FIELD OF THE INVENTION
The present invention provides compositions comprising dichloromethane, polyol ester and one or more compounds selected from a group consisting of hydrofluoroalkenes and hydrofluoroalkanes. These compositions are very useful as blowing agents and are also used in rigid and flexible foams.
BACKGROUND OF THE INVENTION
Foam blowing agent is a substance that produce a cellular structure via foaming
process in a variety of materials such as polymers and plastics through hardening or
phase transition.
European Pub. No. 2666811 provides blowing agent compositions comprising
tetrafluoroalkene such as R1234ze, R1233, or R1233xf, or R1233zd. and
hydrofluorocarbons such as HFC-32, HFC-161, HFC-152, HFC-143, HFC-134,
HFC-125, HFC-245fa, HFC-236, HFC-227ea, HFC-365, andHFC-356.
PCT Pub. No 1999035209 provides an azeotrope-like composition comprising about
80 to about 99.9 weight percent R245fa and from about 0.1 to about 20 weight
percent of methylene chloride.
There remains a need to develop an efficient blowing agent that can be used for wide
variety of applications. The present invention provides compositions comprising
dichloromethane, polyol ester and one or more compounds selected from a group
consisting of hydrofluoroalkenes and hydrofluoroalkanes.
OBJECT OF THE INVENTION
The main object of the present invention is to provide compositions comprising dichloromethane, polyol ester and one or more compounds selected from a group consisting of hydrofluoroalkenes and hydrofluoroalkanes.

SUMMARY OF THE INVENTION
The present invention provides compositions comprising dichloromethane, polyol ester and one or more compounds selected from a group consisting of hydrofluoroalkenes and hydrofluoroalkanes.
DETAILED DESCRIPTION OF THE INVENTION
As used herein the hydrofluoroalkene refers to (cis and/or trans)-l,3,3,3-
tetrafluoropropene (R-1234ze); 2,3,3,3-tetrafluoropropene (R-1234yf); (cis and/or
trans)-l-chloro-3,3,3-trifluoropropene (R-1233zd), and mixtures thereof.
As used herein, the term "hydrofluoroalkane" refers to a component selected from a
group consisting of difluoromethane (R-32), fluoroethane (R-161), difluoroethane
(R-152a), trifluoroethane (R-143a), 1,1,1,2-tetrafluoroethane (R-134a), 1,1,2,2-
tetrafluoroethane (R-134), pentafluoroethane (R-125), 1,1,1,3,3-pentafluoropropane
(R-245fa).
As used herein, the term polyol ester refers to polyol ester oil or POE oil having a
flash point of above 200 and which may contain a phenolic antioxidant, a specified
amine compound and a phosphoric tri-ester to prevent the hydrolysis of the polyol
ester.
As used herein, the zeotropic or non-azeotropic composition is a mixture of two or
more substances that behaves as a simple mixture rather than a single substance.
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 with constant boiling and cannot be separated during a phase
change.
As used herein, the foam refers to a rigid or a flexible foam which is either a
thermoset foam selected from a group consisting of polyurethane, polyisocyanate,

and phenolic foams or a thermoplastic foam selected from a group consisting of
polystyrene, polypropylene, polyvinylchloride or the like.
As used herein, the term flexural strength, also known as modulus of rupture, or bend
strength, or transverse rupture strength is a material property, defined as the stress in
a material just before it yields in a flexure test.
As used herein, the term "compressive strength" or "compression strength" is the
capacity of a material or structure to withstand loads tending to reduce size, as
opposed to which withstands loads tending to elongate. In other words, compressive
strength resists being pushed together, whereas tensile strength resists tension (being
pulled apart).
As used herein, the term "apparent core density" also known as "bulk density", or
"volumetric density" is defined as the mass of the many particles of the material
divided by the total volume they occupy.
As used herein, the term "volume percentage of closed cells" is indicative of the
insulating quality of cellular plastics and is an important variable, requiring control
during manufacture and evaluation after production.
As used herein, the term "heat distortion temperature" or "heat deflection
temperature" (HDT, HDTUL or DTUL) is the temperature at which a polymer or
plastic sample deforms under a specified load.
As used herein, the term "thermal conductivity" measures the ease with which heat
can travel through a material by conduction. Conduction is the main form of heat
transfer through insulation. It is often termed as the X (lambda) value. The lower the
figure, the better the thermal resistance of insulating material.
The present invention provides compositions comprising dichloromethane, polyol
ester and one or more compounds selected from a group consisting of
hydrofluoroalkenes and hydrofluoroalkanes.

In an embodiment, the present invention provides a composition comprising, 20%
by weight to 90% by weight of dichloromethane; 1% by weight to 10% by weight of
polyol esters and 5% by weight to 80% by weight of component selected from a
group consisting of hydrofluoroalkene, hydrofluoroalkane or mixture thereof.
In another embodiment, the present invention provides composition comprising: 65
to 90 by weight of dichloromethane; 10 to 30 by weight of R1234ze; 5 to 10% by
weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising: 70
to 80 by weight of dichloromethane; 16 to 22 by weight of R1234ze; 5 to 10% by
weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 28
to 50% by weight of dichloromethane; 2 to 6% by weight of R1234yf; 40 to 65% by
weight of R1233zd; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 32
to 45% by weight of dichloromethane; 2 to 6% by weight of R1234yf; 45 to 58% by
weight of R1233zd; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 18
to 30% by weight of dichloromethane; 2 to 10% by weight of R1234yf; 50 to 70%
by weight of R1233zd; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 22
to 26% by weight of dichloromethane; 3 to 6% by weight of R1234yf; 60 to 66% by
weight of R1233zd; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 20
to 65% by weight of dichloromethane; 1 to 10% by weight of polyol ester; 2 to 10%
by weight of one or more hydrofluoroalkene and 15 to 70% by weight of one or more
hydrofluoroalkane.

In another embodiment, the present invention provides composition comprising 20
to 65% by weight of dichloromethane; 1 to 10% by weight of polyol ester; 2 to 10%
by weight of 1234yf and 15 to 70% by weight of 245fa.
In another embodiment, the present invention provides composition comprising 52
to 64% by weight of dichloromethane; 21 to 35% by weight of R245fa; 4 to 10% by
weight of R1234yf; and 5 to 10% by weight of poly ol ester oil.
In another embodiment, the present invention provides composition comprising 55
to 64% by weight of dichloromethane; 16 to 20% by weight of R245fa; 12 to 16%
by weight of R1234yf; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 30
to 48% by weight of dichloromethane; 2 to 6% by weight of R1234yf; 42 to 57% by
weight of R245fa; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 22
to 26% by weight of dichloromethane; 3 to 6% by weight of R1234yf; 58 to 67% by
weight of R245fa; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 20
to 65% by weight of dichloromethane; 1 to 10% by weight of polyol ester; 2 to 10%
by weight of 1234ze and 15 to 70% by weight of 245fa.
In another embodiment, the present invention provides composition comprising 52
to 64% by weight of dichloromethane; 21 to 35% by weight of R245fa; 4 to 10% by
weight of R1234ze; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 50
to 70% by weight of dichloromethane; 10 to 25% by weight of R245fa; 10 to 20%
by weight of R1234ze; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 56
to 64% by weight of dichloromethane; 16 to 20% by weight of R245fa; 12 to 16%
by weight of R1234ze; and 5 to 10% by weight of polyol ester oil.

In another embodiment, the present invention provides composition comprising 30
to 50% by weight of dichloromethane; 2 to 6% by weight of R134a; 40 to 65% by
weight of R1233zd; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 32
to 45% by weight of dichloromethane; 2 to 6% by weight of R134a; 45 to 58% by
weight of R1233zd; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 20
to 30% by weight of dichloromethane; 1 to 10% by weight of R134a; 50 to 72% by
weight of R1233zd; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 22
to 26% by weight of dichloromethane; 3 to 7% by weight of R134a; 58 to 67% by
weight of R1233zd; and 5 to 10% by weight of polyol ester oil.
In another embodiment, the present invention provides composition comprising 5%
by weight to 95% by weight of dichloromethane; 5% by weight to 95% by weight of
245fa; and 1 to 10% by weight of polyol ester.
In another embodiment, the present invention provides composition comprising 20%
by weight to 85% by weight of dichloromethane; 10% by weight to 70% by weight
of 245fa; and 1 to 10% by weight of polyol ester.
In another embodiment, the present invention provides composition comprising 50%
by weight to 70% by weight of dichloromethane; 20% by weight to 50% by weight
of R245fa; and 1 to 10% by weight of polyol ester.
In another embodiment, the present invention provides composition comprising 52%
by weight to 60% by weight of dichloromethane; 35% by weight to 42% by weight
of R245fa; and 5 to 10% by weight of polyol ester.
In another embodiment, the present invention provides composition comprising 20%
by weight to 70% by weight of dichloromethane; 10% by weight to 70% by weight

of R245fa; and 1.5% by weight to 20% by weight of R134a; and 5 to 10% by weight
of polyol ester.
In another embodiment, the present invention provides composition comprising 40%
by weight to 70% by weight of dichloromethane; 10% by weight to 60% by weight
of R245fa; and 1.5% by weight to 20% by weight of R134a; and 1 to 10% by weight
of polyol ester.
In another embodiment, the present invention provides composition comprising 40%
by weight to 62% by weight of dichloromethane; 12% by weight to 52% by weight
of R245fa; and 1.5% by weight to 19% by weight of R134a; and 5 to 10% by weight
of polyol ester.
In another embodiment, the present invention provides composition comprising 20%
by weight to 50% by weight of dichloromethane; 40% by weight to 70% by weight
of R245fa; 2% by weight to 5% by weight of R134a and 1 to 10% by weight of polyol
ester.
In another embodiment, the present invention provides composition comprising 23%
by weight to 46% by weight of dichloromethane; 44% by weight to 66% by weight
of R245fa; 2% by weight to 5% by weight of R134a and 5 to 10% by weight of polyol
ester.
In another embodiment, the present invention provides composition comprising 50%
by weight to 70% by weight of dichloromethane; 10% by weight to 40% by weight
of R245fa; and 3% by weight to 19% by weight of R152a; and 1 to 10% by weight
of polyol ester.
In another embodiment, the present invention provides composition comprising 53%
by weight to 62% by weight of dichloromethane; 13% by weight to 30% by weight
of R245fa; and 4% by weight to 15% by weight of R152a; and 5 to 10% by weight
of polyol ester.

In another embodiment, the present invention provides composition comprising 70%
by weight to 95% by weight of dichloromethane; 5% by weight to 20% by weight of
R134a; and 1 to 10% by weight of polyol ester.
In another embodiment, the present invention provides composition comprising 75%
by weight to 88% by weight of dichloromethane; 8% by weight to 16% by weight of
R134a; and 5 to 10% by weight of polyol ester.
In another embodiment, the present invention provides composition comprising 70%
by weight to 90% by weight of dichloromethane; 10% by weight to 20% by weight
of R152a; and 1 to 10% by weight of polyol ester.
In another embodiment, the present invention provides composition comprising 75%
by weight to 82% by weight of dichloromethane; 12% by weight to 16% by weight
of R152a; and 5 to 10% by weight of polyol ester.
The compositions of the present invention are non-flammable and have GWP less
than 700.
The compositions of the present invention are used as a blowing agent, cleaning
solvent and aerosols.
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. They enable the
cleaning and dissolution of flux resin and oils.
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 have lower gas thermal conductivity as
compared to compositions of blowing agents already in use such as HCFC-141b and
provides an efficient replacement for HCFC-141b.

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 & plastics having different applications such as
polyurethane foams useful in refrigeration system, spray foam, rigid foam, flexible
foams useful in mattresses, pillows and cushions.
The compositions of the present invention are used for making moulded foams used
in shoe soles, saddles etc.
The compositions of the present invention are used for making spray foams useful
for insulation of commercial/residential buildings, insulated metal panels, and
appliance insulation.
In an embodiment of the present invention, the compositions provide foams with
flexural strength in the range of 0.32-0.33 N/mm2.
In an embodiment of the present invention the compositions provide foams with
compressive strength in the range of 200.0-206.0 kPa
In an embodiment of the present invention, the compositions provide foams with heat
distortion temperature of 174°C to 180°C.
In an embodiment of the present invention, the compositions provide foams with
thermal conductivity in the range of 0.016-0.018 W/m.K
Also, the foam prepared by the compositions of the present invention have higher
flexural strength, higher compressive strength, better dimensional stability, higher
heat distortion temperature and has comparable volume % of closed cells and showed
negligible dimensional shrinkage with respect to the known compositions.
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.
These compositions 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.

The components of the composition of present invention such as Dichloromethane,
R245fa, R134a, R1233zd, R1234yf, R1234ze and polyol esters 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.

WE CLAIM:

1. A composition comprising, 20% by weight to 90% by weight of
dichloromethane; 1% by weight to 10% by weight of polyol esters and 5% by
weight to 80% by weight of component selected from a group consisting of
hydrofluoroalkene, hydrofluoroalkane or mixture thereof.
2. The composition as claimed in claim 1, wherein the hydrofluoroalkene is selected from a group consisting of (cis and/or trans)-l,3,3,3-tetrafluoropropene (R-1234ze); 2,3,3,3-tetrafluoropropene (R-1234yf); (cis and/or trans)-l-chloro-3,3,3 -trifluoropropene (R-1233 zd).
3. The composition as claimed in claim 1, wherein the hydrofluoroalkane is selected from a group consisting of difluoroethane (HFC-152a), tetrafluoroethane (HFC-134 or HFC-134a), and 1,1,1,3,3-pentafluoropropane (HFC-245fa).
4. The compositions as claimed in claim 1, wherein the compositions are 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 replacement of HCFC-141b.
7. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with compressive strength in the range of 200.00-206.0 kPa.

8. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with flexural strength in the rage of 0.32-0.33 N/mm2.
9. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with thermal conductivity in the range of 0.016-0.018 W/m.K.
10. The blowing agent compositions as claimed in claim 1, wherein the compositions provide foams with heat distortion temperature of 174°C to 180°C.