US20100087557A1 - Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin - Google Patents

Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin Download PDF

Info

Publication number
US20100087557A1
US20100087557A1 US12/532,194 US53219408A US2010087557A1 US 20100087557 A1 US20100087557 A1 US 20100087557A1 US 53219408 A US53219408 A US 53219408A US 2010087557 A1 US2010087557 A1 US 2010087557A1
Authority
US
United States
Prior art keywords
blowing agent
hfo
isomers
hcfo
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/532,194
Inventor
Benjamin Bin Chen
Joseph S. Costa
Brett L. Van Horn
Maher Y. Elsheikh
Philippe Bonnet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema Inc
Original Assignee
Arkema Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=39808678&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20100087557(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Arkema Inc filed Critical Arkema Inc
Priority to US12/532,194 priority Critical patent/US20100087557A1/en
Assigned to ARKEMA INC. reassignment ARKEMA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BONNET, PHILIPPE, CHEN, BENJAMIN BIN, COSTA, JOSEPH S., ELSHEIKH, MAHER Y., VAN HORN, BRETT L.
Publication of US20100087557A1 publication Critical patent/US20100087557A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/104—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/106—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to blowing agents for thermosetting foams. More particularly, the present invention relates to the use of the unsaturated halogenated hydroolefin, 3,3,3-trifluoropropene (HFO-1243zf or TFP) in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof as a blowing agent in the manufacture of thermosetting foams.
  • HFO-1243zf or TFP unsaturated halogenated hydroolefin, 3,3,3-trifluoropropene
  • HCFO hydrochlorofluoroolefin
  • thermoset foams include HFC-134a, HFC-245fa, HFC-365mfc that have relatively high global warming potential, and hydrocarbons such as pentane isomers flammable and have low energy efficiency. Therefore, new alternative blowing agents are being sought.
  • Halogenated hydroolefinic materials such as hydrofluoropropenes and/or hydrochlorofluoropropenes have generated interest as replacements for HFCs. The inherent chemical instability of these materials in the lower atmosphere provides the low global warning potential and zero or near zero ozone depletion properties desired.
  • U.S. Pat. No. 5,205,956 discloses the use of vinyl fluoroalkanes of the formula CH 2 ⁇ CH—C n —F (2n+1) , where n is an integer from 1 to 6, in blowing agent formulations to replace CFC-11 and/or CFC-12.
  • n is preferably from 3 to 6
  • CFC-12 n is preferably from 1 to 3.
  • the examples disclose longer, higher boiling vinyl fluoroalkanes, including vinyl perfluoro-n-butane and vinyl perfluoro-n-hexane, in blowing agent formulations for polyurethane foaming.
  • U.S. Pat. No. 4,085,073 discloses blowing agent compositions containing chlorofluoromethane, bromochlorodifluoromethane, and mixtures thereof. alone or with minor amounts of other halogen containing carbon compounds as blowing agents.
  • GB 950,876 discloses a process for the production of polyurethane foams. It describes that any suitable halogenated saturated or unsaturated hydrocarbon having a boiling point below 150° C., preferably below 50° C., can be used as the blowing agent. TFP is among the halogenated hydrocarbons listed however the examples all employ CFC-11 as the blowing agent.
  • U.S. Pat. No. 6,858,571 and WO 2004/037742 disclose azeotrope-like compositions that contain pentafluoropropene (HFO-1225) and a second fluid from the group consisting of 3,3,3-trifluoropropene (“HFO-1243zf”), 1,1-difluoroethane (“HFC-152a”), trans-1,3,3,3-tetrafluoropropene (“HFO-1234ze”), and combinations of two or more thereof.
  • HFO-1243zf 3,3,3-trifluoropropene
  • HFC-152a 1,1-difluoroethane
  • HFO-1234ze trans-1,3,3,3-tetrafluoropropene
  • WO 2004/037913 and US Pat. Publication 2004119047 disclose a generic formula for HFOs that includes TFP but teach that fluoropropenes containing additional fluorine are preferred, specifically tetrafluoropropenes and pentafluoropropenes, and even more preferred are HFO-1234ze, HFO-1234yf, and HFO-1225ye, and any stereo isomers thereof. There is no disclosure of any advantages of using TFP.
  • US Pat. Publication 2006243944 discloses numerous compositions comprising combinations of materials which include a combination of TFP and at least one other compound selected from a specific list including numerous HFCs and hydrocarbons. The combinations are described as being useful for a variety of uses including use as blowing agents.
  • the object of the present invention is to provide novel compositions that can serve as blowing agents for thermosetting foams that provide unique characteristics to meet the demands of low or zero ozone depletion potential, lower global warming potential and exhibit low toxicity.
  • the present invention relates to the use of blowing agents with negligible (low or zero) ozone-depletion and low GWP based upon unsaturated halogenated hydroolefins.
  • the blowing agents comprise the hydrofluoropropene HFO-1243zf (3,3,3-trifluoropropene) in a combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd (1-chloro-3,3,3-trifluoropropene), HCFO-1233xf (2-chloro-3,3,3-trifluoropropene), HCFO-1223 (dichlorotrifluoropropene) and mixtures thereof.
  • HCFO hydrochlorofluoroolefin
  • the composition can further comprises a second, different hydrofluoroolefin (HFO), a hydrofluorocarbon, a hydrocarbon, an alcohol, an aldehyde, an esyer, a ketone ether/diether or carbon dioxide.
  • HFO hydrofluoroolefin
  • the HFO-1243zf in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof combination can be used as a foaming agent for thermosetting foams by being mixed in a polyols mixture.
  • HCFO hydrochlorofluoroolefin
  • the resulted products show superior quality including decreased density and improved k-factor.
  • the foaming agent readily dissolves in thermosetting polymers, and provides a degree of plasticization sufficient to produce acceptable foams.
  • the preferred blowing agent composition, HFO-1243zf in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof of the present invention exhibits good solubility in polyol mixture used in producing polyurethane and polyisocyanurate foams.
  • a preferred ratio of the HFO-1243zf component in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof is more than about 5wt % HFO-1243zf.
  • hydrofluoropropene HFO-1243zf in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof composition of the present invention may be used in combination with additional low global warming potential and low or zero ozone depletion value materials including but not limited to: (a) hydrofluorocarbons including but not limited to difluoromethane (HFC32), 1,1,1-trifluoroethane (143a), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,2,2-tetrafluorothane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea), 1,1,1,3,3-pentafluopropane (HFC245fa), 1,
  • hydrofluoroolefins including but not limited to tetrafluoropropene (HFO1234), all tetrafluorobutene isomers (HFO1354), all pentafluorobutene isomers (HFO1345), all hexafluorobutene isomers (HFO1336), all heptafluorobutene isomers (HFO1327), all heptafluoropentene isomers (HFO1447), all octafluoropentene isomers (HFO 1438), all nonafluoropentene isomers (HFO 1429)
  • hydrocarbons including but not limited to, pentane isomers, butane isomers, (d) C1 to C5 alcohols, C1 to C4 aldehydes, C1 to C4 ketones, C1 to C4 esters, C1 to C4 ethers and diethers and carbon dioxide.
  • the foamable compositions of the present invention generally include one or more components capable of forming foam having a generally cellular structure and a blowing agent, typically in a combination, in accordance with the present invention.
  • the one or more components comprise a thermosetting composition capable of forming foam and/or foamable compositions.
  • thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and also phenolic foam compositions.
  • one or more of the present compositions are included as or part of a blowing agent in a foamable composition, or as a part of a two or more part foamable composition, which preferably includes one or more of the components capable of reacting and/or foaming under the proper conditions to form a foam or cellular structure.
  • the invention also relates to foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a blowing agent comprising the compositions of the invention.
  • foamable compositions comprising thermosetting foams, such as polyurethane and polyisocyanurate foams, preferably low-density foams, flexible or rigid.
  • blowing agent combination of the present invention does not generally affect the operability of the present invention.
  • the various components of the blowing agent combination, and even the components of the present composition not be mixed in advance of introduction to the foaming equipment, or even that the components are not added to the same location in the foaming equipment.
  • two or more components of the blowing agent combination are combined in advance and introduced together into the foamable composition, either directly or as part of premix that is then further added to other parts of the foamable composition.
  • the foam was made by small polyurethane dispenser unless otherwise specified.
  • the dispenser consisted of two pressurized cylinders, one for the A side (MDI) and one for the B side (polyol mixtures).
  • the pressure in the cylinders could be adjusted by regulators.
  • B-side mixtures were pre-blended and then charged into pressurized cylinders. Blowing agents were then added into B-side cylinder and mixed thoroughly.
  • the cylinders were connected to a dispensing gun equipped with a static mixer. The pressures of both cylinders were adjusted so that desired ratio of the A and B sides could be achieved.
  • Table 2 summarized B-side vapor pressure of different blowing agents.
  • the B-side vapor pressure decreased significantly as a small amount of HCFO1233zd (15.5 mol % of HCFO1233zd over total of HCFO1233zd and HFO 1234zf) was added.
  • K-factor is a key parameter for thermal insulation of foam.
  • Table 3 with the addition of a small amount of HCFO1233zd (15.5 mol % of HCFO1233zd over total of HCFO1233zd and HFO 1234zf), the k-factor is reduced.
  • the k-factor of the foam made of 15.5 mol % of HCFO1233zd and 84.5 mol % of HFO 1243ze is very close to or even better that the foam made of HCFO 1233zd alone. This is particularly useful for low temperature insulation of appliances.
  • Table 4 shows the free rise density was reduced as a small amount of HCFO1233zd (15.5 mol % of HCFO1233zd over total of HCFO1233zd and HFO 1234zf) was added.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A blowing agent for thermosetting foams is disclosed. The blowing agent is the hydrofluoropropene HFO-1243zf in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf and HCFO-1223. The blowing agent is effective as a blowing agent in the manufacture of thermosetting foams.

Description

    FIELD OF THE INVENTION
  • The present invention relates to blowing agents for thermosetting foams. More particularly, the present invention relates to the use of the unsaturated halogenated hydroolefin, 3,3,3-trifluoropropene (HFO-1243zf or TFP) in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof as a blowing agent in the manufacture of thermosetting foams.
    • BACKGROUND OF THE INVENTION
  • The Montreal Protocol for the protection of the ozone layer, signed in October 1987, mandated the phase out of the use of chlorofluorocarbons (CFCs). Materials more “friendly” to the ozone layer, such as hydrofluorocarbons (HFCs) eg HFC-134a replaced chlorofluorocarbons. The latter compounds have proven to be green house gases, causing global warming and were regulated by the Kyoto Protocol on Climate Change, signed in 1998. The emerging replacement materials, hydrofluoropropenes, were shown to be environmentally acceptable ie has zero ozone depletion potential (ODP) and acceptable low GWP.
  • Currently used blowing agents for thermoset foams include HFC-134a, HFC-245fa, HFC-365mfc that have relatively high global warming potential, and hydrocarbons such as pentane isomers flammable and have low energy efficiency. Therefore, new alternative blowing agents are being sought. Halogenated hydroolefinic materials such as hydrofluoropropenes and/or hydrochlorofluoropropenes have generated interest as replacements for HFCs. The inherent chemical instability of these materials in the lower atmosphere provides the low global warning potential and zero or near zero ozone depletion properties desired.
  • U.S. Pat. No. 5,205,956 discloses the use of vinyl fluoroalkanes of the formula CH2═CH—Cn—F(2n+1), where n is an integer from 1 to 6, in blowing agent formulations to replace CFC-11 and/or CFC-12. For replacement of CFC-11 and CFC-113, n is preferably from 3 to 6, and for replacement of CFC-12 n is preferably from 1 to 3. The examples disclose longer, higher boiling vinyl fluoroalkanes, including vinyl perfluoro-n-butane and vinyl perfluoro-n-hexane, in blowing agent formulations for polyurethane foaming.
  • U.S. Pat. No. 4,085,073 discloses blowing agent compositions containing chlorofluoromethane, bromochlorodifluoromethane, and mixtures thereof. alone or with minor amounts of other halogen containing carbon compounds as blowing agents. The patent mentions TFP, along with a list of other halogenated compounds as possible diluents.
  • GB 950,876 discloses a process for the production of polyurethane foams. It describes that any suitable halogenated saturated or unsaturated hydrocarbon having a boiling point below 150° C., preferably below 50° C., can be used as the blowing agent. TFP is among the halogenated hydrocarbons listed however the examples all employ CFC-11 as the blowing agent.
  • U.S. Pat. No. 6,858,571 and WO 2004/037742 disclose azeotrope-like compositions that contain pentafluoropropene (HFO-1225) and a second fluid from the group consisting of 3,3,3-trifluoropropene (“HFO-1243zf”), 1,1-difluoroethane (“HFC-152a”), trans-1,3,3,3-tetrafluoropropene (“HFO-1234ze”), and combinations of two or more thereof. The use of these azeeotropes as blowing agents is mentioned.
  • WO 2004/037913 and US Pat. Publication 2004119047 disclose a generic formula for HFOs that includes TFP but teach that fluoropropenes containing additional fluorine are preferred, specifically tetrafluoropropenes and pentafluoropropenes, and even more preferred are HFO-1234ze, HFO-1234yf, and HFO-1225ye, and any stereo isomers thereof. There is no disclosure of any advantages of using TFP.
  • US Pat. Publication 2006243944 discloses numerous compositions comprising combinations of materials which include a combination of TFP and at least one other compound selected from a specific list including numerous HFCs and hydrocarbons. The combinations are described as being useful for a variety of uses including use as blowing agents.
  • The object of the present invention is to provide novel compositions that can serve as blowing agents for thermosetting foams that provide unique characteristics to meet the demands of low or zero ozone depletion potential, lower global warming potential and exhibit low toxicity.
    • SUMMARY OF THE INVENTION
  • The present invention relates to the use of blowing agents with negligible (low or zero) ozone-depletion and low GWP based upon unsaturated halogenated hydroolefins. The blowing agents comprise the hydrofluoropropene HFO-1243zf (3,3,3-trifluoropropene) in a combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd (1-chloro-3,3,3-trifluoropropene), HCFO-1233xf (2-chloro-3,3,3-trifluoropropene), HCFO-1223 (dichlorotrifluoropropene) and mixtures thereof. The composition can further comprises a second, different hydrofluoroolefin (HFO), a hydrofluorocarbon, a hydrocarbon, an alcohol, an aldehyde, an esyer, a ketone ether/diether or carbon dioxide.
  • The HFO-1243zf in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof combination can be used as a foaming agent for thermosetting foams by being mixed in a polyols mixture. The resulted products show superior quality including decreased density and improved k-factor. The foaming agent readily dissolves in thermosetting polymers, and provides a degree of plasticization sufficient to produce acceptable foams.
  • The preferred blowing agent composition, HFO-1243zf in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof of the present invention exhibits good solubility in polyol mixture used in producing polyurethane and polyisocyanurate foams. A preferred ratio of the HFO-1243zf component in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof is more than about 5wt % HFO-1243zf.
  • The hydrofluoropropene HFO-1243zf in combination with a hydrochlorofluoroolefin (HCFO) selected from HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof composition of the present invention may be used in combination with additional low global warming potential and low or zero ozone depletion value materials including but not limited to: (a) hydrofluorocarbons including but not limited to difluoromethane (HFC32), 1,1,1-trifluoroethane (143a), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,2,2-tetrafluorothane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea), 1,1,1,3,3-pentafluopropane (HFC245fa), 1,1,1,3,3-pentafluobutane (HFC365mfc)and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee). (b) hydrofluoroolefins including but not limited to tetrafluoropropene (HFO1234), all tetrafluorobutene isomers (HFO1354), all pentafluorobutene isomers (HFO1345), all hexafluorobutene isomers (HFO1336), all heptafluorobutene isomers (HFO1327), all heptafluoropentene isomers (HFO1447), all octafluoropentene isomers (HFO 1438), all nonafluoropentene isomers (HFO 1429) (c) hydrocarbons including but not limited to, pentane isomers, butane isomers, (d) C1 to C5 alcohols, C1 to C4 aldehydes, C1 to C4 ketones, C1 to C4 esters, C1 to C4 ethers and diethers and carbon dioxide.
  • The foamable compositions of the present invention generally include one or more components capable of forming foam having a generally cellular structure and a blowing agent, typically in a combination, in accordance with the present invention. In certain embodiments, the one or more components comprise a thermosetting composition capable of forming foam and/or foamable compositions. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and also phenolic foam compositions. In such thermosetting foam embodiments, one or more of the present compositions are included as or part of a blowing agent in a foamable composition, or as a part of a two or more part foamable composition, which preferably includes one or more of the components capable of reacting and/or foaming under the proper conditions to form a foam or cellular structure.
  • The invention also relates to foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a blowing agent comprising the compositions of the invention. In yet other embodiments, the invention provides foamable compositions comprising thermosetting foams, such as polyurethane and polyisocyanurate foams, preferably low-density foams, flexible or rigid.
  • It will be appreciated by those skilled in the art that the order and manner in which the blowing agent combination of the present invention is formed and/or added to the foamable composition does not generally affect the operability of the present invention. For example, in the case of polyurethane foams, it is possible that the various components of the blowing agent combination, and even the components of the present composition, not be mixed in advance of introduction to the foaming equipment, or even that the components are not added to the same location in the foaming equipment. Thus, in certain embodiments it may be desired to introduce one or more components of the blowing agent combination in a blender with the expectation that the components will come together in the foaming equipment and/or operate more effectively in this manner. Nevertheless, in certain embodiments, two or more components of the blowing agent combination are combined in advance and introduced together into the foamable composition, either directly or as part of premix that is then further added to other parts of the foamable composition.
    • EXAMPLES Example 1
  • In the following examples, the foam was made by small polyurethane dispenser unless otherwise specified. The dispenser consisted of two pressurized cylinders, one for the A side (MDI) and one for the B side (polyol mixtures). The pressure in the cylinders could be adjusted by regulators. B-side mixtures were pre-blended and then charged into pressurized cylinders. Blowing agents were then added into B-side cylinder and mixed thoroughly. The cylinders were connected to a dispensing gun equipped with a static mixer. The pressures of both cylinders were adjusted so that desired ratio of the A and B sides could be achieved. The formulations tested (all had an Iso Index on ROH of 110) each contained Rubinate M, a polymeric methylene diphenyl diisocyanate (MDI) available from Huntsman; Jeffol SG-360 and R-425-X, polyols from Huntsman; TEAP-265, a polyol from Carpenter Company. TegostabB 8465 a surfactant available from Evonik-Degussa. Jeffcat TD33A and ZR-70 are catalysts from Huntsman. NP 9.5, a compatibilizer from Huntsman. Total blowing agent level was 26.0 mls/g. Table 1 summarizes the formulations of the study.
  • TABLE 1
    Formulations
    HFO1243zf +
    HFO1243zf HCFO1233zd HFO1234ze HCFO1233zd
    Jeffol SG-360 15.45 14.77 14.93 15.35
    Jeffol R-425-X 4.41 4.22 4.27 4.39
    TEAP-265 8.83 8.44 8.53 8.77
    DEG 2.21 2.11 2.13 2.19
    Jeffcat TD33A 0.23 0.23 0.23 0.23
    Jeffcat ZR70 0.23 0.23 0.23 0.23
    Tegostab B8465 0.90 0.90 0.89 0.90
    NP 9.5 6.50 6.50 6.43 6.50
    Water 0.42 0.42 0.41 0.42
    HFO 1243zf 8.92 0 0 7.54
    HFO1234ze 0 0 11.56 0
    HCFO1233zd 0 12.11 0 1.89
    HFC 134a 0 0 0 0
    Rubinate M 51.9 50.1 50.4 51.6
    A side/B side 1.08 1.00 1.02 1.07
    • Example 2
  • Table 2 summarized B-side vapor pressure of different blowing agents.
  • TABLE 2
    B-side vapor pressure
    Blowing agent B-side Vapor pressure (psig)
    HFO1243zf 133
    HCFO1233zd 0
    HFO 1234ze 44
    HFO 1243zf + HCFO1233zd 84
  • The B-side vapor pressure decreased significantly as a small amount of HCFO1233zd (15.5 mol % of HCFO1233zd over total of HCFO1233zd and HFO 1234zf) was added.
    • Example 3
  • TABLE 3
    K-factor
    Temp. HFO1243zf +
    (° F.) HFO1243zf HCFO1233zd HFO1234ze HCFO1233zd
    17.6 0.1267 0.1222 0.1337 0.1211
    32.0 0.1324 0.1250 0.1373 0.1265
    50.2 0.1401 0.1302 0.1430 0.1340
    75.2 0.1521 0.1416 0.1542 0.1458
    104.0 0.1659 0.1549 0.1677 0.1595
  • K-factor is a key parameter for thermal insulation of foam. The lower the k-factor, the better the thermal insulation. As shown in Table 3, with the addition of a small amount of HCFO1233zd (15.5 mol % of HCFO1233zd over total of HCFO1233zd and HFO 1234zf), the k-factor is reduced. At low temperatures, the k-factor of the foam made of 15.5 mol % of HCFO1233zd and 84.5 mol % of HFO 1243ze is very close to or even better that the foam made of HCFO 1233zd alone. This is particularly useful for low temperature insulation of appliances.
    • Example 4
  • TABLE 4
    Free Rise Density
    Blowing agent Free Rise Density (pcf)
    HFO1243zf 2.06
    HCFO1233zd 1.71
    HFO1234ze 1.78
    HFO1243zf + HCFO1233zd 1.94
  • Table 4 shows the free rise density was reduced as a small amount of HCFO1233zd (15.5 mol % of HCFO1233zd over total of HCFO1233zd and HFO 1234zf) was added. The lower the free rise density, the higher the blowing efficiency that can bring processing benefits such as better flowability of foam precursor. Low free rise density results in lower fill weight and material savings.
  • Although the invention is illustrated and described herein with reference to specific embodiments, it is not intended that the appended claims be limited to the details shown. Rather, it is expected that various modifications may be made in these details by those skilled in the art, which modifications may still be within the spirit and scope of the claimed subject matter and it is intended that these claims be construed accordingly.

Claims (14)

1. A polymer blowing agent composition for thermosetting foams comprising the hydrofluoropropene HFO-1243zf in combination with a hydrochlorofluoroolefin selected from the group consisting of HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof.
2. The polymer blowing agent composition of claim 1 wherein said hydrofluoropropene HFO-1243zf comprises about 5 wt % or more of the hydrofluoropropene and hydrochlorofluoroolefin composition.
3. The polymer blowing agent composition of claim 1, further comprising a hydroflouorcarbon.
4. The polymer blowing agent composition of claim 3 wherein said hydrofluorocarbon is selected from the group consisting of difluoromethane (HFC32); 1,1,1-trifluoroethane (HFC143a); 1,1,1,2,2-pentafluoroethane (HFC125); 1,1,2,2-tetrafluoroethane (HFC134); 1,1,1,2-tetrafluoroethane (HFC134a); 1,1-difluoroethane (HFC152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea); 1,1,1,3,3-pentafluoropropane (HFC245fa); 1,1,1,3,3-pentafluorobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee).
5. The polymer blowing agent composition of claim 1, further comprising a hydrofluoroolefin.
6. The polymer blowing agent composition of claim 5 wherein said hydrofluoroolefin is selected form the group consisting of tetrafluoropropenes (HFO1234), tetrafluorobutene isomers (HFO1354), pentafluorobutene isomers (HFO1345), hexafluorobutene isomers (HFO1336), heptafluorobutene isomers (HFO1327), heptafluoropentene isomers (HFO1447), octafluoropentene isomers (HFO 1438), nonafluoropentene (HFO 1429).
7. The polymer blowing agent composition of claim 1, further comprising a component selected from the group consisting of a second hydrofluoroolefin (HFO), a hydrofluorocarbon, a hydrocarbon, an alcohol, an aldehyde, an ester, a ketone ether/diether or carbon dioxide.
8. A process of foaming a polyurethane foam comprising mixing polymer foam components with a foam blowing agent comprising the hydrofluoropropene HFO-1243zf in combination with a hydrochlorofluoroolefin (HCFO) selected from the group consisting of HCFO-1233zd, HCFO-1233xf, HCFO-1223 and mixtures thereof.
9. The process of 8 wherein said hydrofluoropropene HFO-1243zf comprises about 5 wt % or more of the hydrofluoropropene and hydrochlorofluoroolefin composition.
10. The process of claim 8, wherein said foam blowing agent further comprising further comprising a hydrofluorocarbon.
11. The process of claim 10 wherein said hydrofluorocarbon is selected from the group consisting of difluoromethane (HFC32); 1,1,1,2,2-pentafluoroethane (HFC125); 1,1,1-trifluoroethane (HFC143a); 1,1,2,2-tetrafluoroethane (HFC134); 1,1,1,2-tetrafluoroethane (HFC134a); 1,1-difluoroethane (HFC152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea); 1,1,1,3,3-pentafluoropropane (HFC245fa); 1,1,1,3,3-pentafluorobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee).
12. The process of claim 8, wherein said foam blowing agent further comprising a hydrofluoroolefin.
13. The process of claim 12 wherein said hydrofluoroolefin is selected form the group consisting of 1,1,1,2-tetrafluoropropenes (HFO1234), tetrafluorobutene isomers (HFO1354), pentafluorobutene isomers (HFO1345), hexafluorobutene isomers (HFO1336), heptafluorobutene isomers (HFO1327), heptafluoropentene isomers (HFO1447), octafluoropentene isomers (HFO 1438) and nonafluoropentene (HFO 1429).
14. The process of claim 8 wherein said blowing agent further comprises a component selected from the group consisting of a second hydrofluoroolefin (HFO), a hydrofluorocarbon, a hydrocarbon, an alcohol, an aldehyde, an ester, a ketone ether/diether or carbon dioxide.
US12/532,194 2007-03-29 2008-03-28 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin Abandoned US20100087557A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/532,194 US20100087557A1 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US90875107P 2007-03-29 2007-03-29
PCT/US2008/058604 WO2008121787A1 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin
US12/532,194 US20100087557A1 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/058604 A-371-Of-International WO2008121787A1 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/339,732 Division US20140336293A1 (en) 2007-03-29 2014-07-24 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin

Publications (1)

Publication Number Publication Date
US20100087557A1 true US20100087557A1 (en) 2010-04-08

Family

ID=39808678

Family Applications (8)

Application Number Title Priority Date Filing Date
US12/532,202 Active US9279039B2 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US12/532,194 Abandoned US20100087557A1 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin
US12/532,189 Abandoned US20100056657A1 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US14/305,287 Active US9228071B2 (en) 2007-03-29 2014-06-16 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US14/339,732 Abandoned US20140336293A1 (en) 2007-03-29 2014-07-24 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin
US14/964,896 Abandoned US20160090462A1 (en) 2007-03-29 2015-12-10 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US15/015,184 Active US9914815B2 (en) 2007-03-29 2016-02-04 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US15/245,412 Abandoned US20160362531A1 (en) 2007-03-29 2016-08-24 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US12/532,202 Active US9279039B2 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin

Family Applications After (6)

Application Number Title Priority Date Filing Date
US12/532,189 Abandoned US20100056657A1 (en) 2007-03-29 2008-03-28 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US14/305,287 Active US9228071B2 (en) 2007-03-29 2014-06-16 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US14/339,732 Abandoned US20140336293A1 (en) 2007-03-29 2014-07-24 Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin
US14/964,896 Abandoned US20160090462A1 (en) 2007-03-29 2015-12-10 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US15/015,184 Active US9914815B2 (en) 2007-03-29 2016-02-04 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin
US15/245,412 Abandoned US20160362531A1 (en) 2007-03-29 2016-08-24 Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin

Country Status (9)

Country Link
US (8) US9279039B2 (en)
EP (3) EP2129715B1 (en)
JP (3) JP5416086B2 (en)
CN (6) CN101646722A (en)
AT (3) ATE518905T1 (en)
CA (3) CA2681838C (en)
ES (3) ES2367542T3 (en)
PL (3) PL2129715T3 (en)
WO (3) WO2008121790A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100216904A1 (en) * 2009-02-24 2010-08-26 E. I. Du Pont De Nemours And Company Foam-forming compositions containing mixtures of 2-chloro-3,3,3-trifluoropropene and at least one hydrofluoroolefin and their uses in the preparation of polyisocyanate-based foams
US20110001080A1 (en) * 2008-03-07 2011-01-06 Arkema Inc. Stable formulated systems with chloro-3,3,3-trifluoropropene
US20110124758A1 (en) * 2008-08-13 2011-05-26 E.I. Du Pont De Nemours And Company Foam-forming compositions containing mixtures of 2-chloro-3,3,3-trifluoropropene and hydrocarbon and their uses in the preparation of polyisocyanate-based foams
US20110124756A1 (en) * 2009-05-21 2011-05-26 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US20120101177A1 (en) * 2007-03-29 2012-04-26 Arkema Inc. Blowing agent compositions of hydrochlorofluoroolefins
WO2012024252A3 (en) * 2010-08-17 2012-05-31 Honeywell International Inc. Compositions containing 1-chloro-3,3,3 trifluoropropene and 1-fluoro-1,1 dichloroethane
WO2013096727A1 (en) * 2011-12-22 2013-06-27 Honeywell International Inc. Azeotrope-like compositions including cis-1-chloro-3,3,3-trifluoropropene
US8680168B2 (en) 2010-11-17 2014-03-25 Fomo Products, Inc. Method for filling wall cavities with expanding foam insulation
US20150210818A1 (en) * 2014-01-27 2015-07-30 E I Du Pont De Nemours And Company Cryogenic insulation foam
WO2015168486A1 (en) * 2014-04-30 2015-11-05 Honeywell International Inc. Flexible, open-cell thermoset foams and blowing agents and methods for making same
US10113046B2 (en) 2009-10-23 2018-10-30 Arkema Inc Tetrafluorobutene blowing agent compositions for polyurethane foams
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase

Families Citing this family (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090253820A1 (en) * 2006-03-21 2009-10-08 Honeywell International Inc. Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming
US9499729B2 (en) * 2006-06-26 2016-11-22 Honeywell International Inc. Compositions and methods containing fluorine substituted olefins
TWI626262B (en) † 2005-06-24 2018-06-11 哈尼威爾國際公司 Foams and products thereof
US9695267B2 (en) * 2009-08-11 2017-07-04 Honeywell International Inc. Foams and foamable compositions containing halogenated olefin blowing agents
US20100210747A1 (en) * 2007-07-20 2010-08-19 E.I. Du Pont De Nemours And Company Compositions and use of trans-1,1,1,4,4,4-hexafluoro-2-butene foam-forming composition in the preparation of polyisocyanate-based foams
US8333901B2 (en) 2007-10-12 2012-12-18 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US8512591B2 (en) 2007-10-12 2013-08-20 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US8628681B2 (en) 2007-10-12 2014-01-14 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
GB201002625D0 (en) 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
WO2009047542A1 (en) * 2007-10-12 2009-04-16 Ineos Fluor Holdings Limited Heat transfer compositions
WO2009089400A1 (en) * 2008-01-11 2009-07-16 E. I. Du Pont De Nemours And Company Compositions and use of 2-chloro-3,3,3-trifluoropropene foam-forming composition in the preparation of polyisocyanate-based foams
EP2634231B1 (en) * 2008-05-07 2022-06-29 The Chemours Company FC, LLC Compositions
US8163196B2 (en) * 2008-10-28 2012-04-24 Honeywell International Inc. Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene
CN102239228A (en) * 2008-12-02 2011-11-09 墨西哥化学阿玛科股份有限公司 Heat transfer compositions
WO2010088320A1 (en) * 2009-01-29 2010-08-05 Arkema Inc. Tetrafluoropropene based blowing agent compositions
TW201103972A (en) 2009-04-01 2011-02-01 Solvay Fluor Gmbh Process for the manufacture of etched items
CA2761720C (en) * 2009-06-02 2017-07-11 E. I. Du Pont De Nemours And Company Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluoro-2-butene
US20120145955A1 (en) * 2009-07-27 2012-06-14 Arkema Inc. COMPOSITION OF HCFO-1233zd AND POLYOL BLENDS FOR USE IN POLYURETHANE FOAM
DE102009028061A1 (en) 2009-07-29 2011-02-10 Evonik Goldschmidt Gmbh Process for the production of polyurethane foam
SI3812360T1 (en) * 2009-09-09 2024-02-29 Honeywell International Inc. Monochlorotrifluoropropene compounds and compositions and methods using same
US8846754B2 (en) * 2009-12-16 2014-09-30 Honeywell International Inc. Azeotrope-like compositions of cis-1,1,1,4,4,4-hexafluoro-2-butene
KR20220104282A (en) 2009-12-22 2022-07-26 더 케무어스 컴퍼니 에프씨, 엘엘씨 Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane
GB201002622D0 (en) 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
US8821749B2 (en) * 2010-04-26 2014-09-02 E I Du Pont De Nemours And Company Azeotrope-like compositions of E-1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene
BR112012029453A2 (en) 2010-05-20 2017-03-07 Mexichem Amanco Holding Sa "heat transfer, foaming and spray compositions, heat transfer and mechanical energy generating devices, use of a composition, blowing agent, foam, and methods for cooling an article, for heating an article, for extract a biomass substance, to clean an article, to extract a material from an aqueous solution, to extract a material from a particulate solid matrix, to reform a heat transfer device, to reduce the environmental impact of operating a product , to prepare a composition and to generate greenhouse gas emission credit "
PL2571956T3 (en) 2010-05-20 2016-06-30 Mexichem Fluor Sa De Cv Heat transfer compositions
GB2481443B (en) 2010-06-25 2012-10-17 Mexichem Amanco Holding Sa Heat transfer compositions
US20120046372A1 (en) * 2010-08-18 2012-02-23 Honeywell International Inc. Blowing agents, foamable compositions and foams
US9145480B2 (en) * 2010-10-28 2015-09-29 Honeywell International Inc. Mixtures containing 1,1,1,3,3,3-hexafluorobutene and 1-chloro-3,3,3-trifluoropropene
US8734671B2 (en) * 2010-11-19 2014-05-27 Honeywell International Inc. Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene
EP3543311B1 (en) * 2010-11-25 2022-11-09 Arkema France Use of compositions of chloro-trifluoropropene and hexafluorobutene
FR2968310B1 (en) * 2010-12-03 2012-12-07 Arkema France COMPOSITIONS BASED ON 1,1,1,4,4,4-HEXAFLUOROBUT-2-ENE AND 3,3,4,4,4-PENTAFLUOROBUT-1-ENE
MX2013007318A (en) 2010-12-21 2013-07-22 Dow Global Technologies Llc Polyol formulations for improved cold temperature skin cure of polyurethane rigid foams.
US9724684B2 (en) 2011-02-21 2017-08-08 The Chemours Company Fc, Llc Selective catalytical dehydrochlorination of hydrochlorofluorocarbons
FR2977256B1 (en) * 2011-07-01 2013-06-21 Arkema France COMPOSITIONS OF 2,4,4,4-TETRAFLUOROBUT-1-ENE AND CIS-1,1,1,4,4,4-HEXAFLUOROBUT-2-ENE
RU2016137830A (en) * 2011-07-28 2018-12-12 Ханивелл Интернешнл Инк. FOAMS AND FIRE-RESISTANT PRODUCTS OBTAINED FROM FOAMS CONTAINING 1-CHLOR-3, 3, 3-TRIFTORPROPEN (1233ZD)
US9896558B2 (en) 2011-08-01 2018-02-20 Basf Se HFO/water-blown rigid foam systems
BR112014002392B1 (en) 2011-08-01 2020-11-10 Basf Se process to produce rigid polyurethane foams, use of a blowing agent mixture, and rigid polyurethane foam
ES2841988T3 (en) 2011-10-14 2021-07-12 Dow Global Technologies Llc Hybrid polyester-polyether polyols for improved release expansion in rigid polyurethane foams
AU2012325962B2 (en) 2011-10-20 2016-05-19 The Chemours Company Fc, Llc. Azeotrope-like compositions of E-1-chloro-2,3,3,3-tetrafluoropropene and uses thereof
WO2013082964A1 (en) * 2011-12-09 2013-06-13 Honeywell International Inc. Foams and articles made from foams containing hcfo or hfo blowing agents
US8921621B2 (en) 2012-02-15 2014-12-30 Honeywell International Inc. Process for the production of HCFC-1233zd
US9000239B2 (en) * 2012-05-15 2015-04-07 Honeywell International Inc. Methods for producing 1-chloro-3,3,3-trifluoropropene from 2-chloro-3,3,3-trifluoropropene
US20150118476A1 (en) 2012-05-25 2015-04-30 Dow Global Technologies Llc Production of polyisocyanurate foam panels
CN104781315B (en) * 2012-09-07 2019-03-08 巴斯夫欧洲公司 Reduce the hard polyurethane foams shunk
CN102850571A (en) * 2012-09-28 2013-01-02 关志强 Foaming agent of heat insulation polyurethane plastics
FR3000094B1 (en) * 2012-12-26 2019-10-18 Arkema France COMPOSITION COMPRISING 1,1-DIFLUOROETHANE AND 3,3,3-TRIFLUOROPROPENE
CN111925775A (en) * 2013-03-14 2020-11-13 霍尼韦尔国际公司 Low GWP fluids for high temperature heat pump applications
EP3495407B1 (en) 2013-03-15 2024-01-03 Owens Corning Intellectual Capital, LLC Processing aids for use in manufacturing extruded polystyrene foams using low global warming potential blowing agents
CN103881131A (en) * 2014-03-17 2014-06-25 浙江衢化氟化学有限公司 Environment-friendly foaming agent composition
US10330364B2 (en) 2014-06-26 2019-06-25 Hudson Technologies, Inc. System and method for retrofitting a refrigeration system from HCFC to HFC refrigerant
CN104119490A (en) * 2014-07-10 2014-10-29 合肥美的电冰箱有限公司 A composition, a foam material prepared from the composition, a preparing method of the foam material and applications of the foam material
CA2955293C (en) * 2014-07-16 2023-03-28 Owens Corning Intellectual Capital, Llc Non-voc processing aids for use in manufacturing foams using low global warming potential blowing agents
JP6626674B2 (en) * 2014-10-08 2019-12-25 積水ソフランウイズ株式会社 Polyol composition for rigid polyurethane foam, and method for producing rigid polyurethane foam
KR102589518B1 (en) * 2015-03-24 2023-10-16 세키스이가가쿠 고교가부시키가이샤 Phenolic resin foam and method for producing phenolic resin foam
JP6208399B2 (en) * 2015-03-24 2017-10-04 旭化成建材株式会社 Phenol resin foam and method for producing the same
CN107849500B (en) * 2015-07-27 2020-11-06 Ａｇｃ株式会社 Solvent composition, cleaning method, method for forming coating film, heat transfer medium, and heat cycle system
CN105885080A (en) * 2016-05-05 2016-08-24 巨化集团技术中心 Foamer composition and preparation method thereof
CH712779A1 (en) * 2016-07-20 2018-01-31 Brugg Rohr Ag Holding Barrier layers.
US10131758B2 (en) 2016-07-25 2018-11-20 Accella Polyurethane Systems, Llc Polyurethane foam-forming compositions, methods of making low density foams using such compositions, and foams formed therefrom
CN106750488B (en) * 2016-12-26 2019-05-17 浙江衢化氟化学有限公司 A kind of low-carbon environment-friendly foaming agent
CN108727551A (en) * 2017-04-19 2018-11-02 科思创德国股份有限公司 A kind of hard polyurethane foams and the preparation method and application thereof
CN108102333A (en) * 2017-12-27 2018-06-01 上海东大聚氨酯有限公司 A kind of ultralow temperature incubator combined polyether, polyurethane raw material composition, polyurethane foam and preparation method thereof
WO2020022478A1 (en) * 2018-07-27 2020-01-30 セントラル硝子株式会社 Solvent composition
CN110105520B (en) * 2019-05-05 2021-09-21 深圳市盈石科技有限公司 Heat-insulating rigid polyurethane foam and preparation method thereof
CA3167790A1 (en) * 2020-02-04 2021-08-12 The Chemours Company Fc, Llc Nucleating agents for pir foams
WO2022009801A1 (en) * 2020-07-08 2022-01-13 Ａｇｃ株式会社 Composition and use thereof
CN114149790B (en) * 2021-11-10 2023-09-05 浙江巨化新材料研究院有限公司 Azeotropic or azeotrope-like compositions and methods of making same
WO2023221693A1 (en) * 2022-05-20 2023-11-23 海信容声(广东)冰箱有限公司 Rigid polyurethane foam, preparation method, and heat preservation material, refrigerator and freezer comprising polyurethane foam

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013846A (en) * 1998-03-05 2000-01-11 Elf Atochem North America, Inc. Azeotrope of HF and 1233zd
US6858571B2 (en) * 2002-10-25 2005-02-22 Honeywell International Inc. Pentafluoropropene-based compositions

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2039008A (en) 1932-07-28 1936-04-28 Burgess Lab Inc C F Method of making a material for absorbing sound
JPH02221388A (en) 1989-02-23 1990-09-04 Asahi Glass Co Ltd Degreasing detergent
JP2751428B2 (en) * 1989-06-30 1998-05-18 旭硝子株式会社 3,3-dichloro-1,1,1,2,2-pentafluoropropane-based composition
JPH05179042A (en) * 1991-11-18 1993-07-20 Daikin Ind Ltd Blowing agent comprising fluoropropene and production of plastic foam
US5710352A (en) 1996-09-19 1998-01-20 Alliedsignal Inc. Vapor phase process for making 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3-trifluoropropene
EP0864554B1 (en) 1997-03-11 2002-09-18 Central Glass Company, Limited Method for purifying crude 1,1,1,3,3-pentafluoropropane
US20050096246A1 (en) * 2003-11-04 2005-05-05 Johnson Robert C. Solvent compositions containing chlorofluoroolefins
US9796848B2 (en) * 2002-10-25 2017-10-24 Honeywell International Inc. Foaming agents and compositions containing fluorine substituted olefins and methods of foaming
US20090253820A1 (en) 2006-03-21 2009-10-08 Honeywell International Inc. Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming
US7279451B2 (en) * 2002-10-25 2007-10-09 Honeywell International Inc. Compositions containing fluorine substituted olefins
US9499729B2 (en) 2006-06-26 2016-11-22 Honeywell International Inc. Compositions and methods containing fluorine substituted olefins
US7098176B2 (en) 2004-04-16 2006-08-29 Honeywell International Inc. Azeotrope-like compositions of tetrafluoropropene and pentafluoropropene
ES2366706T3 (en) 2004-12-21 2011-10-24 Honeywell International Inc. STABILIZED IODOCARBON COMPOSITIONS.
US20060243945A1 (en) * 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
US20060243944A1 (en) * 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
TWI657070B (en) 2005-06-24 2019-04-21 美商哈尼威爾國際公司 Compositions containing fluorine substituted olefins and uses thereof
TWI626262B (en) * 2005-06-24 2018-06-11 哈尼威爾國際公司 Foams and products thereof
CA2681832C (en) 2007-03-29 2016-01-26 Arkema Inc. Blowing agent composition of hydrochlorofluoroolefin
CN100488925C (en) 2007-04-11 2009-05-20 西安近代化学研究所 Method for producing 1,1,1,3-tetrafluoroethylene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013846A (en) * 1998-03-05 2000-01-11 Elf Atochem North America, Inc. Azeotrope of HF and 1233zd
US6858571B2 (en) * 2002-10-25 2005-02-22 Honeywell International Inc. Pentafluoropropene-based compositions

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120101177A1 (en) * 2007-03-29 2012-04-26 Arkema Inc. Blowing agent compositions of hydrochlorofluoroolefins
US20110001080A1 (en) * 2008-03-07 2011-01-06 Arkema Inc. Stable formulated systems with chloro-3,3,3-trifluoropropene
US9254468B2 (en) 2008-03-07 2016-02-09 Arkema Inc. Stable formulated systems with chloro-3,3,3-trifluoropropene
US10072192B2 (en) 2008-03-07 2018-09-11 Arkema Inc. Stable formulated systems with chloro-3,3,3-trifluoropropene
US20110124758A1 (en) * 2008-08-13 2011-05-26 E.I. Du Pont De Nemours And Company Foam-forming compositions containing mixtures of 2-chloro-3,3,3-trifluoropropene and hydrocarbon and their uses in the preparation of polyisocyanate-based foams
US20100216904A1 (en) * 2009-02-24 2010-08-26 E. I. Du Pont De Nemours And Company Foam-forming compositions containing mixtures of 2-chloro-3,3,3-trifluoropropene and at least one hydrofluoroolefin and their uses in the preparation of polyisocyanate-based foams
US20110124756A1 (en) * 2009-05-21 2011-05-26 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US8541478B2 (en) * 2009-05-21 2013-09-24 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US9587080B2 (en) 2009-05-21 2017-03-07 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US8937107B2 (en) 2009-05-21 2015-01-20 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US9527976B2 (en) 2009-05-21 2016-12-27 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US9238722B2 (en) 2009-05-21 2016-01-19 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US9238721B2 (en) 2009-05-21 2016-01-19 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US10113046B2 (en) 2009-10-23 2018-10-30 Arkema Inc Tetrafluorobutene blowing agent compositions for polyurethane foams
CN103153925A (en) * 2010-08-17 2013-06-12 霍尼韦尔国际公司 Compositions containing 1-chloro-3,3,3 trifluoropropene and 1-fluoro-1,1 dichloroethane
WO2012024252A3 (en) * 2010-08-17 2012-05-31 Honeywell International Inc. Compositions containing 1-chloro-3,3,3 trifluoropropene and 1-fluoro-1,1 dichloroethane
US8680168B2 (en) 2010-11-17 2014-03-25 Fomo Products, Inc. Method for filling wall cavities with expanding foam insulation
WO2013096727A1 (en) * 2011-12-22 2013-06-27 Honeywell International Inc. Azeotrope-like compositions including cis-1-chloro-3,3,3-trifluoropropene
US20150210818A1 (en) * 2014-01-27 2015-07-30 E I Du Pont De Nemours And Company Cryogenic insulation foam
WO2015168486A1 (en) * 2014-04-30 2015-11-05 Honeywell International Inc. Flexible, open-cell thermoset foams and blowing agents and methods for making same
CN106459338A (en) * 2014-04-30 2017-02-22 霍尼韦尔国际公司 Flexible, open-cell thermoset foams and blowing agents and methods for making same
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
US10988422B2 (en) 2015-05-21 2021-04-27 The Chemours Company Fc, Llc Hydrofluoroalkane composition
US11008267B2 (en) 2015-05-21 2021-05-18 The Chemours Company Fc, Llc Hydrofluoroalkane composition
US11572326B2 (en) 2015-05-21 2023-02-07 The Chemours Company Fc, Llc Method for preparing 1,1,1,2,2-pentafluoropropane
US12006274B2 (en) 2015-05-21 2024-06-11 The Chemours Company Fc, Llc Compositions including olefin and hydrofluoroalkane

Also Published As

Publication number Publication date
EP2129714B1 (en) 2011-08-03
US20140296360A1 (en) 2014-10-02
ATE528341T1 (en) 2011-10-15
EP2129715A4 (en) 2010-03-24
CA2681642A1 (en) 2008-10-09
US9914815B2 (en) 2018-03-13
CA2681838C (en) 2015-05-26
CN104962070A (en) 2015-10-07
WO2008121790A1 (en) 2008-10-09
JP2010522822A (en) 2010-07-08
EP2129715A1 (en) 2009-12-09
EP2129714A1 (en) 2009-12-09
CN101652412A (en) 2010-02-17
CA2681642C (en) 2015-05-26
ATE547459T1 (en) 2012-03-15
ES2380080T3 (en) 2012-05-08
CN101646723A (en) 2010-02-10
CN104962070B (en) 2018-06-01
JP2010522820A (en) 2010-07-08
PL2129713T3 (en) 2012-10-31
US20160152787A1 (en) 2016-06-02
US20100076100A1 (en) 2010-03-25
ES2372785T3 (en) 2012-01-26
EP2129715B1 (en) 2011-10-12
WO2008121787A1 (en) 2008-10-09
JP2010522821A (en) 2010-07-08
CN103992498B (en) 2017-11-07
US9228071B2 (en) 2016-01-05
JP5416086B2 (en) 2014-02-12
CN101652413A (en) 2010-02-17
US20160090462A1 (en) 2016-03-31
CN101646722A (en) 2010-02-10
US9279039B2 (en) 2016-03-08
JP5416087B2 (en) 2014-02-12
US20140336293A1 (en) 2014-11-13
WO2008121785A1 (en) 2008-10-09
CA2681872A1 (en) 2008-10-09
PL2129714T3 (en) 2012-04-30
ATE518905T1 (en) 2011-08-15
EP2129713A4 (en) 2010-03-31
US20100056657A1 (en) 2010-03-04
US20160362531A1 (en) 2016-12-15
CA2681872C (en) 2015-06-09
CN101652412B (en) 2012-07-25
EP2129713A1 (en) 2009-12-09
EP2129713B1 (en) 2012-02-29
JP5539854B2 (en) 2014-07-02
PL2129715T3 (en) 2012-02-29
CA2681838A1 (en) 2008-10-09
ES2367542T3 (en) 2011-11-04
EP2129714A4 (en) 2010-03-24
CN103992498A (en) 2014-08-20

Similar Documents

Publication Publication Date Title
CA2681838C (en) Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin
JP6441983B2 (en) Hydrochlorofluoroolefin blowing agent composition
EP2606019A2 (en) Compositions containing 1-chloro-3,3,3 trifluoropropene and 1-fluoro-1,1 dichloroethane

Legal Events

Date Code Title Description
AS Assignment

Owner name: ARKEMA INC.,PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHEN, BENJAMIN BIN;COSTA, JOSEPH S.;VAN HORN, BRETT L.;AND OTHERS;SIGNING DATES FROM 20090914 TO 20090915;REEL/FRAME:023276/0688

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION