US20140336293A1 - Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin - Google Patents
Blowing agent composition of hydrofluoropropene and hydrochlorofluoroolefin Download PDFInfo
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- US20140336293A1 US20140336293A1 US14/339,732 US201414339732A US2014336293A1 US 20140336293 A1 US20140336293 A1 US 20140336293A1 US 201414339732 A US201414339732 A US 201414339732A US 2014336293 A1 US2014336293 A1 US 2014336293A1
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- 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
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- 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 (HFO-1354), 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.
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
- This application is a divisional of U.S. application Ser. No. 12/532,194 filed Sep. 21, 2009, which is the United States national phase of and claims priority to International Application serial number PCT/US08/58604 filed Mar. 28, 2008 which designated the United States, which claims priority to U.S. provisional application Ser. No. 60/908,751, filed Mar. 29, 2007, all of which are incorporated herein by references.
- 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.
- 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.
- 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 (HFO-1354), 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.
- 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.
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TABLE 1 Formulations HFO1243zf HCFO1233zd HFO1234ze HFO1243Zf + 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 - Table 2 summarized B-side vapor pressure of different blowing agents.
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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.
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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.
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TABLE 4 Free Rise Density Free Rise Density Blowing agent (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 polyurethane foam comprising polymer foam components and 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.
2. The polyurethane foam of claim 1 , wherein said hydrofluoropropene HFO-1243zf comprises about 5 wt % or more of the hydrofluoropropene and hydrochlorofluoroolefin composition.
3. The polyurethane foam of claim 1 , wherein said foam blowing agent further comprising further comprising a hydrofluorocarbon.
4. The polyurethane foam of claim 3 , 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).
5. The polyurethane foam of claim 1 , wherein said foam blowing agent further comprising a hydrofluoroolefin.
6. The polyurethane foam of claim 5 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).
7. The polyurethane foam of claim 1 , wherein said blowing agent further comprises a component selected from the group consisting of a second hydrofluoroolefin (HFO), 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 claim 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.
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Families Citing this family (81)
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 |
TW201815923A (en) † | 2005-06-24 | 2018-05-01 | 美商哈尼威爾國際公司 | Foaming agents and compositions containing fluorine substituted olefins, and methods of foaming |
US9695267B2 (en) * | 2009-08-11 | 2017-07-04 | Honeywell International Inc. | Foams and foamable compositions containing halogenated olefin blowing agents |
PL2129711T5 (en) * | 2007-03-29 | 2020-09-21 | Arkema, Inc. | Blowing agent compositions of hydrofluoroolefins and hydrochlorofluoroolefins |
JP2010534254A (en) * | 2007-07-20 | 2010-11-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Compositions and use of trans-1,1,1,4,4,4-hexafluoro-2-butene foam molding compositions in the production of polyisocyanate-based foams |
US8628681B2 (en) | 2007-10-12 | 2014-01-14 | Mexichem Amanco Holding S.A. De C.V. | Heat transfer compositions |
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 |
WO2009047542A1 (en) | 2007-10-12 | 2009-04-16 | Ineos Fluor Holdings Limited | Heat transfer compositions |
GB201002625D0 (en) | 2010-02-16 | 2010-03-31 | Ineos Fluor Holdings Ltd | 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 |
EP2250144A4 (en) | 2008-03-07 | 2014-06-04 | Arkema Inc | Stable formulated systems with chloro-3,3,3-trifluoropropene |
CN104164214B (en) * | 2008-05-07 | 2018-04-24 | 科慕埃弗西有限公司 | It can be used as the composition of heat transfer composition |
JP2011530646A (en) * | 2008-08-13 | 2011-12-22 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Foam-forming composition containing a mixture of 2-chloro-3,3,3-trifluoropropene and hydrocarbon and its use in the production of polyisocyanate based foam |
US8163196B2 (en) * | 2008-10-28 | 2012-04-24 | Honeywell International Inc. | Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene |
JP2012510550A (en) * | 2008-12-02 | 2012-05-10 | メキシケム、アマンコ、ホールディング、ソシエダッド、アノニマ、デ、カピタル、バリアブレ | Heat transfer composition |
BRPI1007524A2 (en) * | 2009-01-29 | 2017-03-01 | Arkema Inc | tetrafluoropropene blowing agent compositions |
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 |
TW201103972A (en) | 2009-04-01 | 2011-02-01 | Solvay Fluor Gmbh | Process for the manufacture of etched items |
US8481605B2 (en) | 2009-05-21 | 2013-07-09 | Huntsman International Llc | Rigid polyurethane foam and system and method for making the same |
WO2010141527A1 (en) * | 2009-06-02 | 2010-12-09 | E. I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluoro-2-butene |
BR112012001918A2 (en) * | 2009-07-27 | 2016-03-15 | Arkema Inc | hcfo-1233zd composition 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 |
JP2013504658A (en) * | 2009-09-09 | 2013-02-07 | ハネウェル・インターナショナル・インコーポレーテッド | Monochlorotrifluoropropene compound and composition and method using the same |
PL2491075T3 (en) * | 2009-10-23 | 2017-05-31 | Arkema Inc. | Tetrafluorobutene blowing agent compositions for polyurethane foams |
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 |
EP2845891B1 (en) | 2009-12-22 | 2019-10-02 | The Chemours Company FC, LLC | Compositions comprising 2,3,3,3-tetrafluoropropene and 2,3-dichloro-3,3-difluoropropene |
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 |
CA2799836C (en) | 2010-05-20 | 2015-11-24 | Mexichem Amanco Holding S.A. De C.V. | Heat transfer compositions |
CN102947409A (en) | 2010-05-20 | 2013-02-27 | 墨西哥化学阿玛科股份有限公司 | Heat transfer compositions |
GB2481443B (en) | 2010-06-25 | 2012-10-17 | Mexichem Amanco Holding Sa | Heat transfer compositions |
US20120043492A1 (en) * | 2010-08-17 | 2012-02-23 | Honeywell International Inc. | Compositions Containing 1-Chloro-3,3,3 Trifluoropropene And 1-Fluoro-1,1 Dichloroethane |
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 |
JP5731008B2 (en) | 2010-11-17 | 2015-06-10 | エフオーエムオー、プロダクツ、インク | Method for filling wall cavities with expanded foam insulation |
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 |
EP2655464A1 (en) | 2010-12-21 | 2013-10-30 | 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 |
CA2843012A1 (en) * | 2011-07-28 | 2013-01-31 | Honeywell International Inc. | Foams and flame resistant articles made from foams containing 1-chloro-3,3,3-trifluoropropene (1233zd) |
RU2611493C2 (en) | 2011-08-01 | 2017-02-27 | Басф Се | Hydrofluorolefin/water-blown systems for rigid foam materials |
US9896558B2 (en) | 2011-08-01 | 2018-02-20 | Basf Se | HFO/water-blown rigid foam systems |
JP6228122B2 (en) | 2011-10-14 | 2017-11-08 | ダウ グローバル テクノロジーズ エルエルシー | Hybrid polyester-polyether polyols for improved demold expansion in polyurethane rigid foams |
CN103890065B (en) | 2011-10-20 | 2016-02-03 | 纳幕尔杜邦公司 | Azeotrope-like compositions of chloro-2,3,3, the 3-tetrafluoeopropenes of E-1-and uses thereof |
MX350555B (en) * | 2011-12-09 | 2017-09-11 | Honeywell Int Inc | Foams and articles made from foams containing hcfo or hfo blowing agents. |
JP2015507039A (en) * | 2011-12-22 | 2015-03-05 | ハネウェル・インターナショナル・インコーポレーテッド | An azeotrope-like composition comprising cis-1-chloro-3,3,3-trifluoropropene |
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 |
CN104046331A (en) * | 2013-03-14 | 2014-09-17 | 霍尼韦尔国际公司 | Low GWP fluids for high temperature heat pump applications |
BR112015023773A2 (en) | 2013-03-15 | 2017-07-18 | Owens Corning Intellectual Capital Llc | processing support for use in the manufacture of extruded polystyrene foam using potential global warming blowing agents |
US20150210818A1 (en) * | 2014-01-27 | 2015-07-30 | E I Du Pont De Nemours And Company | Cryogenic insulation foam |
CN103881131A (en) * | 2014-03-17 | 2014-06-25 | 浙江衢化氟化学有限公司 | Environment-friendly foaming agent composition |
CA2947458A1 (en) * | 2014-04-30 | 2015-11-05 | Honeywell International Inc. | Flexible, open-cell thermoset foams and blowing agents and methods for making same |
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 |
US20160017111A1 (en) * | 2014-07-16 | 2016-01-21 | 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 |
AU2016237952B2 (en) * | 2015-03-24 | 2018-08-09 | Asahi Kasei Construction Materials Corporation | Phenol resin foam and method for producing same |
EP3275927B1 (en) * | 2015-03-24 | 2021-07-28 | Sekisui Chemical Co., Ltd. | Phenolic resin foam and method for producing phenolic resin foam |
EP3297980A4 (en) | 2015-05-21 | 2018-12-26 | The Chemours Company FC, LLC | HYDROFLUORINATION OF 1233xf TO 244bb BY SbF5 |
EP3330347B1 (en) * | 2015-07-27 | 2020-07-08 | AGC Inc. | Solvent composition, cleaning method, coating film formation method, 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 |
JP7372553B2 (en) * | 2018-07-27 | 2023-11-01 | セントラル硝子株式会社 | Solvent compositions, solutions, methods for cleaning articles, and methods for forming coatings |
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 |
MX2022009160A (en) * | 2020-02-04 | 2022-08-16 | Chemours Co Fc Llc | Nucleating agents for pir foams. |
JPWO2022009801A1 (en) * | 2020-07-08 | 2022-01-13 | ||
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 |
CN117940474A (en) * | 2022-05-20 | 2024-04-26 | 海信容声(广东)冰箱有限公司 | Polyurethane foam material and preparation method thereof, refrigerator and freezer |
Family Cites Families (21)
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 |
US6013846A (en) * | 1998-03-05 | 2000-01-11 | Elf Atochem North America, Inc. | Azeotrope of HF and 1233zd |
US20050096246A1 (en) * | 2003-11-04 | 2005-05-05 | Johnson Robert C. | Solvent compositions containing chlorofluoroolefins |
PT2258819T (en) * | 2002-10-25 | 2017-11-13 | Honeywell Int Inc | Use as a cleaning composition of a composition comprising 1,3,3,3-tetrafluoropropene (hfo-1234ze) |
US7279451B2 (en) * | 2002-10-25 | 2007-10-09 | Honeywell International Inc. | Compositions containing fluorine substituted olefins |
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 |
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 |
WO2006069362A2 (en) * | 2004-12-21 | 2006-06-29 | 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 |
TW201815923A (en) | 2005-06-24 | 2018-05-01 | 美商哈尼威爾國際公司 | Foaming agents and compositions containing fluorine substituted olefins, and methods of foaming |
EP3135720B1 (en) | 2007-03-29 | 2020-07-01 | 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 |
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