Low GWP blowing agent blends and uses thereof

Abstract

In some embodiments, a blowing agent blend for use in a polyurethane foam formulation comprises E-1-chloro-3, 3, 3-trifluoropropene (HCFO-1233zd-E) and at least one of E-1, 1, 1, 4, 4, 4-hexafluoro-2-butene (HFO-1336mz-E) and Z-1, 1, 1, 4, 4, 4-hexafluoro-2-butene (HFO-1336mz-Z). The blowing agent blend may be used in a polyurethane foam formulation. The polyurethane foam comprises a plurality of polymer cells and a blowing agent blend. In some embodiments, the polyurethane foam exhibits a thermal conductivity at 35 DEG F of not greater than 0.120 BTU in / ft2 hr DEG F. A method of forming a polyurethane foam includes combining at least one isocyanate and a polyol resin blend to initiate polymerization and form the polyurethane foam. The polyol resin blend comprises a polyol premixed blend and the blowing agent.

Description

Cross-references to related applications

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 546,496, filed October 30, 2023, the disclosure of which is incorporated herein by reference in its entirety. Background Technology Technical Field

[0002] This disclosure relates to the use of fluorinated blends as blowing agents. More specifically, this disclosure relates to the use of blends of at least one of E-1-chloro-3,3,3-trifluoropropylene (HCFO-1233zd-E) and E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E) and Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z) as blowing agents for polyurethane insulation foams. Related technical descriptions

[0003] The low-temperature insulation performance of closed-cell polyurethane foam in appliances is a key enabling factor for achieving energy efficiency targets and environmental sustainability. Improved insulation performance using blowing agent blends with low global warming potential (GWP) unlocks further energy savings and drives insulation technology choices toward sustainability.

[0004] Currently, industrial practice for polyurethane cryogenic insulation utilizes hydrofluorocarbons (HFCs), hydrocarbons (HCs), and more recently, low-GWP hydrochlorofluoroolefins (HCFOs) and hydrofluoroolefins (HFOs). Hydrocarbons are flammable and their cryogenic insulation performance is inferior to that of HFCs. HFCs have high GWPs and are being phased out under regulatory pressure. HCFOs and HFOs have low GWPs and can be used to meet both performance and sustainability objectives. HCFOs and HFOs can also be blended with other HCFOs and HFOs or HFCs to produce low-GWP blends, and can be blended with HCs to suppress flammability, achieving a synergistic effect that provides improved insulation performance while addressing sustainability concerns.

[0005] WO 2008 / 118627 (assigned to Dow Global Technologies) discloses blowing agents with zero ozone depletion potential (ODP) and a GWP of less than 50, as well as solubility in olefin polymers (especially polystyrene), enabling these blowing agents, comprising more than 50 weight percent (wt%) of the total blowing agent, to produce high-quality foam. Table 2 of WO 2008 / 118627 discloses HFO-1336mzz (CF3-CH=CH-CF3) as having moderate solubility compared to the compounds in Table 1 of WO 2008 / 118627. It also discloses that although the olefins in Table 2 can comprise more than 50 weight percent of the blowing agent composition, additional blowing agents that are more soluble in the polymer are necessary to achieve high-quality foam (see page 15, lines 9-12). High-quality foam is described as having an average cell size of 0.02 mm to 5 mm, being closed-cell, and having a strength of 64 kg / m³. 3 Or even lower density foam. A sign of inferior quality is a small average cell size, greater than 64 kg / m³. 3 High density, high open-cell content, and porosity (see page 2, lines 9-13). High-quality foam is also essentially free of pores, which are described as having a multi-pore size and can break at the foam surface to create an irregular surface (see page 2, lines 15-20). Unbroken pores can be referred to as macropores, and the irregular surface resulting from broken pores is in contrast to a smooth surface (skin).

[0006] WO 2008 / 0154612 (assigned to EI du Pont de Nemours and Company) discloses azeotropic and azeotropic-like compositions comprising the E stereoisomer of HFO-1336mzz and methyl formate, n-pentane, 2-methylbutane, E-1,2-dichloroethylene (E-HFO-1130), 1,1,1,3,3-pentafluoropropane (HFC-245fa), n-butane, or isobutane.

[0007] US 2011 / 0144216 (assigned to Honeywell International Inc.) discloses compositions comprising the Z stereoisomer of HFO-1336mzz and their potential uses, including as a blowing agent. US 2011 / 0144216 discloses blends of Z-HFO-1336mzz with HFO, HFCs, hydrofluoroethers (HFEs), chlorofluorocarbons (CFCs), carbon dioxide, olefins, organic acids, alcohols, hydrocarbons, ethers, aldehydes, ketones, and other substances such as methyl formate.

[0008] US 9,145,480 (assigned to Honeywell International Inc.) discloses compositions comprising a mixture of 1,1,1,4,4,4-hexafluorobutene (HFO-1336mzz) and 1-chloro-3,3,3-trifluoropropylene (HCFO-1233zd) as foaming agents, solvents, aerosol propellants, and heat transfer media for use in polymer foams. Summary of the Invention

[0009] In some embodiments, the blowing agent blend for polyurethane foam formulations comprises E-1-chloro-3,3,3-trifluoropropylene (HCFO-1233zd-E) and at least one compound selected from the group consisting of E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), and combinations thereof.

[0010] In some embodiments, the polyurethane foam comprises a plurality of polymeric cells and a blowing agent blend comprising E-1-chloro-3,3,3-trifluoropropylene (HCFO-1233zd-E) and at least one compound selected from the group consisting of E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), and combinations thereof. In some embodiments, the polyurethane foam exhibits a strength of no more than 0.12 BTU·in / ft at 35℉. 2 Thermal conductivity of ·hr·℉.

[0011] In some embodiments, a method of forming polyurethane foam includes combining at least one isocyanate and a polyol resin blend to form polyurethane foam. The polyol resin blend comprises a polyol premix and a blowing agent. The blowing agent comprises E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E) and at least one compound selected from the group consisting of Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), E-1-chloro-3,3,3-trifluoropropylene (HCFO-1233zd-E), and combinations thereof.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Methods and materials used in this invention are described herein; alternatively, suitable methods and materials known in the art may also be used. The materials, methods, and examples described are exemplary only and are not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated herein by reference in their entirety. In case of any conflict, this specification and its included definitions shall prevail.

[0013] Various aspects and embodiments of the present invention can be used alone or in combination with each other. Other features and advantages of the invention will become apparent from the following more detailed description of preferred embodiments of the principles of the invention, illustrated by way of example. Detailed Implementation

[0014] It has been unexpectedly found that blower blends containing at least one of E-1-chloro-3,3,3-trifluoropropylene (HCFO-1233zd-E) and E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E) and Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z) produce high-quality polyurethane foams. In some embodiments, the high-quality polyurethane foams exhibit better properties than polyurethane foams formed using blower blends with higher global warming potential.

[0015] In some implementations, the blowing agent blend provides a polyurethane foam having a lower thermal conductivity than that provided by any individual compound of the blowing agent blend alone.

[0016] In an exemplary embodiment, the blowing agent blend for the polyurethane foam formulation comprises at least one of E-1-chloro-3,3,3-trifluoropropylene (HCFO-1233zd-E), E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), and Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z).

[0017] In some embodiments, the blowing agent is a blend of HCFO-1233zd-E and HFO-1336mzz-E. Suitable blends may include, but are not limited to, amounts of about 50 mol% to about 95 mol% of HCFO-1233zd-E and about 5 mol% to about 50 mol% of HFO-1336mzz-E, alternatively about 55 mol% to about 90 mol% of HCFO-1233zd-E and about 10 mol% to about 45 mol% of HFO-1336mzz-E, alternatively about 65 mol% to about 80 mol% of HCFO-1233zd-E and about 20 mol% to about 35 mol% of HFO-1336mzz-E, or any values, ranges, or subranges thereof. In some embodiments, the blowing agent is a binary blend of HCFO-1233zd-E and HFO-1336mzz-E.

[0018] In some embodiments, the blowing agent is a blend of HCFO-1233zd-E and HFO-1336mzz-Z. Suitable blends may include, but are not limited to, amounts of about 60 mol% to about 85 mol% of HCFO-1233zd-E and about 15 mol% to about 40 mol% of HFO-1336mzz-Z, alternatively about 70 mol% to about 85 mol% of HCFO-1233zd-E and about 15 mol% to about 30 mol% of HFO-1336mzz-Z, alternatively about 75 mol% to about 80 mol% of HCFO-1233zd-E and about 20 mol% to about 25 mol% of HFO-1336mzz-Z, or any values, ranges, or subranges thereof. In some embodiments, the blowing agent is a binary blend of HCFO-1233zd-E and HFO-1336mzz-Z.

[0019] In some embodiments, the foaming agent blend comprises HFCO-1233zd-E, HFO-1336mzz-E, and HFO-1336mzz-Z. Suitable blends may include, but are not limited to, amounts of about 10 mol% to about 90 mol% of HCFO-1233zd-E, about 5 mol% to about 45 mol% of HFO-1336mzz-E and about 5 mol% to about 45 mol% of HFO-1336mzz-Z; alternatively, about 30 mol% to about 70 mol% of HCFO-1233zd-E, about 15 mol% to about 35 mol% of HFO-1336mzz-E and about 15 mol% to about 35 mol% of HFO-1336mzz-Z; alternatively, about 50 mol% to about 70 mol% of HCFO-1233zd-E, about 15 mol% to about 25 mol% of HFO-1336mzz-E and about 15 mol% to about 25 mol% of HFO-1336mzz-Z; or any value, range or subrange thereof. In some implementations, the blowing agent is a ternary blend of HFCO-1233zd-E, HFO-1336mzz-E, and HFO-1336mzz-Z.

[0020] In some embodiments, the foaming agent blend comprises HFO-1336mzz-E and HFO-1336mzz-Z in aggregate amounts of about 10 mol% to about 90 mol%, alternatively about 30 mol% to about 70 mol%, alternatively about 30 mol% to about 50 mol%, or any value, range, or subrange thereof.

[0021] In some embodiments, the molar ratio of HFO-1336mzz-E to HFO-1336mzz-Z in the foaming agent blend is about 1:1 to about 1:4, alternatively about 1:1 to about 1:2, alternatively about 1:2 to about 1:3, alternatively about 1:3 to about 1:4, alternatively about 1:2 to about 1:4, or any value, range or subrange in between.

[0022] In some embodiments, the isocyanate blend includes a blend of methylene diphenyl diisocyanate and polymethylene polyphenyl isocyanate.

[0023] In some embodiments, the polyol resin blend comprises a polyol premix and a foaming agent. In some embodiments, the polyol resin blend also comprises a foaming catalyst, a gelling catalyst, a surfactant, and / or a compatibilizer.

[0024] In some embodiments, the polyol resin blend comprises about 100 parts by weight of a polyol premix and about 20 to about 30 parts by weight, alternatively about 20 to about 25 parts by weight, alternatively about 22 to about 28 parts by weight, alternatively about 25 to about 30 parts by weight, or any value, range, or subrange thereof of a blowing agent blend. In some embodiments, the polyol resin blend further comprises about 2.5 to about 3.5 parts by weight, alternatively about 3 parts by weight, or any value, range, or subrange thereof of a surfactant. In some embodiments, the polyol resin blend further comprises about 3 to about 5 parts by weight, alternatively about 3.5 to about 4.5 parts by weight, alternatively about 4 parts by weight, or any value, range, or subrange thereof of a foaming catalyst and a gelling catalyst blend.

[0025] In some embodiments, the polyol premixed blend comprises, by weight of the polyol premixed blend, an amount of polyether polyol of about 60% to about 90%, alternatively about 60% to about 70%, alternatively about 70% to about 80%, alternatively about 80% to about 90%, or any value, range, or subrange thereof, and an amount of polyester polyol of about 10% to about 40%, alternatively about 10% to about 20%, alternatively about 20% to about 30%, alternatively about 30% to about 40%, or any value, range, or subrange thereof.

[0026] In some embodiments, the polyester polyol is selected from the group consisting of: aliphatic polyols, aromatic polyamides, aromatic polyethylene terephthalate and diethylene glycol phthalic anhydride.

[0027] In some embodiments, the polyether polyol is selected from the group consisting of: aliphatic polyols, glycerol, propylene glycol, aromatic amines or phenolic amines, and polyethers based on sucrose / amine, sucrose / glycerol, or sorbitol propoxylated or ethoxylated / propoxylated o-toluenediamine.

[0028] In some embodiments, the weight ratio of the foaming catalyst to the gel catalyst is in the range of about 10:1 to about 6:1, alternatively about 10:1 to about 8:1, alternatively about 9:1 to about 7:1, alternatively about 8:1 to about 6:1, or any value, range or subrange thereof.

[0029] In some implementations, the foaming catalyst is selected from the group consisting of alkylamines, ethanolamines, and tertiary amines.

[0030] In some embodiments, the gel catalyst is selected from the group consisting of tertiary amines, quaternary ammonium carboxylates, potassium octanoate, potassium acetate, and organometallic compounds.

[0031] In some embodiments, the surfactant is selected to have balanced nucleating and emulsifying activities and is a silicone-based surfactant having both lipophilic propylene oxide and ethylene oxide polyether side chains. Suitable surfactants may include, but are not limited to, Dabco. ® SI3202 (Evonik Industries, Essen, DE) silicone surfactant, Dabco ® DC5585 (Evonik Industries) silicone surfactant, Tegostab ® B 8496 (Evonik Industries) silicone surfactant, Tegostab ® B 8490 (Evonik Industries) silicone surfactant, Silstab ® 2580 (Siltech Corporation, Toronto, CA) Dimethylsiloxane / polyoxyethylene block copolymer or combinations thereof.

[0032] In some embodiments, the weight ratio of surfactant to solubilizer is in the range of about 3:1 to about 1:1, alternatively about 3:1 to about 2:1, alternatively about 2:1 to about 1:1, or any value, range, or subrange in between. Suitable compatibilizers may include, but are not limited to, Dabco. ® PM301 (Evonik Industries) surfactant, Dabco ® PM300 (Evonik Industries) surfactant, Dabco ® PM200 (Evonik Industries) surfactant, Dabco ® EM400 (Evonik Industries) surfactant, nonylphenol ethoxylate (NP-12) 7 mol to 12 mol nonionic surfactant, ethoxylated alcohol 7 mol to 12 mol nonionic surfactant, or combinations thereof.

[0033] In some embodiments, the polyurethane foam comprises a plurality of polymer cells and a blowing agent blend. The blowing agent blend comprises at least one of E-1-chloro-3,3,3-trifluoropropylene (HCFO-1233zd-E), E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), and Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z). The polyurethane foam exhibits a strength of no more than 0.122 BTU·in / ft at 35℉. 2•hr•℉, alternative location not exceeding 0.120 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.1195 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.119 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.1185 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.118 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.1175 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.117 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.1165 BTU·in / ft 2 Thermal conductivity of ·hr·℉, or any value, range, or subrange in between.

[0034] In some implementations, the polyurethane foam exhibits a strength of no more than 0.126 BTU·in / ft at 50℉. 2 •hr•℉, alternative location not exceeding 0.125 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.124 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.123 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.122 BTU·in / ft 2 Thermal conductivity of ·hr·℉, or any value, range, or subrange in between.

[0035] In some implementations, the polyurethane foam exhibits a strength of no more than 0.120 BTU·in / ft at 75℉. 2 •hr•℉, alternative location not exceeding 0.135 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.134 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.133 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.132 BTU·in / ft 2 •hr•℉, alternative location not exceeding 0.131 BTU·in / ft 2 Thermal conductivity of ·hr·℉, or any value, range, or subrange in between.

[0036] In some embodiments, a method of forming polyurethane foam includes combining at least one isocyanate and a polyol resin blend to initiate polymerization and form a polyurethane foam, wherein the polyol resin blend comprises a polyol premix blend and a blowing agent blend as described herein.

[0037] In some embodiments, the method includes cooling a mixture of all components of the polyol resin blend, excluding the blowing agent blend, to a temperature below room temperature, alternatively to below about 50℉ (about 10°C), alternatively to about 39℉ (about 4°C), or any value, range, or subrange in between. In some embodiments, the method includes cooling the blowing agent blend to a temperature below room temperature, alternatively to below about 50℉ (about 10°C), alternatively to about 39℉ (about 4°C), or any value, range, or subrange in between, before combining the blowing agent blend with a mixture of the other components of the polyol resin blend.

[0038] At least one isocyanate and polyol resin blend can be combined in any suitable manner, in a manner that rapidly mixes the two compositions together to react and form polyurethane. In some embodiments, the combination includes pouring at least one isocyanate into the polyol resin blend and stirring at about 2000 rpm or greater, alternatively about 2000 rpm to about 6000 rpm, alternatively about 4000 rpm or greater, or any value, range or subrange therebetween for less than five seconds, alternatively about two to four seconds, alternatively about three seconds, or any value, range or subrange therebetween, followed by allowing it to react for up to about 24 hours to complete the formulation of the polyurethane foam.

[0039] In some implementations, polyurethane foam is commercially manufactured using high-pressure machinery, wherein the resin and isocyanate are heated to a temperature ranging from about 70℉ to about 85℉ (about 21°C to about 29°C) and pumped to a mixing head at a pressure ranging from about 1500 PSI to about 2500 PSI (about 10.3 MPa to about 17.2 MPa).

[0040] In some implementations, molded polyurethane foam formed with a foaming agent blend has better low-temperature insulation properties and a higher percentage of closed cells compared to molded polyurethane foam formed with any single component of the foaming agent blend.

[0041] In some embodiments, the thermal insulation property is thermal conductivity, and the low temperature is in the range of about 30℉ to about 80℉ (about -1°C to about 27°C), alternatively about 35℉ to about 75℉ (about 2°C to about 24°C), alternatively about 35℉ (about 2°C), alternatively about 50℉ (about 10°C), alternatively about 75℉ (about 24°C), or any value, range or subrange in between.

[0042] In an exemplary embodiment, the polyurethane foam has a closed-cell content greater than 87%, alternatively greater than 88%, alternatively greater than 90%, alternatively greater than 92%, alternatively greater than 94%, alternatively greater than 96%, alternatively greater than 98%, or any value, range, or subrange thereof.

[0043] In an exemplary embodiment, the polyurethane foam has a compressive strength greater than 35 pounds per square inch (PSI) (0.24 MPa).

[0044] In some implementations, polyurethane foam insulates appliances (e.g., residential refrigerators, commercial refrigerators, residential water heaters, or commercial water heaters).

[0045] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article of manufacture, or apparatus.

[0046] The transitional phrase "consisting of..." excludes any unspecified elements, steps, or ingredients. If in a claim, such language, apart from impurities typically associated with it, will not include protection for materials other than those described. When the phrase "consisting of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claim. The transitional phrase "substantially composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect one or more essential and novel features of the invention protected by the claim, particularly the mode of action for achieving any desired result in the method of the invention. The term "substantially composed of..." occupies an intermediate position between "comprising" and "consisting of...".

[0047] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the specification should be interpreted as also using the terms “consistently consisting of” or “comprises of” to describe such inventions. Example

[0048] The invention will be described in more detail through specific embodiments. The following embodiments are provided for illustrative purposes and are not intended to limit the invention in any way.

[0049] The low-temperature properties of blowing agent blends containing HFO and / or HCFO were investigated using selected polyols, surfactants, and additives. Blowing agent blends were produced by weight, and formulation substitution studies were conducted on a molar basis to achieve target densities.

[0050] The effectiveness of blends of HFCO-1233zd-E with HFO-1336mzz-Z and / or HFO-1336mzz-E as polyurethane blowing agents was evaluated relative to HCFO-1233zd-E alone (Comparative Example 1; CE1), HFO-1336mzz-Z alone (Comparative Example 2; CE2), and 50:50 HFO-1336mzz-E / HFO-1336mzz-Z (Comparative Example 3; CE3).

[0051] The polyol resin blend (B-side) of the formulation typically comprises 100 parts polyol premix, 20 to 30 parts blowing agent blend, 3 parts surfactant, and 4 parts catalyst blend. The B-side components, excluding the blowing agent blend, are weighed on a balance, mixed together in a beaker, and cooled to 4°C. The blowing agent blend is cooled to below 10°C and then added to the B-side mixture until it is completely incorporated into the other polyol side components.

[0052] Side A (which mainly contains polymethylene polyphenyl isocyanate (PAPI) containing methylene diphenyl diisocyanate (MDI)) ™ 27, Dow Chemical Company, Midland, MI) was weighed in a beaker with an additional margin to obtain sufficient headspace for pouring, and then poured into the polyol side component.

[0053] Use an arrow-shaped mixer to mix sides A and B together at 4000 rpm for 3 seconds. After mixing, quickly pour the composition into a wax-coated cardboard box and start the reaction timer.

[0054] Polyurethane foams were prepared using binary blowing agent blends of HFCO-1233zd-E:HFO-1336mzz-Z in molar ratios of 90:10, 80:20, 70:30, 50:50, and 30:70.

[0055] Polyurethane foams were also prepared using binary blowing agent blends of HFCO-1233zd-E and HFO-1336mzz-E in molar ratios of 90:10, 80:20, 65:35, and 50:50.

[0056] Polyurethane foams were also prepared using ternary foaming agent blends of HFCO-1233zd-E:HFO-1336mzz-E:HFO-1336mzz-Z with molar ratios of 70:15:15, 50:25:25, 30:35:35 and 10:45:45.

[0057] The resulting foam was placed under a fume hood for 24 hours to allow the polyurethane reaction to complete. The foam was then cut into 8"×8"×1.5" blocks. The compressive strength and closed-cell percentage of the foam blocks were tested. The thermal conductivity of the foam blocks was also tested using a heat flow meter at 35℉ (1.7℃), 50℉ (10℃), and 75℉ (23.9℃) according to ASTM C-518. The obtained thermal conductivity values ​​are expressed in BTU·in / ft. 2 Report in hr·℉ as the average of three measurements.

[0058]

[0059] All foams exhibit a good foam appearance. The optimal blowing agent blend provides lower thermal conductivity than CE1, CE2, and CE3.

[0060] All of the above references are incorporated herein by reference.

[0061] It should be understood that although the invention has been described in conjunction with a detailed description, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. Those skilled in the art to which this invention pertains will understand that any feature of any particular aspect and / or embodiment of the invention described herein may be combined with one or more features of any other aspect and / or embodiment of the invention described herein, modified where appropriate to ensure compatibility of the combination. Such combinations are considered part of the invention contemplated by this disclosure.

Claims

1. A blowing agent blend for use in polyurethane foam formulations, said blowing agent blend comprising: E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd-E); and At least one compound selected from the group consisting of: E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E), Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z), and combinations thereof.

2. The foaming agent blend according to claim 1, wherein the foaming agent blend is a binary blend of 50 mol% to 95 mol% HCFO-1233zd-E and 5 mol% to 50 mol% HFO-1336mzz-E.

3. The foaming agent blend according to claim 2, wherein the foaming agent blend is a binary blend of 55 mol% to 90 mol% HCFO-1233zd-E and 10 mol% to 45 mol% HFO-1336mzz-E.

4. The foaming agent blend according to claim 1, wherein the foaming agent blend is a binary blend of 60 mol% to 85 mol% HCFO-1233zd-E and 15 mol% to 40 mol% HFO-1336mzz-Z.

5. The foaming agent blend according to claim 4, wherein the foaming agent blend is a binary blend of 70 mol% to 85 mol% HCFO-1233zd-E and 15 mol% to 30 mol% HFO-1336mzz-Z.

6. The foaming agent blend according to claim 1, wherein the foaming agent blend is a ternary blend of 10 mol% to 90 mol% HCFO-1233zd-E, 5 mol% to 45 mol% HFO-1336mzz-E and 5 mol% to 45 mol% HFO-1336mzz-Z.

7. The foaming agent blend according to claim 6, wherein the foaming agent blend is a ternary blend of 10 mol% to 90 mol% HCFO-1233zd-E, 5 mol% to 45 mol% HFO-1336mzz-E and 5 mol% to 45 mol% HFO-1336mzz-Z.

8. A polyurethane foam comprising a plurality of polymer cells and a foaming agent blend according to any one of claims 1 to 7.

9. The polyurethane foam of claim 8, wherein the polyurethane foam exhibits an intensity of not more than 0.120 BTU·in / ft at 35℉. 2 Thermal conductivity of ·hr·℉.

10. The polyurethane foam of claim 8, wherein the polyurethane foam exhibits an intensity of not more than 0.125 BTU·in / ft at 50℉. 2 Thermal conductivity of ·hr·℉.

11. The polyurethane foam of claim 8, wherein the polyurethane foam exhibits a strength of not more than 0.134 BTU·in / ft at 75℉. 2 Thermal conductivity of ·hr·℉.

12. The polyurethane foam according to any one of claims 8 to 11, wherein the plurality of polymer cells are formed by a polyol premixed blend comprising about 60% to about 90% polyether polyol and about 10% to about 40% polyester polyol by weight of the polyol premixed blend.

13. The polyurethane foam according to claim 12, wherein the polyester polyol is selected from the group consisting of: aliphatic polyols, aromatic polyamides, aromatic polyethylene terephthalate and diethylene glycol phthalic anhydride.

14. The polyurethane foam according to claim 12 or 13, wherein the polyether polyol is selected from the group consisting of: aliphatic polyols, glycerol, propylene glycol, aromatic amines or phenolic amines, and polyethers based on sucrose / amine, sucrose / glycerol, or sorbitol propoxylated or ethoxylated / propoxylated o-toluenediamine.

15. The polyurethane foam according to any one of claims 8 to 14, the polyurethane foam further comprising a foaming catalyst and a gelling catalyst, wherein the weight ratio of the foaming catalyst to the gelling catalyst is in the range of 10:1 to 6:1, and wherein the foaming catalyst is selected from the group consisting of alkylamines, ethanolamines and tertiary amines, and the gelling catalyst is selected from the group consisting of tertiary amines, quaternary ammonium carboxylates, potassium octanoate, potassium acetate and organometallic compounds.

16. The polyurethane foam according to any one of claims 8 to 15, wherein the polyurethane foam further comprises a surfactant, wherein the surfactant is selected to have balanced nucleating and emulsifying activities and is a silicone-based surfactant having both lipophilic propylene oxide and ethylene oxide polyether side chains.

17. The polyurethane foam according to any one of claims 8 to 16, wherein the polyurethane foam further comprises a compatibilizer.

18. The polyurethane foam of claim 17, wherein the weight ratio of the surfactant to the compatibilizer is in the range of 3:1 to 1:

1.

19. A method for forming polyurethane foam, the method comprising: At least one isocyanate and polyol resin blend is combined to initiate polymerization and form the polyurethane foam, wherein the polyol resin blend comprises a polyol premix blend and a blowing agent blend according to any one of claims 1 to 7.

20. The method of claim 19, wherein the polyol premix comprises about 60% to about 90% of a polyether polyol and about 10% to about 40% of a polyester polyol by weight of the polyol premix.

21. The method according to claim 19 or 20, wherein the polyol resin blend further comprises a foaming catalyst, a gelling catalyst, and a surfactant.

22. The method according to any one of claims 19 to 21, wherein the polyol resin blend further comprises a compatibilizer.

23. The method according to any one of claims 19 to 22, wherein the at least one isocyanate comprises polymethylene polyphenyl isocyanate and methylene diphenyl diisocyanate.

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