WO2011069203A1 - Blowing agents for foams - Google Patents
Blowing agents for foams Download PDFInfo
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- WO2011069203A1 WO2011069203A1 PCT/AU2010/001664 AU2010001664W WO2011069203A1 WO 2011069203 A1 WO2011069203 A1 WO 2011069203A1 AU 2010001664 W AU2010001664 W AU 2010001664W WO 2011069203 A1 WO2011069203 A1 WO 2011069203A1
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- dichloroethylene
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- composition according
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- nonafluorobutane
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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
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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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
- 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
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/146—Saturated hydrocarbons containing oxygen and halogen atoms, e.g. F3C-O-CH2-CH3
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
Definitions
- This invention relates to environmentally acceptable foaming or blowing agents for preparing polymeric foams and to articles made from such foams.
- the invention relates to compositions for use as foaming or blowing agents that comprise 1,2-dichloroethylene and a suitable fluorinated ether or preferably an alkoxy substituted perfluoro compound.
- Polyurethane foams can take many forms, but they are generally divided into two major groups: flexible foams and rigid foams.
- Flexible polyurethane foams are useful in the manufacture of articles of furniture where their resilience makes them suitable for incorporation in cushions and mattresses. These foams are characterised by a cell structure that is essentially open, permitting the free passage of gas through the structure of the foam. Consequently, flexible polyurethane foams have insulation properties inferior to those of rigid closed cell foams. Rigid polyurethane foams have particular application where low densities combined with high levels of thermal insulation are required. Such properties are characteristic of closed cell foams. The rigid closed cell foams have a fine cellular structure that frequently preserves some of the foaming agent within the cells.
- Rigid polyurethane foams are commonly prepared by reacting two separate component mixtures that are generally liquids at room temperature, even though they may contain minor quantities of dissolved substances that are normally gases at room temperature.
- An example of such a gas is 1,1,1,2-tetrafluoroethane, or HFC 134a which has a boiling point of approximately -26.2 degrees Celsius but which, when added as a minor component, does not substantially reduce the boiling point of the mixture.
- Polyurethanes are materials formed by the reaction of a polyisocyanate with a polyalcohol, or polyol, in the presence of a catalyst and other additives.
- a polyisocyanate is a molecule with two or more isocyanate functional groups
- a polyol is a molecule with two or more hydroxyl functional groups.
- the product of the reaction is a polymer containing a urethane linkage.
- a nomenclature used in identifying the reaction components refers to the component containing predominantly isocyanates as the "A side” and the component containing predominantly polyols the "B side".
- the blowing or foaming agent may be added to either or both sides, but it is more customary to include it in the B side. Small additions of water may be added to the B side or at the time of mixing.
- the components react and generate heat, causing gases entrained within the liquid components to nucleate and form cells. If water is present, it reacts with isocyanate to liberate carbon dioxide. With the increase in temperature, the blowing agent or agents form gases through mechanisms including dissolution, evaporation and boiling. Gases thus liberated combine to expand the cells while the mixture remains a liquid. As the polymerisation reaction proceeds, the cell walls become rigid, trapping some of the gases within the cells.
- the structure ideally consists of a framework of polymeric material surrounding entrapped gases.
- the cells are predominantly closed such that the entrapped gases are held for a considerable period of time within the structure.
- the period for which the gases are held within the cells is dependent upon a number of factors including the permeability of the polymeric material to the gases, the pressure of gas within the cells and the temperature to which the rigid foam is exposed.
- blowing agents The physical and chemical properties taken into consideration in the selection of blowing agents include boiling point, stability, solvency, compatibility with premix components, surface tension, vapour phase thermal conductivity, flammability and enthalpy of vaporisation.
- environmental considerations such as Ozone Depleting Potential (ODP) and Global Warming Potential (GWP) have increasingly become factors in the selection of blowing agents.
- ODP Ozone Depleting Potential
- GWP Global Warming Potential
- chlorofluorocarbons were found to be excellent blowing or foaming agents.
- CFCs chlorofluorocarbons
- their implication in the destruction of tropospheric ozone led to international action under the Montreal Protocol to cease manufacture according to an agreed timetable.
- the phaseout of the CFCs in developed countries in the 1990s triggered a search for suitable alternatives. While some manufacturers selected hydrocarbon foaming agents despite flammability and performance shortcomings, many preferred the alternative dichlorofluoroethane, or HCFC-141b, sometimes in combination with chlorodifluoromethane, or HCFC-22.
- the HFC alternatives all have global warming potentials greater than 900 times that of carbon dioxide.
- the HFCs are described under the Kyoto Protocol as "synthetic greenhouse gases" and it is probable that their use will come under progressively increasing restrictions as governments act to limit the release of greenhouse gases. Being particularly powerful greenhouse gases, the HFCs are likely to be among the first considered for regulatory controls. Consequently, there remains a need for an alternative with a relatively low global warming potential.
- TDCE trans- 1,2-dichloroethylene
- TDCE trans- 1,2-dichloroethylene
- HCFC-141b which has no flash point
- TDCE has a flash point of about 2°C.
- trans- 1,2-dichloroethylene is a powerful solvent and such substances are known to cause softening in the structure of polyurethane foams resulting in poor compressive strengths. It is commonly understood by formulators of rigid polyurethane foams that the incorporation of high levels of powerful solvents leads to foams of poor compressive strength. For this reason, trans- 1,2-dichloroethylene has not formerly been contemplated for use as the major blowing or foaming agent in a foam composition.
- US2005009932 describes the use of trans- 1,2-dichloroethylene to improve the processability of foam compositions.
- EP 1471101 describes the use of trans-1,2- dichloroethylene as a means of improving the fire resistance of resultant foams. In these and other cases where trans- 1,2-dichloroethylene is used in foam compositions, its application is that of an additive.
- WO2007008278 describes the use of 1-methoxy nonafluorobutane to modify the flash point of trans- 1,2-dichloroethylene.
- the selection of a flash point suppressant with minimal flammability characteristics would be preferable. It follows that the selection of 1-methoxy nonafluorobutane, which has no lower flammability limit when tested in accordance with ASTM E681-94 and no upper flammability limit when tested in accordance with ASTM E681-94, would be preferable to other alkoxy substituted perfluoro compounds, e.g. 1-ethoxy nonafluorobutane which has a lower flammability limit of 210 g/m 3 and an upper flammability limit of 1070 g/m 3 when tested in accordance with the same standards.
- blowing or foaming agent that is a solvent or a solvent mixture that has little flammability, a low or minimal flash point and low or minimal global warming potential compared to conventional industry solvents.
- the present invention provides a composition for use as a foaming or blowing agent comprising a mixture of 1,2-dichloroethylene and a fluorinated ether, said ether capable of lowering the flash point of 1,2-dichloroethylene and present in a flash point lowering amount.
- the 1,2-dichloroethylene is trans- 1,2-dichloroethylene.
- the ether is capable of minimising the flash point of trans- 1,2-dichloroethylene and is present in a flash point minimising amount. More preferably the ether is a flash point eliminating ether and is present in a flash point eliminating amount.
- the flash point is lowered such that it is not measurable.
- a suitable amount of fluorinated ether is required to be added to trans- 1,2- dichloroethylene in order to minimise the flash point.
- the amount is at least 1%, more preferably it is at least 5% and in the most preferred embodiments does not exceed 20% of the composition.
- the fluorinated ether is about 3% to about 6% of the composition.
- the fluorinated ether is an alkoxy substituted perfluoro compound.
- the composition for use as a foaming or blowing agent comprises a mixture of trans- 1,2-dichloroethylene and a fluorinated ether that is 1-ethoxy- nonafluorobutane and is capable of minimising the flash point of 1,2-dichloroethylene.
- a 1-ethoxy-nonafluorobutane is HFE-7200 from 3M.
- the fluorinated ether is 1-ethoxy-nonafluorobutane
- other fluorinated ethers may additionally be present but should not exceed 50% of the total amount of fluorinated ether.
- the amount is not more than 30% and most preferably the amount is not more than 10%.
- An example of an additional fluorinated ether is 1- methoxy-nonafluorobutane.
- the present invention provides a composition for use as a foaming or blowing agent comprising a mixture of 1,2-dichloroethylene and an alkoxy substituted perfluoro compound, said perfluoro compound capable of lowering the flash point of 1,2-dichloroethylene.
- the alkoxy substituted perfluoro compound is capable of minimising the flash point of 1,2-dichloroethylene and is present in a flash point minimising amount. More preferably the alkoxy substituted perfluoro compound is a flash point eliminating ether and is present in a flash point eliminating amount.
- the flash point is lowered such that it is not measurable.
- the alkoxy substituted perfluoro compound is present in an amount of at least 1%, more preferably it is at least 5% and in the most preferred embodiments does not exceed 20%. In most preferred embodiments, the alkoxy substituted perfluoro compound is about 3% to about 6% of the composition.
- the 1,2-dichloroethylene is trans- 1,2-dichloroethylene and an alkoxy substituted perfluoro compound is l-ethoxy-nonafluorobutane.
- alkoxy substituted perfluoro compound is l-ethoxy-nonafluorobutane
- other alkoxy substituted perfluoro compounds may additionally be present but should not exceed 50% of the total amount of alkoxy substituted perfluoro compounds.
- the amount is not more than 30% and most preferably the amount is not more than 10%.
- An example of an additional alkoxy substituted perfluoro compound is 1- methoxy-nonafluorobutane.
- the present invention provides a composition for use as a foaming or blowing agent comprising a mixture of trans- 1,2-dichloroethylene and a fluorinated ether that is l-ethoxy-nonafluorobutane, said l-ethoxy-nonafluorobutane capable of minimising the flash point of 1,2-dichloroethylene.
- a fluorinated ether that is l-ethoxy-nonafluorobutane
- the 1-ethoxy-nonafluorobutane is capable of minimising the flash point of 1,2-dichloroethylene and is present in a flash point minimising amount.
- the 1-ethoxy-nonafluorobutane is a flash point eliminating ether and is present in a flash point eliminating amount.
- the flash point is lowered such that it is not measurable.
- the 1-ethoxy-nonafluorobutane is present in an amount of at least 1%, more preferably it is at least 5% and in the most preferred embodiments does not exceed 20%. In most preferred embodiments, the 1-ethoxy-nonafluorobutane is about 3% to about 6% of the composition.
- fluorinated ethers may additionally be present but should not exceed 50% of the total amount of fluorinated ether. Preferably the amount is not more than 30% and most preferably the amount is not more than 10%.
- An example of an additional fluorinated ether is 1-methoxy-nonafluorobutane.
- the present invention provides a composition for use as a foaming or blowing agent comprising a mixture of 1,2-dichloroethylene and a fluorinated ether, said ether capable of lowering the flash point of 1,2-dichloroethylene and present in a flash point lowering amount and wherein a polymeric foam prepared from said foaming or blowing agent has an improved compressive strength.
- the 1,2-dichloroethylene is TDCE and the fluorinated ether is 1- methoxy-nonafluorobutane or 1-ethoxy-nonafluorobutane.
- the present invention provides a composition for use as a foaming or blowing agent comprising a mixture of 1,2-dichloroethylene and an alkoxy substituted perfluoro compound, said perfluoro compound capable of lowering the flash point of 1,2-dichloroethylene and wherein a polymeric foam prepared from said foaming or blowing agent has an improved compressive strength.
- a foaming or blowing agent comprising a mixture of 1,2-dichloroethylene and an alkoxy substituted perfluoro compound, said perfluoro compound capable of lowering the flash point of 1,2-dichloroethylene and wherein a polymeric foam prepared from said foaming or blowing agent has an improved compressive strength.
- the 1,2-dichloroethylene is TDCE and the alkoxy substituted perfluoro compound is 1-methoxy-nonafluorobutane or 1-ethoxy-nonafluorobutane.
- the present invention provides a composition for use as a foaming or blowing agent comprising a mixture of trans 1,2-dichloroethylene and 1- ethoxy-nonafluorobutane, said 1-ethoxy-nonafluorobutane capable of lowering the flash point of 1,2-dichloroethylene and wherein a polymeric foam prepared from said foaming or blowing agent has an improved compressive strength.
- a foaming or blowing agent comprising a mixture of 1,2-dichloroethylene and a fluorinated ether, said ether capable of lowering the flash point of 1,2-dichloroethylene and present in a flash point lowering amount in the preparation of a foam.
- the fluorinated ether is an alkoxy substituted perfluoro compound.
- the 1,2-dichloroethylene is TDCE and the alkoxy substituted perfluoro compound is l-methoxy-nonafluorobutane or 1-ethoxy-nonafluorobutane.
- the foam has an improved compressive strength.
- fluorinated ether is 1-ethoxy-nonafluorobutane
- other fluorinated ethers may additionally be present but should not exceed 50% of the total amount of fluorinated ether.
- the amount is more than 30% and most preferably the amount is not more than 10%.
- a suitable additional fluorinated ether is l-methoxy- nonafluorobutane .
- the present invention provides a composition for preparing a polymeric foam comprising a mixture of 1,2-dichloroethylene and a fluorinated ether, said ether capable of lowering the flash point of 1,2-dichloroethylene.
- the fluorinated ether is an alkoxy substituted perfluoro compound.
- the 1,2-dichloroethylene is trans- 1,2-dichloroethylene and the alkoxy substituted perfluoro compound is 1-ethoxy-nonafluorobutane.
- the polymeric foam is a polyurethane foam that is a rigid closed cell foam.
- the invention in a ninth aspect relates to a process of preparing a polymeric foam comprising reacting a foamable composition comprising a mixture of 1,2- dichloroethylene and a fluorinated ether, said ether capable of lowering the flash point of 1,2-dichloroethylene with one or more polymers or one or more compounds capable of forming a polymer to form a foam or cellular structure.
- a foamable composition comprising a mixture of 1,2- dichloroethylene and a fluorinated ether, said ether capable of lowering the flash point of 1,2-dichloroethylene with one or more polymers or one or more compounds capable of forming a polymer to form a foam or cellular structure.
- the foam is a rigid closed cell foam.
- the process comprises the steps of preparing polyurethane or poiyisocyanurate foams by combining an isocyanate, a polyol or mixture of polyols, the composition of the invention, and other materials as required including catalysts, surfactants, colourants and the like.
- the invention provides a blown or polymeric foam prepared from the composition according to the invention.
- the polymeric foam is a polyurethane foam that is a rigid closed cell foam and is prepared by the process of the invention. More preferably the foam comprises small amounts of a blowing or foaming agent according to the invention contained within the cells.
- the present invention relates to compositions for use as a foaming agent that have little flammability, a low or minimal flash point and low or minimal global warming potential. While the term blowing agent may be said to refer to agents that have a role in filling polymeric cells with gas and the foaming agent to one that initiates form formation, the terms "blowing agent” and “foaming agent” are often used interchangeably and are therefore used in a similar manner throughout the specification.
- compositions comprise at least 1,2-dichloroethylene and a fluorinated ether that is capable of minimising the flash point of 1,2-dichloroethylene.
- this mixture comprises 1,2-trans-dichloroethylene (TDCE) and a fluorinated ether that is an alkoxy substituted perfluro compound.
- TDCE 1,2-trans-dichloroethylene
- a highly preferred alkoxy substituted perfluro compound is 1-ethoxy-nonafluorobutane.
- An example of a 1-ethoxy-nonafluorobutane is HFE-7200 from 3M. As is known, HFE-7200 from 3M consists of two inseparable isomers with essentially identical properties, (CF3)2CFCF20C2H5 (CAS No. 163702-06-5) and CF3CF2CF2CF20C2H5 (CAS No. 163702-05-4).
- Fluorinated ethers like HFE-7200 are advantageously used in the invention as they are not classed as a hazardous substance, so its use introduces no additional occupational health and safety concerns. Further it has minimal ozone depleting potential and a global warming potential 55 times that of carbon dioxide, which is not high when compared with many commercially available fluorinated hydrocarbons. Like TDCE, its time weighted average (TWA) exposure limit is 200 ppm.
- a suitable amount of fluorinated ether is required to be added to 1,2-trans- dichloroethylene in order to minimise the flash point such that it is not measurable.
- the amount is at least 1%, more preferably it is at least 5% and in the most preferred embodiments does not exceed 20%.
- an amount of from about 3% to about 10% is advantageous for the invention. While not critical, the amount is generally v/v of the composition.
- the fluorinated ether is an alkoxy substituted perfluro compound.
- the alkoxy substituted perfluro compound is 1 -ethoxy - nonafluorobutane .
- an amount of l-ethoxy-nonafluorobutane from about 3% to about 10% is sufficient for the invention.
- An amount of as little as 3% to about 6% of the l-ethoxy- nonafluorobutane is also advantageous.
- l-ethoxy-nonafluorobutane exhibits flash point suppression such that when tested no flash point was measured and no sustained burning was detected, l-ethoxy-nonafluorobutane is therefore effective at suppressing the flash point of trans- 1,2-dichloroethylene when tested in accordance with ASTM D93 and ASTM D 4206.
- fluorinated ether While a mixture of fluorinated ethers may be present, it is preferred that the fluorinated ether is largely l-ethoxy-nonafluorobutane.
- a reason for a preference for 1- ethoxy nonafluorobutane over 1-methoxy nonafluorobutane is their relative environmental impact. Neither of the substances has an Ozone Depletion Potential (ODP) and neither is considered to be a Volatile Organic Compound (VOC).
- ODP Ozone Depletion Potential
- VOC Volatile Organic Compound
- the two substances differ substantially in their atmospheric lifetimes, with 1-methoxy nonafluorobutane having an atmospheric lifetime of 4.1 years and 1 -ethoxy nonafluorobutane having an atmospheric lifetime of 0.8 years.
- 1-methoxy nonafluorobutane has a GWP of 320 while 1-ethoxynonafluorobutane has a GWP of 55.
- 1-ethoxynonafluoropropane is preferable.
- other ethers e.g. 1-methoxy-nonafluorobutane (HFE-7100)
- HFE-7100 1-methoxy-nonafluorobutane
- the amount of such ethers should not exceed 50%. More preferably the amount is not more than 30% and most preferably the amount is not more than 10%. It may be necessary in some circumstances to lower the boiling point by the addition of a small quantity of a lower boiling point fluid.
- An example of such fluids is low boiling hydrocarbon compounds that may be advantageously added to the compositions of the invention. Preferably these compounds are non-halogenated. Examples include carbon dioxide, ethers like dimethyl ether and C1-C4 alkanes with butane being the fluid of choice. As dimethyl ether and the alkanes tend to be flammable, an additional quantity of 1-ethoxy-nonafluorobutane may be added if required. An alternative would be to use additional water in the blended foaming composition provided the thermal and mechanical properties of the final polyurethane product are not compromised. A small amount of other ingredients commonly employed with foaming or blowing agents prior to their use may be added without departing from the scope of the invention.
- the compressive strengths of foams blown with compositions of the present invention are within the range expected of foams produced with the aid of the commonly used commercial blowing agents. Further foams produced using TDCE as the principal blowing agent have higher compressive strengths than would have been expected for such a powerful solvent.
- compositions for use as a foaming or blowing agent including a mixture of 1,2- dichloroethylene and a fluorinated ether, wherein the ether is capable of lowering the flash point of 1,2-dichloroethylene and present in a flash point lowering amount can be used to prepare polymeric foams with an improved compressive strength.
- 1,2-dichloroethylene is trans- 1,2-dichloroethylene and the fluorinated ether is an alkoxy substituted perfluoro compound.
- the fluorinated ether can also be comprised of 1-methoxy-nonafluorobutane or 1- ethoxy-nonafluorobutane or mixtures thereof, the 1-methoxy-nonafluorobutane or 1- ethoxy-nonafluorobutane or the mixture thereof being capable of minimising the flash point of 1,2-dichloroethylene.
- the fluorinated ether is 1-ethoxy-nonafhiorobutane it is present in an amount of at least 1 %, preferably at least 5% and preferably not greater than about 20%. Ideally the amount is about 3 % to about 6%.
- a rigid polyurethane foam blown using a blend of 19% trans- 1,2-dichloroethylene and 1% 1-ethoxy nonafluorobutane as the blowing agent has an average compressive strength of 145 kPa and a density of 32.5 kg/m .
- the invention also relates to all foams, (including but not limited to closed cell foam, open cell foam, rigid foam, flexible foam, integral skin and the like) prepared from a polymer foam formulation comprising a composition according to the invention.
- compositions previously described can also be used to make polymeric foams.
- a composition for preparing a polymeric foam may include a mixture of 1,2- dichloroethylene and a fluorinated ether, with the ether being capable of lowering the flash point of 1,2-dichloroethylene.
- 1,2-dichloroethylene is trans- 1,2-dichloroethylene and the fluorinated ether is an alkoxy substituted perfluoro compound.
- the 1,2-dichloroethylene is trans- 1,2- dichloroethylene and the fluorinated ether is l-ethoxy-nonafluorobutane.
- the polymeric foam is a polyurethane foam that is a rigid closed cell foam.
- the invention therefore also relates to use of a foaming or blowing agent including a mixture of 1,2-dichloroethylene and a fluorinated ether, wherein the ether is capable of lowering the flash point of 1,2-dichloroethylene and is present in a flash point lowering amount in the preparation of a foam.
- foams have an improved compressive strength.
- a foaming or blowing agent including a mixture of 1,2-dichloroethylene and a fluorinated ether is used to prepare a foam. These foams have improved compressive strength.
- the foamable or foam forming composition of the invention may be foamed by known methods.
- the foaming or blowing agent undergoes volumetric expansion as required.
- the type of foams includes those well known in the art, including thermosetting foams, thermoplastic foams and foams prepared in-situ.
- the present invention also relates to the use of the compositions of the invention in conventional foaming equipment, such as polyurethane foaming equipment, at conventional processing conditions.
- the present methods therefore include masterbatch type operations, blending type operations, third stream blowing agent addition, and blowing agent addition at the foam head.
- the 1,2-dichloroethylene is trans- 1,2-dichloroethylene and the fluorinated ether is a alkoxy substituted perfluoro compound.
- the 1,2-dichloroethylene is trans- 1,2-dichloroethylene and the fluorinated ether is 1-methoxy-nonafluorobutane or l-ethoxy-nonafluorobutane or their mixtures thereof.
- the fluorinated ether is largely l-ethoxy- nonafluorobutane though not more than 50%, preferably not more than 30%, more preferably not more than 10% l-methoxy-nonafluorobutane may be present.
- the amount of the fluorinated ether is at least 1%, more preferably it is at least 5% and in the most preferred embodiments does not exceed 20% of the composition. In most preferred embodiments, the fluorinated ether is about 3% to about 6% of the composition.
- a process of preparing a polymeric foam includes the steps of reacting a foamable composition including a mixture of 1,2-dichloroethylene and a fluorinated ether.
- the ether is capable of lowering the flash point of 1,2-dichloroethylene with one or more polymers or one or more compounds capable of forming a polymer to form a foam or cellular structure.
- the foam is a rigid closed cell foam.
- steps of preparing polyurethane or polyisocyanurate foams includes combining an isocyanate, a polyol or mixture of polyols, any of the the compositions as described above and other materials as required including catalysts, surfactants, colourants and the like.
- the fluorinated ether is present in an amount of at least 1 %, preferably at least 5% and preferably not greater than about 20%. Ideally the amount is about 3 % to about 6%.
- the 1,2-dichloroethylene is trans- 1,2-dichloroethylene and the fluorinated ether is an alkoxy substituted perfluoro compound.
- the 1,2-dichloroethylene is trans- 1,2-dichloroethylene and the fluorinated ether is 1-ethoxy- nonafluorobutane .
- the fluorinated ether is l-ethoxy-nonafluorobutane
- other fluorinated ethers may additionally be present but should not exceed 50% of the total amount of fluorinated ether.
- the amount is more than 30% and most preferably the amount is not more than 10%.
- a suitable additional fluorinated ether is 1-methoxy- nonafluorobutane .
- Blown or polymeric foams are prepared from compositions of the invention as described above.
- foams include polyurethane foam which is a rigid closed cell foam and is prepared by the process of the invention. Small amounts of a composition according to the invention may be contained within the cells.
- the invention is directed in particular to polyurethane and polyisocyanurate foams.
- the methods generally comprise adding the blowing or foaming agent of the present invention to a foamable composition, and reacting the foamable composition with one or more polymers or one or more compounds capable of forming a polymer to form a foam or cellular structure, in particular a rigid closed cell foam.
- such preferred methods comprise preparing polyurethane or polyisocyanurate foams by combining an isocyanate, a polyol or mixture of polyols, the blowing or foaming agent of the invention, and other materials as required including catalysts, colourants and the like.
- Rigid polyurethane products are supplied generally in the form of two liquid components which are mixed in a precise ratio to produce a foam which expands and then cures to a stable low density mass.
- the "A” component generally is formulated with polymeric isocyanates containing reactive isocyanate groups while the “B” component contains polyols, catalytic agents and the blowing agent or agents.
- the "B” component contains polyols, catalytic agents and the blowing agent or agents.
- TDCE in the B component has the effect of lowering the viscosity of the composition, thus enhancing its mixing characteristics.
- the use of TDCE as part of the blowing agent mixture is expected to enhance the fire performance of the finished product, despite itself being flammable.
- TDCE in the B component has the effect of lowering the viscosity of the composition, thus enhancing its mixing characteristics.
- the use of TDCE as part of the blowing agent mixture is expected to enhance the fire performance of the finished product, despite itself being flammable.
- the A and B side components are combined in a 1:1 ratio with stirring, catalyst is added and stirring continued for a further 30 seconds.
- TDCE in the B component has the effect of lowering the viscosity of the composition, thus enhancing its mixing characteristics.
- the use of TDCE as part of the blowing agent mixture is expected to enhance the fire performance of the finished product, despite itself being flammable.
- mixtures of TDCE and HFE-7200 with the optional inclusion of a low boiling non-halogenated compounds such as the CI - C5 hydrocarbons or other compounds such as dimethyl ether and carbon dioxide provide for little flammability, a minimal flash point and minimal global warming potential compared to conventional industry solvents, in particular for use as a foaming agent.
Abstract
Description
Claims
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AU2010330691A AU2010330691A1 (en) | 2009-12-08 | 2010-12-08 | Blowing agents for foams |
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AU2009905981A AU2009905981A0 (en) | 2009-12-08 | Blowing agents for foams | |
AU2009905981 | 2009-12-08 |
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WO2011069203A1 true WO2011069203A1 (en) | 2011-06-16 |
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PCT/AU2010/001664 WO2011069203A1 (en) | 2009-12-08 | 2010-12-08 | Blowing agents for foams |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013186336A2 (en) * | 2012-06-15 | 2013-12-19 | Bayer Materialscience Ag | A microcellular polyurethane composition, method of preparation and uses thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020061935A1 (en) * | 1998-05-15 | 2002-05-23 | Kingspan Industrial Insulation Limited | Closed cell phenolic foam |
US20030224956A1 (en) * | 2002-06-03 | 2003-12-04 | Crc Industries, Inc. | Cleaner for electronic parts and method for using the same |
US20070010421A1 (en) * | 2005-07-07 | 2007-01-11 | Jinhuang Wu | Trans-1, 2-dichloroethylene and hydrofluorocarbon or alkoxy perfluoroalkane compositions having elevated flash points |
FR2899234A1 (en) * | 2006-03-31 | 2007-10-05 | Arkema Sa | Foaming agent, useful to manufacture polyurethane foams, comprises an organic solvent e.g. dimethylcarbonate and a fluorinated compound e.g. 1-methoxynonafluorobutane |
FR2921664A1 (en) * | 2007-09-28 | 2009-04-03 | Arkema France | Composition, useful as foaming agent in manufacturing polyurethane foams/polyisocyanurate, and as solvents, aerosols and/or refrigerants, comprises trans-1,2 dichloroethylene and hydrofluoroolefin |
-
2010
- 2010-12-08 AU AU2010330691A patent/AU2010330691A1/en not_active Abandoned
- 2010-12-08 WO PCT/AU2010/001664 patent/WO2011069203A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020061935A1 (en) * | 1998-05-15 | 2002-05-23 | Kingspan Industrial Insulation Limited | Closed cell phenolic foam |
US20030224956A1 (en) * | 2002-06-03 | 2003-12-04 | Crc Industries, Inc. | Cleaner for electronic parts and method for using the same |
US20070010421A1 (en) * | 2005-07-07 | 2007-01-11 | Jinhuang Wu | Trans-1, 2-dichloroethylene and hydrofluorocarbon or alkoxy perfluoroalkane compositions having elevated flash points |
FR2899234A1 (en) * | 2006-03-31 | 2007-10-05 | Arkema Sa | Foaming agent, useful to manufacture polyurethane foams, comprises an organic solvent e.g. dimethylcarbonate and a fluorinated compound e.g. 1-methoxynonafluorobutane |
FR2921664A1 (en) * | 2007-09-28 | 2009-04-03 | Arkema France | Composition, useful as foaming agent in manufacturing polyurethane foams/polyisocyanurate, and as solvents, aerosols and/or refrigerants, comprises trans-1,2 dichloroethylene and hydrofluoroolefin |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013186336A2 (en) * | 2012-06-15 | 2013-12-19 | Bayer Materialscience Ag | A microcellular polyurethane composition, method of preparation and uses thereof |
WO2013186336A3 (en) * | 2012-06-15 | 2014-04-03 | Bayer Materialscience Ag | A microcellular polyurethane composition, method of preparation and uses thereof |
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AU2010330691A1 (en) | 2012-07-26 |
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