any embodiment of the blowing agents disclosed herein, preferably in an amount of about 5 wt% to about 30 wt%, or about 10 wt% to about 30 wt%, or about 15 wt% to about 30 wt%.

[0138] Polyol In connection with the polyol premix composition, the polyol can be present in the polyol premix in a wide range of amounts depending on the type of foam to be formed and other factors well known to those skilled in the art. Generally, the polyol component of the polyol premix preferably is present in an amount of about 50% to about 98% by weight, based on the total weight of the components in the polyol premix composition. In a preferred embodiment, the amount of polyol in the polyol premix composition is about 55% to about 98%, or about 60% to about 98%, or about 65% to about 98%, or about 70% to about 98%, or about 75% to about 98%, or about 80% to about 98%, or about 85% to about 98%, or about 90% to about 98%, or about 50% to about 95%, or about 50% to about 90%, or about 50% to about 85%, or about 60% to about 95%, or about 60% to about 90%, or about 60% to about 85%, or about 60% to about 80%, or about 65% to about 95%, or about 65% to about 90%, or about 65% to about 85%, or about 65% to about 80% of the polyol premix composition, based on the total weight of the components in the premix composition.

[0139] In connection with the polyol premix composition, the polyol component preferably contains at least about 40% by weight of polyester polyol, more preferably at least about 50% by weight of polyester polyol, even more preferably at least about 60% by weight of polyester polyol, based on all the polyols present.

[0140] The polyester polyol may include one or more polyester polyols. A wide variety of polyester polyols can be used. Suitable polyester polyols include, but are not limited to, aromatic polyester polyols, aromatic polyethylene terephthalate polyols, aromatic carboxylic acid anhydrides, linear poly(diethylene adipate) glycol-based polyester polyols, dipropylene glycol, and combinations thereof.

[0141] In addition to the polyester polyol(s), one or more additional polyols may be present. The additional polyol may be any polyol that reacts with isocyanate in a known manner when preparing a polyurethane or polyisocyanurate foam. Useful additional polyols include sucrose-containing polyols, phenol-formaldehyde-containing polyols, glucose-containing polyols, sorbitol-containing polyols, methyl glucoside-containing polyols, toluene diamine-containing polyols, Mannich base polyols, glycerin-containing polyols, ethylene glycol-containing polyols, diethylene glycol-containing polyols, propylene glycol-containing polyols, graft copolymers of polyether polyols and vinyl polymers, copolymers of polyether polyols and polyureas, one or more of (a) condensed with one or more of (b) ((a) glycerin, ethylene glycol, diethylene glycol, trimethylolpropane, ethylenediamine, pentaerythritol, soybean oil, lecithin, tall oil, palm oil, castor oil, (b) ethylene oxide, propylene oxide, butylene oxide, mixtures of ethylene oxide and propylene oxide), or one or more of combinations thereof.

[0142] Preferred premix formulations for use in the manufacture of electrical appliances, PIR panels, and foams for PUR panels, based on the total polyol premix composition, include from about 65 wt% to about 85 wt% of polyester polyol and any additional polyol (from about 20 wt% to about 99 wt% of polyester polyol and from about 1 wt% to about 80 wt% of additional polyol, if present, based on the total weight of the polyols). The polyol premix composition may contain any of the blowing agents of the present invention described herein and each in an amount of from about 15 wt% to about 30 wt% (based on the total polyol premix). In such premix formulations, preferably, from about 0.2 to about 5 wt% of surfactant and from about 0.1 wt% to about 6 wt% of catalyst may be present. The polyol premix in the composition for such applications may preferably optionally contain from about 15 wt% of flame retardant and from about 10 wt% of other additives.

[0143] Preferred polyol premixes for use in spray foam applications, based on the total polyol premix composition, include from about 65 wt% to about 85 wt% of polyester polyol and any additional polyol (from about 40 wt% to about 99 wt% of polyester polyol and from about 1 wt% to about 60 wt% of additional polyol, if present, based on the total weight of the polyols). Preferably, the polyol premix composition in such embodiments contains any of the blowing agents of the present invention described herein and each in an amount of from about 6 wt% to about 12 wt% (based on the total polyol premix). In such formulations, preferably, from about 0.2 to about 5 wt% of surfactant and from about 0.1 wt% to about 8 wt% of catalyst may be present. The polyol premix composition may optionally contain, in preferred embodiments, 15 wt% of flame retardant and 10 wt% of other additives.

[0144] Other components Auxiliary blowing agents may be present. Suitable auxiliary blowing agents include, but are not limited to, other hydrohaloolefins, fluorocarbons, chlorocarbons, chlorofluorocarbons, hydrocarbons, ethers, esters, aldehydes, ketones, acetals, organic acids, atmospheric gases, gas generating materials, or combinations thereof. Gas generating materials mean chemical blowing agents (as opposed to physical blowing agents) that produce a gas, such as CO2, by decomposition or chemical reaction related to / part of the foaming reaction. Examples of gas generating materials (chemical blowing agents) include, but are not limited to, water, formic acid, or azodicarbonamide. Water reacts with isocyanate to form carbon dioxide. Formic acid reacts with isocyanate to form carbon dioxide and carbon monoxide.

[0145] The polyol premix composition may contain a surfactant. Surfactants are used to form a foam from the mixture and to control the size of the foam cells (cells) so that a foam with a desired cell structure is obtained. Preferably, a foam having small, uniformly sized cells is desired for having the most desirable physical properties such as compressive strength and thermal conductivity. Also, the foam should have stable cells that do not collapse before or during foaming.

[0146] Suitable surfactants include silicone surfactants and non-silicone surfactants. The surfactant component is preferably present in the polyol premix composition in an amount of about 0.1 wt% to about 10 wt%, or about 0.2 wt% to about 5 wt%, or about 0.2 wt% to about 3.0 wt%, or about 0.5 wt% to about 3.0 wt% based on the weight of the polyol premix composition.

[0147] The polyol premix composition contains a catalyst. Suitable catalysts include amine catalysts and non-amine catalysts. The catalyst is preferably present in the polyol premix composition in an amount of about 0.2 wt% to about 8.0 wt%, or about 0.4 wt% to about 7.0 wt%, or about 0.5 wt% to about 6.0 wt% based on the weight of the polyol premix composition.

[0148] Conventional flame retardants can optionally be incorporated in an amount of preferably 20 wt% or less, or about 15 wt% or less, or about 10 wt% or less of the polyol premix. Some embodiments, such as foams for electrical appliances, typically do not contain flame retardants. Examples of optional flame retardants include tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, tris(1,3-dichloropropyl) phosphate, tris(2-chloroisopropyl) phosphate, tricresyl phosphate, tris(2,2-dichloroisopropyl) phosphate, diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate, dimethyl methylphosphonate, tris(2,3-dibromopropyl) phosphate, tris(1,3-dichloropropyl) phosphate, and tetra-cis-(2-chloroethyl)ethylene diphosphate, triethyl phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, melamine, etc., but are not limited thereto.

[0149] In addition to the components already described, other components such as dyes, fillers, pigments, dispersants, cell stabilizers, nucleating agents (such as 3M's perfluorinated compounds, PF-5056 and FA-188, etc.) can be included in the preparation of the foam. Other components are typically included in an amount of up to a total of 20 wt%, or 15 wt% or less, or 10 wt% or less, or 5 wt% or less of the polyol premix composition. 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. Pigments that can be used herein include any conventional pigment, such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, iron blue prussian, molybdenum orange, and organic pigments, such as para red, benzidine yellow, toluidine red, toner, and phthalocyanine.

[0150] In general, it is contemplated that the order and method of addition of the components for forming the polyol premix can vary widely within the scope of the present invention. The blowing agent may be added to one or more of the polyol components or vice versa, and this may be before or after adding the other remaining components of the premix composition. Alternatively, all of the components can be added simultaneously.

[0151] The amount and composition of the polyol used to form the foamable composition and the foam depend in part on the type of foam to be produced and can be determined by one of ordinary skill in the art without undue experimentation in view of the teachings contained herein. Flexible foams can preferably contain, for example, from about 80% to about 95% by weight of total polyol (polyester polyol and additional polyol, if present), based on the weight of the polyol premix composition. In spray foams, preferably, for example, from about 65% to about 85% by weight of total polyol can be present, based on the weight of the polyol premix composition. For foams for electrical appliances preferably, for example, from about 65% to about 85% by weight of total polyol can be present, based on the weight of the polyol premix composition. For polyurethane (PUR) panel foams, preferably, for example, from about 65% to about 80% by weight of total polyol can be present, based on the weight of the polyol premix composition. For polyisocyanurate (PIR) panel foams, preferably, for example, from about 65% to about 85% by weight of total polyol can be present, based on the weight of the polyol premix composition. PIR panel foams can be, for example, substantially all polyester polyol.

[0152] Preferred premix formulations for use in the manufacture of electrical appliances, PIR panels, and PUR panel foams, based on the total polyol premix composition, include from about 65 wt% to about 85 wt% polyester polyol and any additional polyol (from about 20 wt% to about 99 wt% polyester polyol and from about 1 wt% to about 80 wt% additional polyol, if present, based on the total weight of the polyols). The polyol premix composition may contain any and each of the blowing agents of the present invention described herein from about 15 wt% to about 30 wt% (based on the total polyol premix). In such premix formulations, preferably, from about 0.2 to about 5 wt% surfactant and from about 0.1 wt% to about 6 wt% catalyst may be present. The polyol premix in compositions for such applications may preferably optionally contain up to about 15 wt% flame retardant and about 10 wt% other additives.

[0153] Preferred polyol premixes for use in spray foam applications, based on the total polyol premix composition, include from about 65 wt% to about 85 wt% polyester polyol and any additional polyol (from about 40 wt% to about 99 wt% polyester polyol and from about 1 wt% to about 60 wt% additional polyol, if present, based on the total weight of the polyols). Preferably, the polyol premix composition in such embodiments contains any and each of the blowing agents of the present invention described herein from about 6 wt% to about 12 wt% (based on the total polyol premix). In such formulations, preferably, from about 0.2 to about 5 wt% surfactant and from about 0.1 wt% to about 8 wt% catalyst may be present. The polyol premix composition may optionally contain, in preferred embodiments, up to 15 wt% flame retardant and 10 wt% other additives.

[0154] A polyol premix that is preferred for use in a flexible foam comprises, based on the total polyol premix composition, about 80 wt% to about 95 wt% polyester polyol and any additional polyol (from about 10 wt% to about 99 wt% polyester polyol and from about 1 wt% to about 90 wt% additional polyol (if present), based on the total weight of the polyols). The polyol premix composition may contain any of the blowing agents of the present invention described herein and each at from about 0.5 wt% to about 4 wt%. There may be present from about 0.2 to about 5 wt% surfactant, and from about 0.1 wt% to about 3.5 wt% catalyst. The polyol premix composition may optionally contain about 10 wt% flame retardant and about 10 wt% other additives.

[0155] Foamable composition A foamable composition suitable for forming a polyurethane or polyisocyanurate foam can be formed by reacting an organic polyisocyanate and the above polyol premix composition. Any organic polyisocyanate, including aliphatic and aromatic polyisocyanates, can be used in the synthesis of polyurethane or polyisocyanurate foams. 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. Aromatic polyisocyanates are preferred as a class.

[0156] Representative organic polyisocyanates have the formula: R(NCO)z Corresponding thereto, in the formula, R is an aliphatic group, an aromatic group, or a mixture thereof, z is an integer corresponding 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, a mixture 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’-dimethyl diphenylmethane-2,2’5,5-’tetraisocyanate, etc.; arylalkyl polyisocyanates such as xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene-1,6-diisocyanate, lysine diisocyanate methyl ester, and mixtures thereof. Other organic polyisocyanates include polymethylene polyphenyl isocyanate, hydrogenated methylene diphenyl isocyanate, 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’-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). Typical aromatic polyisocyanates include m- and p-phenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 2,4- and 2,6-toluene diisocyanate, dianisidine diisocyanate, bitolylene isocyanate, 1,4-diisocyanate, bis(4-isocyanatophenyl)methine, bis(2-methyl-4-isocyanatophenyl)methane, and the like.Preferred polyisocyanates are polymethylene polyphenyl polyisocyanates, especially mixtures containing about 30 to about 85% by weight of methylene bis(phenyl isocyanate), the remainder of the mixture being polymethylene polyphenyl polyisocyanates of functionality higher than 2. In certain cases, so-called isocyanate prepolymers may also be used. The prepolymers are formed by combining an excess of diisocyanate with a polyol (a polyester polyol or a polyether polyol). These polyisocyanates are prepared by conventional methods known in the art. In the present invention, the polyisocyanate and the polyol are used in amounts that result in 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 from about 0.9 to about 4, or from about 0.95 to about 3. Suitable organic polyisocyanates include polymethylene polyphenyl polyisocyanates, methylene bis(phenyl isocyanate), toluene diisocyanate, or combinations thereof.

[0157] In the preparation of polyisocyanurate foams, a trimerization catalyst is preferably used for the purpose of converting the blend, together with an excess of component A, into a polyisocyanurate-polyurethane foam. The trimerization catalysts used include, but are 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, and can be any catalyst known to those skilled in the art. Preferred species within this class are potassium acetate, potassium octoate, and N-(2-hydroxy-5-nonylphenyl)methyl-N-methylglycine.

[0158] The resulting polyurethane or polyisocyanurate foam can have a density that can vary from 0.5 pounds per cubic foot to about 60 pounds per cubic foot, or from about 0.5 to about 20.0 pounds per cubic foot, or from about 0.5 to about 15 pounds per cubic foot. The resulting density is a function of how much blowing agent or blowing agent mixture, in addition to the amount of auxiliary blowing agents such as water or co-blowing agents, is present in Component A and / or B or added when the foam is prepared. These foams can be rigid, flexible, or semi-rigid foams and can have a closed cell structure, an open cell structure, or a mixture of open and closed cells. These foams are used in a variety of well-known applications including, but not limited to, insulation, cushioning, flotation, packaging, adhesives, void filling, crafts and decoration, and shock absorption.

[0159] The following examples are provided for the purpose of illustrating the invention and are not intended to limit its scope.

[0160] Comparative Example 1: trans 1233zd in a polyester polyol premix A polyol premix representative of the polyol premix formulations of polyester polyol-based spray foams is formed as shown in Table C1A below.

[0161]

Table C1A

[0162] The polyol premix compositions used according to this example did not contain water or catalyst, this is to ensure that any stabilizing effects that their components might exhibit do not distort the observed foamability.

[0163] Approximately 80 grams of the polyol premix of Table 1 was mixed with approximately 20 parts of trans-1,2,3,3-tetrafluoropropene (trans-1233zd) in a test tube, shaken vigorously for about 20 seconds, and then placed in a furnace maintained at about 45 °C. The test tube was removed from the furnace at the time intervals shown in Table C1B below, the valve on the test tube was opened to expose the contents of the test tube to atmospheric pressure, and the foaming behavior at that time interval was observed. Then, the test tube was returned to the furnace until the next interval. The results of this test are reported in Table C1B below.

[0164]

Table C1B

[0165] The results reported in the above table indicate that when the blowing agent consists of trans-1233zd, a substantial and detrimental delay will occur from the formation of the polyol / blowing agent combination. . Similarly, the results reported in the above table indicate that when the blowing agent consists of trans-1233zd, a substantial and detrimental delay will occur from the opening or tapping of the container containing the polyol / blowing agent combination.

[0166] Comparative Example 2: trans-1233zd / tDCE in a polyester polyol premix Using the same polyol premix as shown in Table C1A above, combined with a blowing agent containing 99 wt% trans-1,2,3,3-tetrafluoropropene (trans-1233zd) and 1 wt% trans-dichloroethylene (tDCE), and using the same total amount of the blowing agent (20 wt%), the foaming behavior was tested using the same procedure as described in Comparative Example 1. As shown in Table CE2 below, no improvement in the foaming behavior was observed.

[0167]

Table CE2

[0168] Example 1: trans-1233zd and more than 1 wt% tDCE in a polyester polyol premix Using the same polyol premix as shown in Table C1A above, it is combined with a combination of a series of blowing agents consisting of trans-1233zd and tDCE, but the amount of tDCE is more than 1 wt% based on the amounts of trans-1233zd and tDCE. The total amount of blowing agent used is 20 wt%. The various ratios tested are shown in Table 1 below together with the foaming results, and for convenience, the results of Comparative Example 2 are included.

[0169]

Table 1

[0170] Based on the results reported in Table 1 above, 1 wt% of tDCE does not result in a shortening of the defoaming time compared to trans-1233zd alone, but increasing the relative amount of tDCE to 3% to a maximum of about 10% results in a substantial improvement in the foaming behavior (substantially no foaming occurs after 25 minutes or earlier), and it can be seen that an amount of tDCE of about 10% based on the total of trans-1233zd and tDCE produces a polyol premix that substantially does not foam after only about 20 minutes.

[0171] Example 2: trans-1233zd and methylal in a polyester polyol premix Using the same polyol premix as shown in Table C1A above, it is combined with a combination of a series of blowing agents and the same total amount of blowing agent (20 wt%) is used, and the foaming behavior is tested using the same procedure as described in Comparative Example 1. However, the blowing agent consists of a combination of trans-1233zd and methylal in various ratios as shown in Table 2 below, which resulted in the foaming results shown in Table 2.

[0172]

Table 2

[0173] Based on the results reported in Table 2 above, even 1 wt% of methylal results in a substantial improvement in the foaming behavior, and an amount of methylal in the range of about 1 wt% to about 30 wt% based on the total of trans 1233zd and methylal results in a substantial improvement in the behavior, particularly producing a polyol premix that does not substantially foam after about 30 minutes or earlier. Even more surprisingly, Applicants have found that the presence of an amount of methylal of about 30% results in a further dramatic improvement in the defoaming behavior, i.e., substantial foaming ceases after only 10 minutes according to this test, whereas amounts of about 20 wt% or less result in substantial foaming or bubble formation.

[0174] Comparative Example 3: trans 1233zd / cis 1336mmz in a polyester polyol premix The same polyol premix as shown in Table C1A above was combined with blowing agents consisting of various amounts by weight of trans 1233zd and cis 1336mmz, using the same total amount (20 wt%) of the blowing agent, and the foaming behavior was tested using the same procedure as described in Comparative Example 1. As shown in Table CE3 below, no improvement in the foaming behavior was observed with amounts of cis 1336mmz up to about 10 wt% based on the total of trans 1233zd and cis 1336mmz.

[0175]

Table CE3

[0176] As can be seen from the test results reported above, no improvement in the foaming behavior was observed with weight percentages of cis 1336mzz up to 10% compared to trans 1233zd alone.

[0177] Example 3: trans 1233zd and more than 10% cis 1336mmz in a polyester polyol premix The same polyol premix as shown in Table C1A above is used and combined with a combination of a series of blowing agents consisting of trans-1233zd and tDCE, where the amount of tDCE is more than 1 wt% based on the amounts of trans-1233zd and tDCE. The total amount of blowing agent used is 20 wt%. The various ratios tested are shown in Table 3 below together with the foaming results, and for convenience, the 90 / 10 results of Comparative Example 3 are included.

[0178]

Table 3

[0179] Based on the results reported in Table 3 above, an amount of cis-1336mmz up to a maximum of 10 wt% does not result in a shortening of the defoaming time compared to trans-1233zd alone. Surprisingly, it is found that increasing the relative amount of cis-1336mmz to about 20% to a maximum of about 75% of 1336mmz results in a substantial improvement in the foaming behavior (substantially no foaming occurs after 30 minutes).

[0180] Example 4: trans-1233zd and methyl formate in a polyester polyol premix The same polyol premix as shown in Table C1A above is used and combined with a combination of a series of blowing agents, and the foaming behavior is tested using the same procedure as described in Comparative Example 1 using the same total amount (20 wt%) of the blowing agent. However, the blowing agent consists of a combination of trans-1233zd and methyl formate in various ratios as shown in Table 4 below, resulting in the foaming results shown in Table 4.

[0181]

Table 4

[0182] Example 5: trans-1233zd and an antifoaming surfactant in a polyester polyol premix Using the same polyol premix as shown in Table C1A above, it is combined in various amounts with a silicone surfactant sold under the trade name PM301 by Dabco, based on the amounts of trans 1233zd and PM301. The total amount of blowing agent used is 20% by weight. The various ratios tested are shown in Table 5 below along with the foaming results, and for convenience, the results of Comparative Example 2 are included.

[0183]

Table 5

[0184] Based on the results reported in Table 1 above, it was found that 1% by weight of surfactant does not result in a substantial shortening of the defoaming time compared to trans 1233zd alone, and it was further found that an amount of surfactant up to about 5% by weight results in an improvement in the foaming behavior. Surprisingly, this data indicates that an amount of defoaming surfactant greater than 5% by weight, particularly and preferably at least about 10% by weight, based on the total of trans 1233zd and defoaming surfactant, produces a polyol premix that substantially does not foam after only about 20 minutes.

[0185] Comparative Example 4: 100% cis 1336mzzm in a polyester polyol premix A polyol premix representative of the polyol premix formulations of polyester polyol-based spray foams is formed as shown in Table C4A below.

[0186]

Table C4A

[0187] The polyol premix composition used according to this example did not contain water or catalyst, this being to ensure that any stabilizing effect that these components might exhibit does not distort the observed foamability.

[0188] Approximately 80 grams of the polyol premix of Table 1 was mixed in a test tube with approximately 20 parts of cis 1336mzzm (without co - blowing agent), shaken vigorously for approximately 20 seconds, and then placed in an oven maintained at approximately 45°C. The test tube was removed from the oven at the time intervals shown in Table C1B below, the valve on the test tube was opened to expose the contents of the test tube to atmospheric pressure, and the foaming behavior at that time interval was observed. Thereafter, the test tube was returned to the oven until the next interval. The results of this test are reported in Table C4B below.

[0189]

Table C4B

[0190] The results reported in the above table indicate that when the blowing agent consists of cis 1336mzzm, substantial and detrimental delays will occur from the formation of the polyol / blowing agent combination. Similarly, the results reported in the above table indicate that when the blowing agent consists of cis 1336mzzm, substantial and detrimental delays will occur from the opening or tapping of the container containing the polyol / blowing agent combination.

[0191] Comparative Example 5: cis 1336mmz / trans 1233zd in a polyester polyol premix The same polyol premix as shown in Table C4A above was combined with blowing agents consisting of various amounts by weight of trans 1233zd and cis 1336mmz, using the same total amount of blowing agent (20% by weight), and the foaming behavior was tested using the same procedure as described in Comparative Example 4. As shown in Table C5A below, no improvement in foaming behavior was observed with amounts of trans 1233zd in the range of approximately 90% to a maximum of approximately 99% by weight based on the total of trans 1233zd and cis 1336mmz.

[0192]

Table C5A

[0193] As can be seen from the test results reported above, when the amount of trans-1,2,3,3,3-pentafluoropropene (trans-1233zd) is added as a co-blowing agent in an amount of 90% to 99% by weight, no improvement in the foaming behavior is observed compared to cis-1,3,3,3-tetrafluoropropene (cis-1336mzz) alone.

[0194] Example 6: 20% to about 75% of cis-1,3,3,3-tetrafluoropropene (cis-1336mmz) and about 25% to about 80% of trans-1,2,3,3,3-pentafluoropropene (trans-1233zd) in a polyester polyol premix Using the same polyol premix as shown in Table C4A above, it is combined with a series of combinations of blowing agents consisting of cis-1336mzzm and trans-1233zd, where the amount of trans-1233zd is about 25% to about 80% based on the amounts of cis-1336mzzm and trans-1233zd. The total amount of blowing agent used is 20% by weight as in the comparative examples. The various ratios tested are shown in Table 6 below together with the foaming results, and for convenience, the results of 100% cis-1336mzzm in Comparative Example 4 and 99% trans-1233zd in Comparative Example 5 are included.

[0195]

Table 6

[0196] Based on the results reported in Table 6 above, an amount of trans-1233zd less than about 25% by weight does not result in a shortening of the defoaming time compared to cis-1336mmz alone. Surprisingly, it is found that increasing the relative amount of trans-1233zd to about 25% to a maximum of about 80% results in a substantial improvement in the foaming behavior (substantially no foaming occurs after 30 minutes). The present invention includes the following aspects. [1] A polyol premix having improved anti-foaming properties, (a) one or more polyols, (b) at least about 70% by weight of trans HFCO-1233zd and a physical co-foaming agent having anti-foaming properties selected from the group consisting of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm), methylal, methyl formate, glycerin, trans-dichloroethylene (tDCE), and mixtures of two or more thereof, wherein the amount of the anti-foaming co-foaming agent is effective to reduce the anti-foaming time of the polyol premix by at least about 30%, a foaming agent, [2] A polyol premix having improved anti-foaming properties, (a) one or more polyols, (b) at least about 20% to about 75% by weight of cis 1336mzzm and trans HFCO-1233zd in an amount effective to reduce the anti-foaming time of the polyol premix by at least about 20 relative percent, a physical co-foaming agent having anti-foaming properties, [3] The polyol premix according to [1] or [2], wherein the amount of the anti-foaming co-foaming agent is effective to reduce the anti-foaming time of the polyol premix by at least about 50%. [4] The polyol premix according to [1] or [2], wherein the amount of the anti-foaming co-foaming agent is effective to reduce the anti-foaming time of the polyol premix by at least about 80%. [5] The polyol premix according to [1] or [2], wherein the polyol includes a polyester polyol. [6] The polyol premix according to [1] or [2], wherein the polyol includes at least about 50% by weight of a polyester polyol. [7] The polyol premix according to [1] or [2], wherein the polyol includes at least about 90% by weight of a polyester polyol. [8] The polyol premix according to [1], wherein the foaming agent includes cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z)) in an amount effective to reduce the anti-foaming time of the polyol premix by at least about 30%. [9] The polyol premix according to [1], wherein the blowing agent comprises cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm) in an amount effective to reduce the defoaming time of the polyol premix by at least about 50%.

[10] The polyol premix according to [1], wherein the blowing agent comprises methylal in an amount effective to reduce the defoaming time of the polyol premix by at least about 30%.

Claims

**Claim 1** A method of forming a polyol premix having improved foam resistance, comprising: (a) combining one or more polyols with a blowing agent comprising at least 70% by weight of trans-HFCO-1233zd and a physical co-blowing agent having foam-suppressing properties selected from the group consisting of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm), methylal, methyl formate, glycerin, trans-dichloroethylene (tDCE), and mixtures of two or more thereof; (b) forming a polyol premix that does not substantially foam from the combination, wherein the amount of the physical co-blowing agent having foam-suppressing properties is effective to ensure that the time from the completion of the combining step to the formation of the polyol premix that does not substantially foam is 30 minutes or less; wherein the time is measured from when the polyol premix is placed in a furnace at 45° C. until the polyol premix is removed from the furnace and exposed to atmospheric pressure and no foaming is observed. **Claim 2** A method of forming a polyol premix having improved foam resistance, comprising: (a) combining one or more polyols with a blowing agent comprising at least 20% by weight of cis-1336mzzm and trans-HFCO-1233zd, and a physical co-blowing agent having foam-suppressing properties; (b) forming a polyol premix that does not substantially foam from the combination, wherein the amount of the physical co-blowing agent having foam-suppressing properties is effective to ensure that the time from the completion of the combining step to the formation of the polyol premix that does not substantially foam is 30 minutes or less; wherein the time is measured from when the polyol premix is placed in a furnace at 45° C. until the polyol premix is removed from the furnace and exposed to atmospheric pressure and no foaming is observed. **Claim 3** The method according to claim 1 or 2, wherein the amount of the physical co-blowing agent having foam-suppressing properties is effective to ensure that the time from the completion of the combining step to the formation of the polyol premix that does not substantially foam is 20 minutes or less. **Claim 4** The method according to claim 1 or 2, wherein the amount of the physical co-foaming agent having defoaming properties is effective to ensure that the time from the completion of the combination step to the formation of the polyol premix that substantially does not cause foaming is 10 minutes or less.

5. The method according to claim 1 or 2, wherein the amount of the physical co-foaming agent having defoaming properties is effective to ensure that the time from the completion of the combination step to the formation of the polyol premix that substantially does not cause foaming is 5 minutes or less.

6. The method according to claim 1 or 2, wherein the amount of the physical co-foaming agent having defoaming properties is effective to ensure that the time from the completion of the combination step to the formation of the polyol premix that substantially does not cause foaming is 1 minute or less.

7. The method according to claim 1 or 2, wherein the polyol contains a polyester polyol.

8. The method according to claim 1 or 2, wherein the polyol contains at least 50% by weight of a polyester polyol.

9. The method according to claim 1 or 2, wherein the polyol contains at least 90% by weight of a polyester polyol.

10. The method according to claim 1, wherein the blowing agent contains cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z)) in an amount effective to ensure that the time from the completion of the combination step to the formation of the polyol premix that substantially does not cause foaming is 30 minutes or less.

11. The method according to claim 1, wherein the blowing agent contains cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzm(Z) or cis-1336mzzm) in an amount effective to ensure that the time from the completion of the combination step to the formation of the polyol premix that substantially does not cause foaming is 20 minutes or less.

12. The method according to claim 1, wherein the blowing agent contains methylal in an amount effective to ensure that the time from the completion of the combination step to the formation of the polyol premix that substantially does not cause foaming is 30 minutes or less.

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