Low-gwp blowing agent blends and uses thereof

Abstract

In some embodiments, a blowing agent blend for a polyurethane foam formulation includes 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-1336mzz-E) and Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z). A polyurethane foam includes a plurality of polymeric cells and a blowing agent blend. In some embodiments, the polyurethane foam exhibits a thermal conductivity at 35ºF of not greater than 0.120 BTU·in / ft2·hr·°F. A process 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 includes a polyol premix blend and the blowing agent.

Description

TITLELOW-GWP BLOWING AGENT BLENDS AND USES THEREOFCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 546,496 filed October 30, 2023, the disclosures of which is incorporated herein by reference in its entirety.BACKGROUND INFORMATIONField of the Disclosure

[0002] This disclosure relates to the use of fluorine-containing blends as blowing agents. More specifically, this disclosure relates to the use of blends of 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-1336mzz-E) and Z-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z) as blowing agents for polyurethane insulation foams.Description of the Related Art

[0003] Low temperature insulation performance with closed cell polyurethane foam in appliances is a key enabler in achieving energy efficiency targets and environmental sustainability. Improved insulation performance using blowing agents blends having a low global warming potential (GWP) unlocks further energy savings and drives insulation technology selection towards sustainability.

[0004] Currently, the industry practice for polyurethane low temperature insulation employs the use of hydrofluorocarbons (HFCs), hydrocarbons (HCs), and, more recently, low GWP hydrochlorofluoroolefins (HCFOs) and hydrofluoroolefins (HFOs). Hydrocarbons are flammable and their low temperature insulation performance is inferior to HFCs. HFCs have a high GWP and are under regulatory pressure for phase-down. HCFOs and HFOs have a low GWP and can be leveraged to meet both performance and sustainability goals. HCFOs and HFOs can also be blended with other HCFOs and HFOs or HFCs to create low GWP blends and with HCs to suppress flammability for synergistic interactions that deliver improved insulation performance while addressing sustainability concerns.

[0005] WO 2008 / 118627 (assigned to Dow Global Technologies) discloses blowing agents that have a zero-ozone depletion potential (ODP) and a GWP of less than 50 and solubility in alkenyl polymers, notably polystyrene, that enable these blowing agents comprising more than 50 weight percent (wt%) of the total blowing agent to produce quality foam. Table 2 of WO 2008 / 118627 discloses HFO-1336mzz (CF3-CH=CH-CF3) as having a moderate solubility as compared to the compounds of Table 1 of WO 2008 / 1 18627. It is further disclosed that while the alkenes of Table 2 can comprise over 50 wt% of the blowing agent composition, additional blowing agent that is more soluble in the polymer is necessary to achieve quality foam (see page 15, lines 9-12). Quality foam is described as the foam having an average cell size of 0.02 to 5 mm, being close-celled, and having a density of 64 kg / m3or less. Indicia of lack of quality are small average cell size, density greater than 64 kg / m3, high open cell content and blowholes (see page 2, lines 9-13). The quality foam is also essentially free of blowholes, which are described as being the size of multiple cell diameters and which can rupture at the foam surface to give an irregular surface (see page 2, lines 15-20). The blowholes that do not rupture can be called macrovoids, and the irregular surface caused by the rupturing blowholes is the opposite of a smooth surface (skin).

[0006] WO 2008 / 0154612 (assigned to E.l. du Pont de Nemours and Company) discloses azeotropic and azeotrope-like compositions including 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 201 1 / 0144216 (assigned to Honeywell International Inc.) discloses compositions including 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 HFOs, HFCs, hydrofluoroethers (HFEs), chlorofluorocarbons (CFCs), carbon dioxide, olefins, organic acids, alcohols, hydrocarbons, ethers, aldehydes, ketones, and others such as methyl formate.

[0008] US 9,145,480 (assigned to Honeywell International Inc.) discloses compositions including mixtures of 1 , 1 , 1 ,4,4,4-hexafluorobutene (HFO-1336mzz)and 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) as being are useful as blowing agents for polymer foam, solvents, aerosol propellants and heat transfer media.SUMMARY

[0009] In some embodiments, a blowing agent blend for a polyurethane foam formulation includes 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 a combination thereof.

[0010] In some embodiments, a polyurethane foam includes a plurality of polymeric cells and a blowing agent blend including 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 a combination thereof. In some embodiments, the polyurethane foam exhibits a thermal conductivity at 35°F of not greater than 0.12 BTU in / ft2hr °F.

[0011] In some embodiments, a process of forming a polyurethane foam includes combining at least one isocyanate and a polyol resin blend to form the polyurethane foam. The polyol resin blend includes a polyol premix blend and a blowing agent. The blowing agent includes 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-trifluoropropene (HCFO- 1233zd-E), and a combination 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 belongs. Methods and materials are described herein for use in the present invention; other, suitable methods and materials known in the art can also be used. The materials, methods, and examples are illustrative only and not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control.

[0013] The various aspects and embodiments of the invention can be used alone or in combinations with each other. Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment which illustrates, by way of example, the principles of the invention.DETAILED DESCRIPTION

[0014] It has been unexpectedly discovered that blowing agent blends including 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-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 have better properties than polyurethane foams formed with blowing agent blends having higher global warming potentials.

[0015] In some embodiments, the blowing agent blend provides a polyurethane foam with a lower thermal conductivity than the thermal conductivity provided by any of the individual compounds of the blowing agent blend alone.

[0016] In exemplary embodiments, the blowing agent blend for a polyurethane foam formulation includes 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-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. Appropriate blends may include, but are not limited to, an amount of about 50 to about 95 mol% HCFO-1233zd-E and about 5 to about 50 mol% HFO-1336mzz-E, alternatively about 55 to about 90 mol% HCFO-1233zd-E and about 10 to about 45 mol% HFO-1336mzz-E, alternatively about 65 to about 80 mol% HCFO-1233zd-E and about 20 to about 35 mol% HFO-1336mzz-E, or any value, range, or sub-range therebetween. In some embodiments, the blowing agent is a binary blend of the 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. Appropriate blends may include, but are not limited to, an amount of about 60 to about 85 mol% HCFO-1233zd-E and about 15 to about 40 mol% HFO-1336mzz-Z, alternatively about 70 to about 85 mol% HCFO-1233zd-Eand about 15 to about 30 mol% HFO-1336mzz-Z, alternatively about 75 to about 80 mol% HCFO-1233zd-E and about 20 to about 25 mol% HFO-1336mzz-Z, or any value, range, or sub-range therebetween. In some embodiments, the blowing agent is a binary blend of the HCFO-1233zd-E and HFO-1336mzz-Z.

[0019] In some embodiments, the blowing agent blend includes HFCO-1233zd-E, HFO-1336mzz-E, and HFO-1336mzz-Z. Appropriate blends may include, but are not limited to, an amount of about 10 to about 90 mol% HCFO-1233zd-E, about 5 to about 45 mol% HFO-1336mzz-E, and about 5 to about 45 mol% HFO-1336mzz-Z; alternatively about 30 to about 70 mol% HCFO-1233zd-E, about 15 to about 35 mol% HFO-1336mzz-E, and about 15 to about 35 mol% HFO-1336mzz-Z; alternatively about 50 to about 70 mol% HCFO-1233zd-E, about 15 to about25 mol% HFO-1336mzz-E, and about 15 to about 25 mol% HFO-1336mzz-Z; or any value, range, or sub-range therebetween. In some embodiments, the blowing agent is a ternary blend of the and HFCO-1233zd-E, HFO-1336mzz-E, and HFO-1336mzz-Z.

[0020] In some embodiments, the blowing agent blend includes HFO-1336mzz-E and HFO-1336mzz-Z in a combined total amount of about 10 to about 90 mol%, alternatively about 30 to about 70 mol%, alternatively about 30 to about 50 mol%, or any value, range, or sub-range therebetween.

[0021] In some embodiments, the HFO-1336mzz-E and HFO-1336mzz-Z are at a molar ratio in the blowing agent blend of 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 sub-range therebetween.

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

[0023] In some embodiments, the polyol resin blend includes a polyol premix blend and a blowing agent. In some embodiments, the polyol resin blend further includes a blow catalyst, a gel catalyst, a surfactant, and / or a compatibilizer.

[0024] In some embodiments, the polyol resin blend includes about 100 parts by weight polyol premix and blowing agent blend in parts by weight of about 20 to about30, alternatively about 20 to about 25, alternatively about 22 to about 28, alternatively about 25 to about 30, or any value, range, or sub-range therebetween. In some embodiments, the polyol resin blend also includes surfactant in parts by weight of about 2.5 to about 3.5, alternatively about 3, or any value, range, or subrange therebetween. In some embodiments, the polyol resin blend also includes a catalyst blend of blow catalyst and a gel catalyst in parts by weight of about 3 to about 5, alternatively about 3.5 to about 4.5, alternatively about 4, or any value, range, or sub-range therebetween.

[0025] In some embodiments, the polyol premix blend includes a polyether polyol in an amount 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 sub-range therebetween and a polyester polyol in an amount 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 sub-range therebetween, by weight of the polyol premix blend.

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

[0027] In some embodiments, the polyether polyol is selected from the group consisting of an aliphatic polyol, glycerine, propylene glycol, an aromatic or phenolic amine, and a polyether based on sucrose / amine, sucrose / glycerine, or sorbitol propoxylated or ethoxylated / propoxylated ortho-toluenediamine.

[0028] In some embodiments, the weight ratio of blow catalyst to 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 sub-range therebetween.

[0029] In some embodiments, the blow catalyst is selected from the group consisting of an alkyl, ethanol, and a tertiary amine.

[0030] In some embodiments, the gel catalyst is selected from the group consisting of a tertiary amine, a quaternary ammonium carboxylate, potassium octoate, potassium acetate, and an organometallic.

[0031] In some embodiments, the surfactant is selected to have balanced nucleation and emulsification activity and is silicone-based with both lipophilic propylene oxide and ethylene oxide polyether side chains. Appropriate 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 / polyoxyalkylene block copolymer, or a combination thereof.

[0032] In some embodiments, the surfactant and compatibilizer are at a weight ratio 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 sub-range therebetween. Appropriate 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) 7-12 mol nonionic surfactant, ethoxylated alcohol 7-12 mol nonionic surfactant, or a combination thereof.

[0033] In some embodiments, a polyurethane foam includes a plurality of polymeric cells and a blowing agent blend. The blowing agent blend includes 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-1336mzz-E) and Z-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z). The polyurethane foam exhibits a thermal conductivity at 35°F of not greater than 0.122 BTU in / ft2hr °F, alternatively not greater than 0.120 BTU in / ft2hr °F, alternatively not greater than 0.1195 BTU in / ft2hr °F, alternatively not greater than 0.119 BTU in / ft2hr °F, alternatively not greater than 0.1185BTU in / ft2hr °F, alternatively not greater than 0.118 BTU in / ft2hr °F, alternatively not greater than 0.1 175 BTU in / ft2hr °F, alternatively not greater than 0.117BTU in / ft2hr °F, alternatively not greater than 0.1165 BTU in / ft2hr °F, or any value, range, or sub-range therebetween.

[0034] In some embodiments, the polyurethane foam exhibits a thermal conductivity at 50°F of not greater than 0.126 BTU in / ft2hr °F, alternatively not greater than 0.125 BTU in / ft2hr °F, alternatively not greater than 0.124BTU in / ft2-hr-°F, alternatively not greater than 0.123 BTU in / ft2hr °F, alternatively not greater than 0.122 BTU in / ft2hr °F, or any value, range, or sub-range therebetween.

[0035] In some embodiments, the polyurethane foam exhibits a thermal conductivity at 75 °F of not greater than 0.120 BTU in / ft2hr °F, alternatively not greater than 0.135 BTU in / ft2hr °F, alternatively not greater than 0.134 BTU in / ft2hr °F, alternatively not greater than 0.133 BTU in / ft2hr °F, alternatively not greater than 0.132 BTU in / ft2hr °F, alternatively not greater than 0.131 BTU in / ft2hr °F, or any value, range, or sub-range therebetween.

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

[0037] In some embodiments, the process includes cooling a mixture of all of the components of the polyol resin blend except for the blowing agent blend to a temperature below room temperature, alternatively to below about 50°F (about 10°C), alternatively to about 39°F (about 4°C), or any value, range or sub-range therebetween. In some embodiments, the process includes cooling the blowing agent blend to a temperature below room temperature, alternatively to below about 50°F (about 10°C), alternatively to about 39°F (about 4°C), or any value, range or sub-range therebetween, before combining the blowing agent blend and the mixture of the other components of the polyol resin blend.

[0038] The at least one isocyanate and the polyol resin blend may be combined in any appropriate manner that quickly mixes the two compositions together for reaction to form the polyurethane. In some embodiments, the combining includes pouring the at least one isocyanate into the polyol resin blend and stirring for less than five seconds, alternatively about two to four seconds, alternatively about three seconds, or any value, range, or sub-range therebetween at about 2000 revolutions per minute (rpm) or greater, alternatively about 2000 to about 6000 rpm, alternatively about 4000 rpm or greater, or any value, range, or sub-range therebetween before being allowed to react for up to about 24 hours to complete formulation of the polyurethane foam.

[0039] In some embodiments, the polyurethane foam is commercially manufactured using a high-pressure machine, where the resin and the isocyanate are heated to a temperature in the range of about 70 to about 85°F (about 21 to about 29°C) and are pumped to the mixing head at a pressure in the range of about 1500 to about 2500 PSI (about 10.3 to about 17.2 MPa).

[0040] In some embodiments, the formed polyurethane foam formed with the blowing agent blend has better low temperature insulation properties and a higher closed cell percentage than a formed polyurethane foam with a blowing agent of any of the individual components of the blowing agent blend.

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

[0042] In exemplary embodiments, the polyurethane foam has greater than 87% closed cells, alternatively greater than 88% closed cells, alternatively greater than 90% closed cells, alternatively greater than 92% closed cells, alternatively greater than 94% closed cells, alternatively greater than 96% closed cells, alternatively greater than 98% closed cells, or any value, range, or sub-range therebetween.

[0043] In exemplary embodiments, the polyurethane foam has a compressive strength of greater than 35-pound force per square inch (PSI) (0.24 MPa).

[0044] In some embodiments, the polyurethane foam insulates an appliance, such as, for example, a residential refrigerator, a commercial refrigerator, a residential hot water heater, or a commercial hot water heater.

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

[0046] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. If in the claim, such language would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. The transitional phrase "consisting essentially of" is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of’.

[0047] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising”, it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of”.EXAMPLES

[0048] The invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes and are not intended to limit the invention in any manner.

[0049] Select polyols, surfactants, and additives were used to study blowing agent blends including an HFO and / or an HCFO for low temperature performance. Blowing agent blends were created on a weight basis and formulation substitution studies were done 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 blowing agents for polyurethane 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) was assessed.

[0051] The polyol resin blend (B-side) of the formulations generally included 100 parts of a polyol premix, 20 to 30 parts of the blowing agent blend, 3 parts of a surfactant, and 4 parts of a catalyst blend. The B-side components except for the blowing agent blend were weighed on a mass balance, mixed together in a beaker, and chilled to 4°C. The blowing agent blend was chilled down below 10°C and then added to the B-side mixture until it was fully incorporated into the other polyol side components.

[0052] The A-side, primarily polymethylene polyphenylisocyanate containing methylene diphenyl diisocyanate (MDI) (PAPI™ 27, Dow Chemical Company, Midland, Ml), was weighed in a beaker with an extra weight for sufficient head-room pouring, then poured into the polyol-side components.

[0053] The A-side and the B-side were mixed together for 3 s at 4000 rpm with an arrow-head mixer. After mixing, the composition was quickly poured into a wax- coated cardboard box and a reaction timer was started.

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

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

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

[0057] The resulting foam was placed under an air-hood for 24 hours to complete the polyurethane reaction. The foam was then cut into 8”x8”x1 .5” blocks. The foam blocks were tested for compressive strength and percentage of closed cells. The foam blocks were also tested for thermal conductivity at 35°F (1 .7°C), 50°F (10°C), and 75°F (23.9°C) utilizing a heat flow meter per ASTM C-518. The T able shows the resulting thermal conductivity values being reported in BTU in / ft2hr °F as the average of three measurements.Table - Foam Thermal Conductivities

[0058] All foams had a good foam appearance. The best blowing agent blends provided lower thermal conductivities than CE1 , CE2, and CE3.

[0059] All above-mentioned references are hereby incorporated by reference herein.

[0060] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be appreciated by those persons having ordinary skill in the art(s) to which the present invention relates that any of the features described herein in respect of any particular aspect and / or embodiment of the present invention can be combined with one or more of any of the other features of any other aspects and / or embodiments of the present invention described herein, with modifications as appropriate to ensure compatibility of the combinations. Such combinations are considered to be part of the present invention contemplated by this disclosure.

Claims

CLAIMSWhat is claimed is:1 . A blowing agent blend for a polyurethane foam formulation, the 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 a combination thereof.

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

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

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

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

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

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

8. A polyurethane foam comprising a plurality of polymeric cells and the blowing agent blend of any of claims 1 to 7.

9. The polyurethane foam of claim 8, wherein the polyurethane foam exhibits a thermal conductivity at 35 °F of not greater than 0.120 BTU in / ft2hr °F.

10. The polyurethane foam of claim 8, wherein the polyurethane foam exhibits a thermal conductivity at 50 °F of not greater than 0.125 BTU in / ft2hr °F.11 . The polyurethane foam of claim 8, wherein the polyurethane foam exhibits a thermal conductivity at 75 °F of not greater than 0.134 BTU in / ft2hr °F.

12. The polyurethane foam of any of claims 8 to 11 , wherein the plurality of polymeric cells are formed from a polyol premix blend comprising 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 blend.

13. The polyurethane foam of claim 12, wherein the polyester polyol is selected from the group consisting of an aliphatic polyol, an aromatic polyamide, an aromatic polyethylene terephthalate, and a diethylene glycol phthalic anhydride.

14. The polyurethane foam of claim 12 or 13, wherein the polyether polyol is selected from the group consisting of an aliphatic polyol, glycerine, propylene glycol, an aromatic or phenolic amine, and a polyether based on sucrose / amine, sucrose / glycerine, or sorbitol propoxylated or ethoxylated / propoxylated ortho-toluenediamine.

15. The polyurethane foam of any of claims 8 to 14 further comprising a blow catalyst and a gel catalyst, wherein the weight ratio of blow catalyst to gel catalyst is in the range of 10:1 to 6:1 and wherein the blow catalyst is selected from the group consisting of an alkyl, ethanol, and a tertiary amine, and the gel catalyst is selected from the group consisting of a tertiary amine, a quaternary ammonium carboxylate, potassium octoate, potassium acetate, and an organometallic.

16. The polyurethane foam of any of claims 8 to 15 further comprising a surfactant, wherein the surfactant is selected to have balanced nucleation and emulsification activity and is silicone-based with both lipophilic propylene oxide and ethylene oxide polyether side chains.

17. The polyurethane foam of any of claims 8 to 16 further comprising a compatibilizer.

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

19. A process of forming a polyurethane foam comprising: combining at least one isocyanate and a polyol resin blend to initiate polymerization and form the polyurethane foam, wherein the polyol resin blend comprises a polyol premix blend and the blowing agent blend of any of claims 1 to 7.

20. The process of claim 19, wherein the polyol premix blend 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 blend.21 . The process of claim 19 or 20, wherein the polyol resin blend further comprises a blow catalyst, a gel catalyst, and a surfactant.

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

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

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