The present invention provides a composition comprising dichloromethane and hydrofluoroalkenes for use as blowing agents, cleaning solvent or for deposition of certain types of lubricants, as a dust off, freeze spray, or tire inflator.

BACKGROUND OF THE INVENTION
Foam blowing agent is a substance, which is capable of producing a cellular structure via a foaming process in a variety of materials that undergo hardening or phase transition, such as polymers & plastics. Different kind of foams have different applications e.g., Polyurethane foams are useful in refrigeration system, spray foam, rigid foam. Flexible foams are useful in mattresses, pillows and cushions.
Fluorocarbons have found widespread use in many commercial and industrial applications, including as aerosol propellants and as foam blowing agents. Owing to their high global warming potentials (GWP), chlorofluorocarbons ("CFCs") and hydrochlorofluorocarbons ("HCFCs") have increasingly being replaced by low to zero ozone depletion potential (ODP), and low GWP compounds such as hydrofluoroalkenes.
European Pub. No. 2666811 provides blowing agent composition comprising tetrafluoroalkene such as R1234ze, R1233, or R1233xf or R1233zd and hydrofluorocarbons such as difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365) and hexafluorobutane (HFC-356).
PCT Pub. No 1999035209 provides an azeotrope-like composition comprising about 80 to about 99.9 weight percent of 1, 1, 1, 3, 3-pentafluoropropane (R245fa) and from about 0.1 to about 20 weight percent of a chlorinated ethylene such as methylene chloride.
There, still remains a need to develop efficient blowing agents that can be used for wide variety of applications. The present invention provides a composition comprising dichloromethane and hydrofluoroalkenes, which can be used for wide varieties of foam blowing applications.

OBJECT OF THE INVENTION
The main object of the present invention is to provide a composition comprising dichloromethane and hydrofluoroalkenes for use as blowing agents, in cleaning or deposition of certain types of lubricants, as a dust off, freeze spray, or tire inflator.

SUMMARY OF THE INVENTION
In an aspect, the present invention provides a composition, comprising 5% by weight to 95% by weight of dichloromethane; and 1% by weight to 95% by weight of one or more hydrofluoroalkene.
In another aspect, the present invention provides a composition, comprising 5% by weight to 95% by weight dichloromethane; and 5% by weight to 95% by weight of a mixture of hydrofluoroalkene and hydrofluoroalkane.

DETAILED DESCRIPTION OF THE INVENTION
As used herein the hydrofluoroalkene refers to hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO) selected from 3,3,3-trifluoropropene (R-1243zf), (cis and/or trans)-1,3,3,3-tetrafluoropropene (R-1234ze), 2,3,3,3-tetrafluoropropene (R-1234yf), (cis and/or trans)-1,2,3,3,3-pentafluoropropene (R-1225ye), (cis and/or trans)-1,1,1,4,4,4-hexafluoro-2-butene (R-1336mzz), (cis and/or trans)-1-chloro-3,3,3-trifluoropropene (R-1233zd), 2-chloro-3,3,3-trifluoropropene (R-1233xf), 1,1-dichloro-3,3,3-trifluoropropene (1223za), 1,2-dichloro-3,3,3-trifluoropropene and a mixtures thereof. Hydrofluoroalkene preferably refers to R1234ze, R1234yf, R-1336mzz and R1233zd.
As used herein, the R1234ze includes R1234ze(E), R1234ze(Z) or a mixture thereof.
As used herein, the non-azeotropic composition is a mixture of two or more substances that behaves as a simple mixture rather than a single substance. One way to characterize a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a substantially different composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes with substantial composition change.
As used herein, the term “near azeotropic” is intended in its broad sense to include both compositions that are strictly azeotropic and compositions that behave like azeotropic mixtures. From fundamental principles, the thermodynamic state of a fluid is defined by pressure, temperature, liquid composition, and vapor composition. An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the state pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant boiling and cannot be separated during a phase change.
The “near azeotropic” compositions behave like azeotropic mixtures, that is, they are constant boiling or essentially constant boiling. In other words, for azeotrope-like compositions, the composition of the vapor formed during boiling or evaporation is identical, or substantially identical, to the original liquid composition. Thus, with boiling or evaporation, the liquid composition changes, if at all, only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which, during boiling or evaporation, the liquid composition changes to a substantial degree. All azeotrope-like compositions of the invention within the indicated ranges as well as certain compositions outside these ranges are azeotrope-like.
In an embodiment, the present invention provides a composition, comprising 5% by weight to 95% by weight of dichloromethane; and 1% by weight to 95% by weight of one or more hydrofluoroalkene selected from a group consisting of R1234ze, R1234yf, R1233zd and R1336mzz.
In a preferred embodiment, the present invention provides a composition, comprising 5% by weight to 70% by weight of dichloromethane; and 1% by weight to 95% by weight of one or more hydrofluoroalkene selected from a group consisting of R1234ze, R1234yf, R1233zd and R1336mzz.
In another embodiment, the present invention provides a blowing agent composition, comprising 5% by weight to 70% by weight of dichloromethane; and 1% by weight to 95% by weight of one or more hydrofluoroalkene selected from a group consisting of R1234ze, R1234yf, R1233zd and R1336mzz, wherein the composition has boiling point of more than 20 °C.
In another embodiment, the present invention provides a composition, comprising 5% by weight to 20% by weight of dichloromethane; and 80% by weight to 95% by weight of hydrofluoroalkene selected from a group consisting of R1234ze, R1234yf, R1233zd and R1336mzz.
In another embodiment, the present invention provides a composition, comprising 20% by weight to 50% by weight of dichloromethane; and 50% by weight to 80% by weight of hydrofluoroalkene selected from a group consisting of R1234ze, R1234yf, R1233zd and R1336mzz.
In another embodiment, the present invention provides a composition, comprising 50% by weight to 70% by weight of dichloromethane; and 30% by weight to 50% by weight of hydrofluoroalkene selected from a group consisting of R1234ze, R1234yf, R1233zd and R1336mzz.
In an embodiment, the present invention provides a composition, comprising 5% by weight to 15% by weight of dichloromethane; and 85% by weight to 95% by weight of R1234ze.
In another embodiment, the present invention provides a near azeotropic composition comprising: 20% by weight to 30% by weight of dichloromethane; and 70% by weight to 80% by weight of R1234ze.
In another embodiment, the present invention provides a near azeotropic composition comprising: 40% by weight to 55% by weight of dichloromethane; and 35% by weight to 60% by weight of R1234ze.
In another embodiment, the present invention provides a near azeotropic composition comprising: 60% by weight to 70% by weight of dichloromethane; and 30% by weight to 40% by weight of R1234ze.
In another embodiment, the present invention provides a composition comprising 75% by weight to 85% by weight of dichloromethane; and 15% by weight to 25% by weight of R1234ze.
In another embodiment, the present invention provides a near azeotropic composition comprising: 78% by weight to 82% by weight of dichloromethane; and 18% by weight to 22% by weight of R1234ze.
In another embodiment, the present invention provides a composition comprising 5% by weight to 15% by weight of dichloromethane; and 85% by weight to 95% by weight of R1234yf.
In another embodiment, the present invention provides a near azeotropic composition comprising: 20% by weight to 30% by weight of dichloromethane; and 70% by weight to 80% by weight of R1234yf.
In another embodiment, the present invention provides a near azeotropic composition comprising: 40% by weight to 55% by weight of dichloromethane and 35% by weight to 60% by weight of R1234yf.
In another embodiment, the present invention provides a near azeotropic composition comprising: 60% by weight to 70% by weight of dichloromethane; and 30% by weight to 40% by weight of R1234yf.
In another embodiment, the present invention provides a composition comprising: 75% by weight to 85% by weight of dichloromethane; and 15% by weight to 25% by weight of R1234yf.
In another embodiment, the present invention provides a near azeotropic composition comprising: 78% by weight to 82% by weight of dichloromethane; and 18% by weight to 22% by weight of R1234yf.
In an embodiment, the present invention provides a composition comprising 5% by weight to 15% by weight of dichloromethane and 85% by weight to 95% by weight of R1233zd.
In another embodiment, the present invention provides a near azeotropic composition comprising: 20% by weight to 30% by weight of dichloromethane and 70% by weight to 80% by weight of R1233zd.
In another embodiment, the present invention provides a near azeotropic composition comprising: 40% by weight to 55% by weight of dichloromethane and 35% by weight to 60% by weight of R1233zd.
In another embodiment, the present invention provides a near azeotropic composition comprising: 60% by weight to 70% by weight of dichloromethane and 30% by weight to 40% by weight of R1233zd.
In an embodiment, the present invention provides a composition comprising 75% by weight to 85% by weight of dichloromethane and 15% by weight to 25% by weight of R1233zd.
In another embodiment, the present invention provides a near azeotropic composition comprising: 78% by weight to 82% by weight of dichloromethane and 18% by weight to 22% by weight of R1233zd.
In an embodiment, the present invention provides a composition comprising 5% by weight to 15% by weight of dichloromethane and 85% by weight to 95% by weight of R1336mzz.
In another embodiment, the present invention provides a near azeotropic composition comprising: 20% by weight to 30% by weight of dichloromethane and 70% by weight to 80% by weight of R1336mzz.
In another embodiment, the present invention provides a near azeotropic composition comprising: 60% by weight to 70% by weight of dichloromethane and 30% by weight to 40% by weight of R1336mzz.
In an embodiment, the present invention provides a composition comprising 75% by weight to 85% by weight of dichloromethane and 15% by weight to 25% by weight of R1336mzz.
In another embodiment, the present invention provides a near azeotropic composition comprising: 78% by weight to 82% by weight of dichloromethane and 18% by weight to 22% by weight of R1336mzz.
In another embodiment, the present invention provides a composition, comprising 5% by weight to 95% by weight dichloromethane and 5% by weight to 95% by weight of a mixture of hydrofluoroalkene and hydrofluoroalkane.
In another embodiment, the present invention provides a blowing agent composition, comprising 5% by weight to 95% by weight dichloromethane and 5% by weight to 95% by weight of a mixture of hydrofluoroalkene and hydrofluoroalkane, wherein the composition has boiling point more than 20 °C.
In a preferred embodiment, the present invention provides a blowing agent composition, comprising 5% by weight to 70% by weight dichloromethane and 30% by weight to 95% by weight of a mixture of hydrofluoroalkene and hydrofluoroalkane, wherein the composition has boiling point more than 20 °C.
In an embodiment, the present invention provides a composition, comprising 5% by weight to 95% by weight of dichloromethane; 5% by weight to 95% by weight of hydrofluoroalkene and at least one hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), and hexafluorobutane (HFC-356).
In an embodiment, the present invention provides a blowing agent composition, comprising 5% by weight to 70% by weight of dichloromethane; 30% by weight to 95% by weight of hydrofluoroalkene and at least one hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), and hexafluorobutane (HFC-356) , wherein the composition has boiling point more than 20 °C.
In an embodiment, the present invention provides a composition, comprising 5% by weight to 20% by weight of dichloromethane; 80% by weight to 95% by weight of hydrofluoroalkene and at least one hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), and hexafluorobutane (HFC-356).
In an embodiment, the present invention provides a composition, comprising 20% by weight to 50% by weight of dichloromethane; 50% by weight to 80% by weight of hydrofluoroalkene and at least one hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), and hexafluorobutane (HFC-356).
In an embodiment, the present invention provides a composition, comprising 50% by weight to 75% by weight of dichloromethane; 25% by weight to 50% by weight of hydrofluoroalkene and at least one hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), and hexafluorobutane (HFC-356).
In another embodiment, the present invention provides composition, comprising 20% by weight to 75% by weight of dichloromethane; 40% by weight to 75% by weight of hydrofluoroalkene selected from a group consisting of R1234yf, R1234ze, 1233zd and 1336mzz(Z) and at least one hydrofluorocarbon selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134a/134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365) and hexafluorobutane (HFC-356).
In another embodiment, the present invention provides a composition, comprising 20% by weight to 50% by weight of dichloromethane; 2% by weight to 20% by weight of hydrofluoroalkene selected from a group consisting of R1234yf, R1234ze, 1233zd and 1336mzz(Z) and 40 to 75% by weight of at least one hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134a/134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365) and hexafluorobutane (HFC-356).
In another embodiment, the present invention provides composition comprising 20% by weight to 50% by weight of dichloromethane; 2% by weight to 8% by weight of hydrofluoroalkene selected from a group consisting of R1234yf, R1234ze, 1233zd and 1336mzz(Z) and 40% by weight to 75% by weight of hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), and hexafluorobutane (HFC-356).
In an embodiment, the present invention provides a composition, comprising: 50% by weight to 70% by weight of dichloromethane; 2% by weight to 20% by weight of hydrofluoroalkene selected from a group consisting of R1234yf, R1234ze, 1233zd and 1336mzz(Z); and 10% by weight to 45% by weight of hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), and hexafluorobutane (HFC-356); and
In an embodiment, the present invention provides a composition, comprising: 20% by weight to 70% by weight of dichloromethane; 15% by weight to 70% by weight of R245fa and 2% by weight to 20% by weight of hydrofluoroalkene selected from a group consisting of 1234yf and 1234ze.
In another embodiment, the present invention provides a composition, comprising: 55% by weight to 68% by weight of dichloromethane; 15% by weight to 40% by weight of R245fa and 3% by weight to 18% by weight of hydrofluoroalkene selected from a group consisting of 1234yf and 1234ze.
In another embodiment, the present invention provides a composition, comprising: 60% by weight to 65% by weight of dichloromethane; 20% by weight to 35% by weight of R245fa and 5% by weight to 15% by weight of hydrofluoroalkene selected from a group consisting of 1234yf and 1234ze.
In another embodiment, the present invention provides composition comprising 20% by weight to 50% by weight of dichloromethane; 2% by weight to 15% by weight of R1234yf and 40% by weight to 75% by weight of R245fa.
In another embodiment, the present invention provides composition comprising 25% by weight to 50% by weight of dichloromethane; 2% by weight to 6% by weight of R1234yf and 45% by weight to 70% by weight of R245fa.
In another embodiment, the present invention provides composition comprising 24 to 28 % by weight of dichloromethane; 4 to 6 % by weight of R1234yf and 65 to 70 % by weight of R245fa.
In another embodiment, the present invention provides composition comprising 33 to 38 % by weight of dichloromethane; 4 to 6 % by weight of R1234yf and 55 to 59 % by weight of R245fa.
In another embodiment, the present invention provides composition comprising 40 to 44 % by weight of dichloromethane; 2 to 4 % by weight of R1234yf and 50 to 56 % by weight of R245fa.
In another embodiment, the present invention provides composition comprising 45 to 49 % by weight of dichloromethane; 2 to 4 % by weight of R1234yf and 46 to 52 % by weight of R245fa.
In another embodiment, the present invention provides a composition, comprising 20% by weight to 75% by weight of dichloromethane; 40% by weight to 75% by weight of 1233zd and 2 to 20% be weight of at least one hydrofluorocarbon selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134a/134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365) and hexafluorobutane (HFC-356).
In another embodiment, the present invention provides composition comprising 20% by weight to 60% by weight of dichloromethane; 1% by weight to 10% by weight of R134a and 20% by weight to 75% by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 24% by weight to 48% by weight of dichloromethane; 2% by weight to 6% by weight of R134a and 50% by weight to 70% by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 24 to 27 % by weight of dichloromethane; 4 to 6 % by weight of R134a and 65 to 70 % by weight of R1233zd.
In another embodiment, the present invention provides blowing agent composition comprising 34 to 38 % by weight of dichloromethane; 4 to 6 % by weight of R134a and 55 to 59 % by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 37 to 40 % by weight of dichloromethane; 3 to 4 % by weight of R134a and 56 to 60 % by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 42 to 46 % by weight of dichloromethane; 3 to 4 % by weight of R134a and 50 to 54 % by weight of R1233zd.
In another embodiment, the present invention provides composition, comprising 20% by weight to 65% by weight of dichloromethane; 40% by weight to 75% by weight of hydrochlorofluoroalkene and at least one hydrofluoroalkene.
In another embodiment, the present invention provides composition comprising 20% by weight to 60% by weight of dichloromethane; 1% by weight to 8% by weight of R1234yf and 40% by weight to 75% by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 25% by weight to 50% by weight of dichloromethane; 2% by weight to 6% by weight of R1234yf and 50% by weight to 70% by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 24 to 28 % by weight of dichloromethane; 4 to 6 % by weight of R1234yf and 65 to 72 % by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 33 to 38 % by weight of dichloromethane; 4 to 6 % by weight of R1234yf and 55 to 60 % by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 37 to 40 % by weight of dichloromethane; 2 to 4 % by weight of R1234yf and 55 to 60 % by weight of R1233zd.
In another embodiment, the present invention provides a composition comprising 42 to 45 % by weight of dichloromethane; 2 to 4 % by weight of R1234yf and 50 to 55 % by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 20% by weight to 60% by weight of dichloromethane; 1% by weight to 8% by weight of R1234ze and 40% by weight to 75% by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 25% by weight to 50% by weight of dichloromethane; 2% by weight to 6% by weight of R1234ze and 50% by weight to 70% by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 24 to 28 % by weight of dichloromethane; 4 to 6 % by weight of R1234ze and 65 to 72 % by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 33 to 38 % by weight of dichloromethane; 4 to 6 % by weight of R1234ze and 55 to 60 % by weight of R1233zd.
In another embodiment, the present invention provides composition comprising 37 to 40 % by weight of dichloromethane; 2 to 4 % by weight of R1234ze and 55 to 60 % by weight of R1233zd.
In another embodiment, the present invention provides a composition comprising 42 to 45 % by weight of dichloromethane; 2 to 4 % by weight of R1234ze and 50 to 55 % by weight of R1233zd.
In another embodiment of the present invention, the compositions comprising dichloromethane and hydrofluoroalkenes are useful blowing agents in foams and cleaning agents.
In another embodiment, the compositions of present inventions are capable of producing a cellular structure via a foaming process in a variety of materials that undergo hardening or phase transition, such as polymers and plastics having different applications.
In another embodiment, the compositions of the present invention are used for making rigid foams used in refrigeration and insulation products.
In another embodiment, the compositions of the present invention are used for making foams useful for insulation of commercial/residential buildings, insulated metal panels, and appliance insulation.
In another embodiment, the composition of the present invention finds widespread use in industry for solvent cleaning and solvents in aerosols for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.
The composition of the present invention has good solvent properties to enable the cleaning and dissolution of flux resin and oils.
In another embodiment, the compositions of the present invention are useful as aerosol solvent applications for cleaning or deposition of certain types of lubricants, as a dust off, freeze spray or tire inflator. The compositions of the present invention act to propel and convert user product such as paints, lubricants, fire extinguisher and electrical & instrumentation panel cleaning agents into aerosols.
The compositions of the present invention have high gas thermal conductivity as compared to compositions of HCFC-141b. These compositions are very compatible with base polyols. They are completely soluble in base polyol and do not have any adverse effects on base polyols.
The compositions of the present invention also have zero ozone depletion potential (ODP) and very low global warming potential (GWP), therefore are very environment friendly. The compositions of the present invention are non-flammable.
In an embodiment, the present invention provides blowing agent compositions having zero ODP and having GWP of below 700.
In another embodiment, the blowing agent composition of the present invention provides foams having good dimensional stability at low as well as at higher temperatures. The dimensional stability of a foam is calculated as a percentage reduction at a low temperature range of 0 to 20°C and at higher temperature range of 60-80 °C. The dimensional stability of the blowing agent compositions of the present invention are close to the dimensional stability obtained with HCFC-141b.
In another embodiment, the blowing agent compositions of the present invention provides foams having good compressive strength of 150 to 180 kPa for a foam of density of 40 kg/m3, which is comparable to the compressive strength of foams produced using HCFC-141b. The compressive strength shows the capacity of the foam to withstand the compressive load.
In another embodiment, the blowing agent compositions of the present invention provides foams having good flexural strength, which is comparable to the flexural strength of foams produced using HCFC-141b. Flexural strength also called bending strength is a capacity of foam material to resist deformation under bending moment and is relative to the density of the foam used. The flexural strength of the foams produced using the blowing agent of the present invention is in the range of 0.1 to 0.25 N/mm2 for density of 40 kg/m3.
In another embodiment, the blowing agent compositions of the present invention provides foams having thermal conductivity comparable to the thermal conductivity of foams produced using HCFC-141b. The thermal conductivity is relative to the density of the foam used and the foams produced using the blowing agent of the present invention is in the range of 0.025 to 0.02 W/m-K with density of 40 kg/m3.
In another embodiment, the blowing agent compositions of the present invention provides foams with heat distortion temperature of 160 to 170°C for a density of 40 kg/m3, which is comparable to heat distortion temperature of foams obtained using HCFC-141b.
In another embodiment, the blowing agent compositions of the present invention provides foams, wherein no considerable change in volume percentage was observed at standard temperature pressure.
The blowing agent compositions of the present invention are useful in that they provide sufficient plasticization to permit the production of low density insulating thermoplastic foams with improved k-factor.
In a preferred embodiment, the present invention provides blowing agent compositions comprising dichloromethane and hydrofluoroalkene, wherein the composition has a boiling point of more than 20°C, and have thermal conductivity, heat distortion temperature, flexural strength, dimensional stability, compressive strength and GWP comparable to HCFC-141b and have zero ODP.
In another preferred embodiment, the present invention provides blowing agent compositions comprising dichloromethane and hydrofluoroalkene, wherein the compositions are environment friendly substitute for HCFC-141b.
A foamable polymer composition can contain additional additives such as nucleating agents, cell-controlling agents, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizing agents, antistatic agents, fire retardants, IR attenuating agents and thermally insulating additives. Nucleating agents include, among others, materials such as talc, calcium carbonate, sodium benzoate, and chemical blowing agents such azodicarbonamide or sodium bicarbonate and citric acid. IR attenuating agents and thermally insulating additives can include carbon black, graphite, silicon dioxide, metal flake or powder, among others. Flame retardants can include, among others, brominated materials such as hexabromocyclodecane and polybrominated biphenyl ether.
The blowing agent compositions of the present invention has boiling point more than 20 °C, preferably between 20 to 35 °C.
The process for foam preparation processes may include batch, semi-batch, and continuous processes.
Dichloromethane, R1234yf, R1233zd, and R1234ze are commercially available or may be prepared by methods known in the art.
It is against this and other backgrounds, which shall be filed in a detailed manner in complete specifications, in due course, the present invention is brought out and explained in following non-limiting examples.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention and specific examples provided herein without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention that come within the scope of any claims and their equivalents.
The details of various components as used in the present invention are described in the table below.
Table-1
Components Chemical name Chemical formula
R1234ze 1,3,3,3-tetrafluoropropene CF3CH=CHF
R1234ze(E) Trans-1,3,3,3-tetrafluoropropene CF3CH=CHF
R1234ze(Z) Cis-1,3,3,3-tetrafluoropropene CF3CH=CHF
R134a 1,1,1,2-tetrafluoroethane CH2FCF3
R152a 1,1-difluoroethane CHF2CH3
R245fa 1,1,1,3,3-Pentafluoropropane CF3CH2CHF2

The quantity of various components as used in the present invention are described in the table below.
Table-2
Compositions DCM
(% by weight) 245fa
(% by weight) 1234yf
(% by weight) 1233zd
(% by weight) 134a
(% by weight) 1234ze

1 80 20
2 65 30 5
3 65 25 10
4 65 20 15
5 60 35 5
6 60 30 10
7 65 30 5
8 65 25 10
9 65 20 15
10 60 35 5
11 60 30 10
12 42.11 54.74 3.16 0.000 0.000
13 47.37 49.47 3.16 0.000 0.000
14 36.84 57.89 5.26 0.000 0.000
15 26.32 68.42 5.26 0.000 0.000
16 38.95 0.00 0.00 57.89 3.16
17 44.21 0.00 0.00 52.63 3.16
18 36.84 0.00 0.00 57.89 5.26
19 26.32 0.00 0.00 68.42 5.26
20 38.95 0.00 3.16 57.89 0.00
21 44.21 0.00 3.16 52.63 0.00
22 36.84 0.00 5.26 57.89 0.00
23 26.32 0.00 5.26 68.42 0.00

The various physical and environment properties of compositions of the present invention and prior art composition HCFC-141b are tabulated below.
Table-3
Properties OF HCFC-141b
Molecular weight 116.9
Boiling point (°C) 32.9
Liquid specific gravity at 25°C 1.233
Heat of vaporization at boiling point (kJ/mole) 25.8
Gas phase thermal conductivity (mW/mK) at 10°C 8.8
Gas phase thermal conductivity (mW/mK) at 25°C 10
Vapour pressure (kg/cm2) at 10 °C 0.46
Vapour pressure (kg/cm2) at 25 °C 0.79
Flammable limits in air (vol%) 7.6-17.7
ODP (with CFC-11 =1) 0.1 1
GWP (with C02 = 1) 700

Table-4
Properties of compositions of present invention Range
Molecular weight 70-150
Boiling point (°C) 16-30
Liquid specific gravity at 25°C 1.1-1.3
Heat of vaporization at boiling point (kJ/mole) 25-28
Gas phase thermal conductivity (W/mK) at 10°C 7-8.2
Gas phase thermal conductivity (W/mK) at 25°C 10-12
Vapour pressure (kPa) at 10°C 0.4-1.5
Vapour pressure (kPa) at 25°C 0.8-2.5
Flammable limits in air (vol%) None
ODP 0
GWP Less than 700

Table-5
Physical and environmental properties Composition

1
2
3
4
5
6
Molecular weight 89.50 96.809 96.200 95.598 98.874 98.239
Boiling point (°C) 18 24 18 13 23 17
Specific gravity 1.287 1.321 1.305 1.290 1.323 1.308
Heat of vaporisation at boiling point (kJ/mole) 27.540 27.995 27.984 27.910 27.940 27.928
Gas phase thermal conductivity (mW/mK) at 10°C 8.088 8.475 8.553 8.577 8.664 8.743
Gas phase thermal conductivity (mW/mK) at 25°C 8.814 9.315 9.378 9.441 9.536 9.600
Vapour pressure (kg/cm2) at 10 °C 0.750 0.598 0.749 0.867 0.623 0.777
Vapour pressure (kg/cm2) at 25 °C 1.283 1.056 1.282 1.505 1.100 1.330
Flammable limits in air (vol%) No No No No No No
ODP (with CFC-11 =1)
0 0 0 0 0 0
GWP (with C02 = 1)
138.1 263.45 220.75 178.05 305.9 263.2

Table-6
Physical and environmental properties Composition
7 8 9 10 11
Molecular weight 96.809 96.200 95.598 98.874 98.239
Boiling point °C 26 22 19 25 21
Specific gravity 1.326 1.315 1.304 1.328 1.317
Heat of vaporisation at boiling point (kJ/mole) 27.963 27.921 27.818 27.908 27.865
Gas phase thermal conductivity (mW/mK) at 10 °C 8.456 8.514 8.572 8.644 8.703
Gas phase thermal conductivity (mW/mK) at 25 9.301 9.350 9.399 9.522 9.571
Vapour pressure (kg/cm2) at 10 °C 0.543 0.641 0.737 0.567 0.666
Vapour pressure (kg/cm2) at 25 °C 0.979 1.129 1.277 1.021 1.174
Flammable limits in air (vol%) No No No No No
ODP (with CFC-11 =1) 0 0 0 0 0
GWP (with C02 = 1) 263.6 221.05 178.5 306.05 263.5

Table-7
Properties 12 13 14 15 16 17
Molecular weight 105.6933 104.768 109.672 115.416 107.16 104.7331
Boiling point (°C) 23 23 18 16 23 23
Vapour pressure (kg/cm²) at 10°C -0.59184 -0.60397 -0.55583 -0.49553 -0.5798 -0.59938
Vapour pressure (kg/cm²) at 25°C -0.21365 -0.22755 -0.14002 -0.03131 -0.19283 -0.22672
Vapour pressure (kg/cm²) at 50°C 9.06434 9.13006 9.60027 10.0576 9.17584 8.99041
Gas phase thermal conductivity (W/mK) at 10°C 9.87623 10.0936 10.6324 11.1689 9.99758 9.79576
Gas phase thermal conductivity (W/mK) at 25°C 0.009876 0.010094 0.010632 0.011169 0.009998 0.009796
Heat of vaporization at boiling point (kJ/mole) 270.6754 281.2767 267.7966 251.7979 265.7572 273.2833
Flash point (°C) Above 200 Above 200 Above 200 Above 200 Above 200 Above 200
Flammability of liquid Non- Flammable Non- Flammable Non- Flammable Non- Flammable Non- Flammable Non- Flammable
ODP 0 0 0 0 0 0
GWP 473.5579 428.8737 500.2632 589.6316 47.16316 47.4
Type non-azeotropic non-azeotropic non-azeotropic non-azeotropic non-azeotropic non-azeotropic

Table-8
Properties 18 19 20 21 22 23
Molecular weight 107.6408 112.8986 107.5359 105.0921 108.2737 113.5949
Boiling point (°C) 20 17 23 24 20 18
Vapour pressure (kg/cm²) at 10°C -0.56503 -0.51179 -0.58115 -0.60065 -0.56735 -0.51445
Vapour pressure (kg/cm²) at 25°C -0.16648 -0.07547 -0.19535 -0.2291 -0.17081 -0.08039
Vapour pressure (kg/cm²) at 50°C 9.28391 9.67026 9.19312 9.00723 9.31315 9.7011
Gas phase thermal conductivity (W/mK) at 10°C 10.1147 10.5351 10.0122 9.80996 10.1395 10.5615
Gas phase thermal conductivity (W/mK) at 25°C 0.010115 0.010535 0.010012 0.00981 0.01014 0.010562
Heat of vaporization at boiling point (kJ/mole) 263.6483 247.5874 265.1314 272.7031 262.559 245.7447
Flash point (°C) Above 200 Above 200 Above 200 Above 200 Above 200 Above 200
Flammability of liquid Non- Flammable Non- Flammable Non- Flammable Non- Flammable Non- Flammable Non- Flammable
ODP 0 0 0 0 0 0
GWP 74.34211 73.86842 6.236842 6.473684 6.131579 5.657895
Type non-azeotropic Near Azeotrope non-azeotropic non-azeotropic non-azeotropic Near Azeotrope

EXAMPLE
The compositions of the present invention were prepared by adding different components in increasing order of vapour pressure and were analyzed using ASPEN.

WE CLAIM:

1.A composition comprising, 5% by weight to 95% by weight of dichloromethane; and 1% by weight to 95% by weight of one or more of hydrofluoroalkene.
2. The composition as claimed in claim 1, wherein the hydrofluoroalkene is selected from a group consisting of R1234ze, R1234yf, R1233zd and R1336mzz.
3. The composition as claimed in claim 1, wherein the composition further comprises of at least one hydrofluoroalkane selected from a group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245fa), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365) and hexafluorobutane (HFC-356).
4. The compositions as claimed in claim 1, wherein the composition is used as a blowing agent, cleaning solvent and aerosols.
5. The compositions as claimed in claim 1, wherein the compositions are non-flammable, have zero ozone depletion potential and global warming potential of less than 700.
6. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with good dimensional stability at low as well as at higher temperatures.
7. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with compressive strength, comparable to the compressive strength of foams produced using HCFC-141b.
8. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with flexural strength, comparable to the flexural strength of foams produced using HCFC-141b.
9. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with thermal conductivity comparable to the thermal conductivity of foams produced using HCFC-141b.
10. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with heat distortion temperature of 165°C to 180°C, which is comparable to heat distortion temperature of foams obtained using HCFC-141b.