Search

CN-122029221-A - Low GWP blowing agent blends and uses thereof

CN122029221ACN 122029221 ACN122029221 ACN 122029221ACN-122029221-A

Abstract

In some embodiments of the present invention, in some embodiments, A blowing agent blend for polyurethane foam formulations comprises E-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd-E) and E-1, 4-hexafluoro-2-butene (HFO-1336 mzz-E) and Z-1, 4-at least one of hexafluoro-2-butene (HFO-1336 mzz-Z). Polyurethane foam comprises a plurality of polymer cells and a blowing agent blend. In some embodiments, the polyurethane foam exhibits a thermal conductivity of no greater than 0.120 BTU ·in/ft 2 ·hr·°f at 35°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 includes a polyol premix blend and the blowing agent.

Inventors

  • H. K. mussimi
  • S. A. Ata

Assignees

  • 科慕埃弗西有限公司

Dates

Publication Date
20260512
Application Date
20241015
Priority Date
20231030

Claims (20)

  1. 1. A blowing agent blend for a polyurethane foam formulation, the blowing agent blend comprising: e-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd-E), and At least one compound selected from the group consisting of: E-1, 4-hexafluoro-2-butene (HFO-1336 mzz-E) Z-1, 4-hexafluoro-2-butene (HFO-1336 mzz-Z) and combinations thereof.
  2. 2. The blowing agent blend of claim 1 wherein the blowing agent blend is a binary blend of 50 to 95 mole% HCFO-1233zd-E and 5 to 50 mole% HFO-1336 mzz-E.
  3. 3. The blowing agent blend of claim 2 wherein the blowing agent blend is a binary blend of 55 to 90 mole% HCFO-1233zd-E and 10 to 45 mole% HFO-1336 mzz-E.
  4. 4. The blowing agent blend of claim 1 wherein the blowing agent blend is a binary blend of 60 to 85 mole% HCFO-1233zd-E and 15 to 40 mole% HFO-1336 mzz-Z.
  5. 5. The blowing agent blend of claim 4 wherein the blowing agent blend is a binary blend of 70 to 85 mole% HCFO-1233zd-E and 15 to 30 mole% HFO-1336 mzz-Z.
  6. 6. The blowing agent blend of claim 1 wherein the blowing agent blend is a ternary blend of 10 to 90 mole% HCFO-1233zd-E, 5 to 45 mole% HFO-1336mzz-E, and 5 to 45 mole% HFO-1336 mzz-Z.
  7. 7. The blowing agent blend of claim 6 wherein the blowing agent blend is a ternary blend of 10 to 90 mole% HCFO-1233zd-E, 5 to 45 mole% HFO-1336mzz-E, and 5 to 45 mole% HFO-1336 mzz-Z.
  8. 8. A polyurethane foam comprising a plurality of polymer cells and the blowing agent blend of any of claims 1-7.
  9. 9. The polyurethane foam of claim 8, wherein the polyurethane foam exhibits a thermal conductivity of not greater than 0.120 BTU-in/ft 2 -hr °f at 35°f.
  10. 10. The polyurethane foam of claim 8, wherein the polyurethane foam exhibits a thermal conductivity of no greater than 0.125 BTU-in/ft 2 -hr °f at 50°f.
  11. 11. The polyurethane foam of claim 8, wherein the polyurethane foam exhibits a thermal conductivity of no greater than 0.134 BTU-in/ft 2 -hr °f at 75°f.
  12. 12. The polyurethane foam of any of claims 8-11, wherein the plurality of polymer cells are formed from a polyol premix blend comprising from about 60% to about 90% polyether polyol and from about 10% to about 40% polyester polyol, by weight of the polyol premix blend.
  13. 13. The polyurethane foam of 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. 14. The polyurethane foam of 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. 15. The polyurethane foam of any one of claims 8 to 14, further comprising a foaming catalyst and a gelling catalyst, wherein the weight ratio of foaming catalyst to 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, ethanolamine and tertiary amines, and the gelling catalyst is selected from the group consisting of tertiary amines, quaternary ammonium carboxylates, potassium octoate, potassium acetate and organometallics.
  16. 16. The polyurethane foam of any one of claims 8 to 15, further comprising a surfactant, wherein the surfactant is selected to have balanced nucleation and emulsification activity and is a silicone-based surfactant having both lipophilic propyleneoxy and ethyleneoxy polyether side chains.
  17. 17. The polyurethane foam of any one of claims 8 to 16, further comprising a compatibilizer.
  18. 18. The polyurethane foam of claim 17, wherein the weight ratio of the surfactant and the compatibilizer is in the range of 3:1 to 1:1.
  19. 19. A method of forming a polyurethane foam, the method 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 a blowing agent blend according to any one of claims 1 to 7.
  20. 20. The method of claim 19, wherein the polyol premix blend comprises from about 60% to about 90% polyether polyol and from about 10% to about 40% polyester polyol, by weight of the polyol premix blend.

Description

Low GWP blowing agent blends and uses thereof Cross Reference to Related Applications The present application claims the benefit of priority from U.S. provisional application No. 63/546,496 filed on 10/30 of 2023, the disclosure of which is incorporated herein by reference in its entirety. Background Technical Field The present disclosure relates to the use of fluorine-containing blends as blowing agents. More specifically, the process is carried out, the present disclosure relates to E-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd-E) and E-1, 4-hexafluoro-2-butene (HFO-1336 mzz-E) and Z-1, 4 use of a blend of at least one of hexafluoro-2-butene (HFO-1336 mzz-Z) as a blowing agent for polyurethane insulating foams. Description of related Art The low temperature thermal insulation properties of closed cell polyurethane foams in appliances are key enabling factors for achieving energy efficiency goals and environmental sustainability. Improved thermal insulation properties using blowing agent blends with low Global Warming Potential (GWP) unlock further energy savings and drive thermal insulation technology options towards sustainability. Currently, industry practice for polyurethane low temperature insulation employs Hydrofluorocarbons (HFCs), hydrocarbons (hccs), and more recently low GWP Hydrochlorofluoroolefins (HCFO) and Hydrofluoroolefins (HFO). Hydrocarbons are flammable and their low temperature insulating properties are inferior to HFC. HFC has a high GWP and is under regulatory pressure to shrink. HCFO and HFO have low GWP and can be used to meet both performance and sustainability goals. The HCFO and HFO can also be blended with other HCFO and HFO or HFC to produce low GWP blends and HC to suppress flammability to achieve synergistic interactions, which provides improved thermal insulation properties while solving sustainability problems. WO 2008/118627 (assigned to Dow Global Technologies) discloses blowing agents having zero Ozone Depletion Potential (ODP) and GWP of less than 50, and solubility in alkenyl polymers, especially polystyrene, such that more than 50 weight percent (wt%) of these blowing agents, based on the total blowing agent, can produce a good quality foam. Table 2 of WO 2008/118627 discloses HFO-1336mzz (CF 3-CH=CH-CF3) as having moderate solubility compared to the compound of table 1 of WO 2008/118627. It is also disclosed that although the olefins of table 2 may comprise more than 50% by weight of the blowing agent composition, additional blowing agents that are more soluble in the polymer are necessary to achieve a good quality foam (see page 15, lines 9 to 12). High quality foams are described as foams having an average cell size of 0.02mm to 5mm, being closed cell, and having a density of 64kg/m 3 or less. Poor quality marks are small average cell size, densities of greater than 64kg/m 3, high open cell content and air voids (see page 2, lines 9 to 13). The quality foam is also substantially free of air cells, which are described as having a multi-cell size, and which can break at the foam surface to create an irregular surface (see page 2, lines 15 to 20). The non-ruptured pores may be referred to as macropores, and the irregular surface caused by the ruptured pores is opposite to the smooth surface (skin). WO 2008/0154612 (assigned to e.i. du Pont de Nemours and Company) discloses azeotropic and azeotrope-like compositions comprising the E stereoisomer of HFO-1336mzz and methyl formate, n-pentane, 2-methylbutane, E-1, 2-dichloroethylene (E-HFO-1130), 1, 3-pentafluoropropane (HFC-245 fa), n-butane or isobutane. US 2011/0144216 (assigned to Honeywell International inc.) discloses compositions comprising the Z stereoisomer of HFO-1336mzz and its potential use, including as a blowing agent. US 2011/0144216 discloses blends of Z-HFO-1336mzz with HFO, HFC, hydrofluoroether (HFE), chlorofluorocarbon (CFC), carbon dioxide, olefins, organic acids, alcohols, hydrocarbons, ethers, aldehydes, ketones and other substances such as methyl formate. US 9,145,480 (assigned to Honeywell International inc.) discloses compositions comprising a mixture of 1, 4-hexafluorobutene (HFO-1336 mzz) and 1-chloro-3, 3-trifluoropropene (HCFO-1233 zd) as useful blowing agents, solvents, aerosol propellants and heat transfer media for polymer foams. Disclosure of Invention In some embodiments, a blowing agent blend for a polyurethane foam formulation comprises E-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd-E) and at least one compound selected from the group consisting of: E-1, 4-hexafluoro-2-butene (HFO-1336 mzz-E) Z-1, 4-hexafluoro-2-butene (HFO-1336 mzz-Z) and combinations thereof. In some embodiments, the polyurethane foam comprises a plurality of polymer cells and a blowing agent blend comprising E-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd-E) and at least one compound selected from the group consisting of: E-1, 4-hexafluoro-2-butene (HFO-1336 mzz-E) Z-1, 4-hexafluoro-2-butene (HFO-1336 mzz-Z) and co