Note: Descriptions are shown in the official language in which they were submitted.
' CA 02303709 2000-04-11
y
This application is a division of co-pending
application 2,009,169 filed on February 2, 1990.
The present invention relates to the use of C3 to
C3 polyfluoroalkanes comprising at least two fluorine
atoms as propellants, especially for aerosols and in the
production of plastic foams.
The use of fluorochlorohydrocarbons, for example
trichlorofluoromethane, dichlorodifiuoromethane and
trichlorofluoroethane, as propellants for the above
purposes, is known. According to more recent studies, the
chlorine content of cenventicnal propellants damages the
ozone layer of the earth's atmosphere (see J.F.D. Mills,
Cell. Polym. ~, 343 (I987) and F.S. Rowland et al.,
Nature ~, 8 (19?4)); for this reason limits have been
- specified for the amounts of fluorochlorohydrocarbons pro-
duced. The need has therefore arisen for chlorine-free
propellants.
We have now found that those poiyfluoraalkanes of
the formula
CZ3_CYz_R ( I )
wherein
2d the radicals 8 located on the same carbon atom stand for
hydrogen and/or fluorine,
the radicals Y located on the same carbon atom stand for
hydrogen, fluorine and/or CFA, and
R stands for CHZF, CHF=, C8" CFs, CFs-CH" CFzCHzF,
2 5 C$a-C$3 s ~-~z-~~ ~_ -~ ( ~3 ~ ~3
and Wherein the polyfluoroalkanes of the formula (I) con-
~e A 25 654 - 1 -
CA 02303709 2000-04-11
tain at least two fluorine atoms,
can be used advantageously as propellants.
Those. polyfluoroalkanes of the formula (I) are
preferred which contain 3 to 7, particularly 4 to 6
fluorine atoms. ,
Furthermore, those polyfluoroalkanes of the
formula (I) are preferred in which the C83 group repre-
sents a CF3, CHFz or CHI group and the CYz group represents
a CHZ, CFC?', CFi or C ( CFA ) H group .
For the use according to the invention, those
individual compounds conforming to formula (I) in which
X3, YZ and R are present in one of the combinations listed
in Table l, are particularly preferred.
Le A 26 ,~54 _
CA 02303709 2000-04-11
Table 1
~
z
yz R
F3 Hz CH2F
F3 ~ ~ CHZF
F3 HZ CHFZ
xF2 FZ cHZF
F3 ~ ~
3
H3 Fz CH3
F3 Fz CFZ-CH3
F3 HF CF2-CH3
F3 H2 CFZ-CFH2
F3 HZ CHZ-CH3
H3 F2 CFZ-CH3
F3 H2 CFZ-CH3
F3 HCF3 ~3
F3 Hz CHZ-CHZ-CH3
F3 H2 -CH ( CIi3 ) -CH3
F3 HZ CF3
The methods for preparing the polyfluoroalkanes
for use according to the invention are known (see, for
example, Zh. Org. Rhim. 1980, 1401-1408 and 1982, 946 and
1168; Zh. Org. Rhim. 1988, 1558; J. Chem. Soc. Perk. 1,
1980, 2258; J. Chew. Soc. Perk. Traps. 2, 1983, 1713; J.
Chem. Soc. C 1969, 1739; Chem. Soe. 1949, 2860; Zh. Anal.
Khim. 1981 36 (6), 1125; J. Fluorine Chew. 1979, 325;
Izv. Akad. Nauk. SSSR, Ser. Rhim. ~Q, 2117 (in
Russian); Rosz. Chew. 1974 (48), 1697 and J.A.C.S. ~7,
1195_(1945), ~, 3577 (1950) and J,~, 2343 (1954)).
The propellants for uae according to the
~.~~'~4 _ 3
CA 02303709 2000-04-11
invention.are particularly suitable for aerosols and
production of plastic foams; the individual compounds of
the formula (I), mixtures of compounds of the formula (I)
and mixtures of compounds of the formula (I) with conven-
tional propellants may be used for this purpose.
Individual compounds of the formula (I) or mixtures of
compounds of the formula (I) are preferred.
Suitable aerosols are those employed for cosmetic
and medicinal purposes, for example deodorant aerosols,
anti-asthma sprays and liquid plaster sprays. Aerosols
which employ the propellants for use according to the
invention, are distinguished by the fact that the propel-
lant is inert and the ozone layer of the earth's
atmosphere is no longer negatively affected by the
corresponding amount of propellants according to the
invention, since they are chlorine-free.
The methods of producing plastic foams using
propellants is generally known. In the production of
closed-cell foams the propellants may also act as heat-
insulating cellular gases. This is also true for the
propellants for use according to the invention.
The propellants for use according to the inven-
tion may be employed, for example, in the production of
foams based on isocyanates, polystyrenes, polyvinyl
chlorides and phenol-formaldehyde condensates. They are
preferably used in the production of foams based on
isocyanates, in particular in the production of poly
urethane and/or polyisocyanurate foams; they are
especially preferred in the production of rigid foams
based on isocyanates.
he A 26 654 -
CA 02303709 2000-04-11
The production of foams based on isocyanates is
known per se and is described, for example, in German
Offenlegungsschriften 1,694,142, 1,694,215 and l,?20,?68,
as well as in Bunststoff-Handbuch [Plastics Handbook],
volume VII, Polyurethane, edited by Vieweg and HtSchtlen,
Carl Hanser Verlag, Munich 1966, and in the new edition
of this tome, edited by G. Oertel, Carl Hanser Verlag,
Munich, Vienna, 1983.
These foams are mainly those comprising urethane
and/or isocyanurate and/or allophanate and/or uretdione
and/or urea and/or carbodiimide groups.
The following can be employed for the production
of foams based on isocyanates, using propellants accord-
ing to the inventions
a) As starting components aliphatic, cycloaliphatic,
araliphatic, aromatic and heterocyclic polyiso-
cyanates, such as those described, for example, lay
W. Siefken in Justus Liebigs Annalen der Che>zEi~e,
562, pp. ?5-136, for example those of the formula
Q(NCO)n
in which
n denotes 2-4, preferably 2-3,
and
Q denotes an aliphatic hydrocarbon radical of 2-18,
preferably 6-10 carbon atoms, a cycloaliphatic
hydrocarbon radical of 4-15, preferably 5-10 carbon
atoms, an aromatic hydrocarbon radical of 6-15,
preferably 6-13 carbon atoms or an araliphatic
_hydrocarbon radical of 8-15, preferably 8-13 carbon
atoms, for example such polyisocyanates as described
Le A 26 654 - 5 -
CA 02303709 2000-04-11
in DE-OS 2,832,253, pp. 10-11. Particularly prefer-
red are usually those polyisocyanates which are
technically readily accessible, for example the 2,4-
and 2,6-toluylene diisocyanate as well as any
mixture of~these isomers ("TDI"); polyphenylpoly-
methylenepolyisocyanates, such as those obtained by
an aniline-formaldehyde condensation and subsequent
treatment with phosgene ("crude 1~I"), and poly-
isocyanates comprising carbodiimide groups, urethane
groups, allophanate groups, isocyanurate groups,
urea groups or biuret groups ("modified polyiso
cyanates"), especially those modified polyiso
cyanates which are derived from 2,4- and/or 2,6
toluylene diisocyanate and from 4,4'- and/or 2,4'
diphenylmethane diisocyanate.
b) The starting components may further be compounds of
a molecular weight usually of 400 to 10,000, con-
taining at least two hydrogen atoms reactive toward
isocyanates. These comprise, besides compounds
containing amino, thio or carboxyl groups, preferab-
ly compounds containing hydroxyl groups, in
particular compounds containing 2 to 8 hydroxyl
groups, especially those of a molecular weight of
1,000 to 6,000, preferably 2,000 to 6,000, for
example polyethers and polyesters as well as poly-
carbonates and polyester amides containing at least
2, usually 2 to 8, pr~ferably 2 to 6 hydroxyl
groups; these compounds are known per se for the
_preparation of homogeneous and cellular polyure-
thanes and are disclosed, for example, in DE-OS
Le A 26 654
CA 02303709 2000-04-11
2,832,253, pp. 11-18.
c) When appropriate, compounds comprising at least two
hydrogen atoms reactive toward isocyanates and of a
molecular weight of 32 to 399 may be used as further
starting components. Also in this case compounds
containing hydroxyl groups and/or amino groups
and/or thiol groups and/or carboxyl groups, pre-
ferably compounds containing hydroxyl groups and/or
amino groups, are understood to be those which are
used as chain lengtheners or crosslinking agents.
These compounds usually have 2 to 8, preferably 2 to
4 hydrogen atoms reactive toward isocyanates.
Appropriate examples are disclosed in DE-OS
2,832,253, pp. 19-20.
d) One polyfluoroalkane or several polyfluoroalkanes of
the formula (I) as propellant and insulating gas, if
appropriate in admixture with conventional propel-
lants and insulating gases.
- e) When appropriate, other auxiliary agents and addi
tives may be used at the same time, such as
- water and/or other highly volatile organic
substances as propellants,
- additional catalysts of the type known per se in
amounts up to 10% by weight, based on the com
ponent b),
- surface-active additives, such as emulsifiers and
foam stabilizers,
- reaction retardants, for esample acidic substan
- ces such as hydrochloric acid or organic acid
halides, also cell regulators of the type known
L~ A 26 654 -
CA 02303709 2000-04-11
per se such as paraffins or fatty alcohols or
dimethylpolysiloxanes as well as pigments or dyes
and other flame retardants of the type known per
se, for example tricresyl phosphate, also stabi-
lizers against the effects of ageing and
weathering, plasticizers and fungistats and
bacteriostats as well as fillers such as barium
sulphate, kieselguhr, carbon black or whiting.
Other examples of surface active additives, foam
stabilizers, cell regulators, reaction retardants,
stabilizers, flame retardants, plasticizers, dyes,
fillers, fungistats, bacteriostats to be used at the same
time if appropriate, as well as details concerning the
use and action of these additives are described in
Kunststoff-Handbuch [Plastics Handbook , volume VII,
edited by Vieweg and Htichtlen, Carl Hanser Verlag, Munich
1966, for example on pages 103-113.
The isocyanate-based foams can be prepared in a
manner known per se.
The preparation of polyurethane plastics may be
prepared, for example, as followss the reactants are
caused to react by the single-stage process known per se,
the prepolymer process or the semiprepolymer process,
frequent use being made of plant machinery, for example
that disclosed in US 2,764,565. Details concerning the
processing plant which are likewise relevant according to
the invention, are described in lCunatatoff-Handbuch,
volume VII, edited by Vieweg and HtSchtlen, Carl Hanser
Verlag, Munich 1966, for example on pages 121 to 205.
.
Le A 26 654 _ g
CA 02303709 2000-04-11
23189-7061D
According to the invention it is also possible to
produce cold-curing foams (cf. GB-PS 1,162,517, DE-OS
2, 153, 086) .
Foams may of course also be produced by block foaming
or by the double conveyor belt process known per se.
The products obtainable according to the invention
may be used, for example, as insulation panels for roof
insulation.
In foam production, the propellants for use according
to the invention may be employed, for example, in amounts of 1
to 30o by weight, preferably 2 to loo by weight, in each case
based on the foam.
Compared with conventional foams of similar or
virtually identical cell structure, foams produced by
propellants for use according to the invention are
distinguished by the fact that in their production, application
and disposal they no longer negatively affect the ozone layer
of the earth's atmosphere by the corresponding amount of the
propellants according to the invention.
Polyfluoroalkanes of the formula (I) may be further
employed as degreasing and cleansing agents, for example in the
electrical industry. The same polyfluoroalkanes are preferred
for this purpose as those referred to above as being preferred.
Here, too, the individual compounds of the formula (I),
mixtures of compounds of the formula (I) and mixtures of
compounds of the formula (I) with conventional degreasing and
cleansing agents may be employed.
9
CA 02303709 2000-04-11
'_
Example 1
100 g of a polyether with a hydroxyl value of 380,
which has resulted from the addition of propylene
oxide to a solution of saccharose, propylene
glycol and water,
2 g of a :~Filoxane polyether copolymer as foam
stabilizer,
3.8 g of water and
3 g of dimethylcyclohexylamine were mixed.
100 g of this mixture were thoroughly mixed with
15 g of 1,1,1,3,3,3-hexafluoro-2-methylpropane as
propellant, using a laboratory stirrer'.
This mixture was foamed with 152 g of crude 4,4 ~-
diisocyanatodiphenylmethane. A rigid polyurethane foam
was obtained. Foaming and physical datas
Induction time (s) s 10
Setting time (s) s 42
Free density (kg/m') s 24
Cell structure s fine
Example 2
100 g of a polyether with a hydroxyl value of 380 which
results from the addition of propylene oxide to
a solution of saccharose, propylene glycol and
water,
2 g of a siloxane polyether copolymer as foam
stabilizer,
3.8 g of water and
3 - g of dimethylcyclohexylamine were mixed.
Le A 26 654 - 10 -
- CA 02303709 2000-04-11
~-" ,
100 g of this mixture were thoroughly mixed with
15 g of 1,1,1,3,3,3-hexafluoropropane as propellant,
using a laboratory stirrer.
This mixture was foamed with 152 g of crude 4,4'
diisocyanatodiphenylmethane. A rigid polyurethane foam
was obtained. Foam and physical datas
Induction time (s) : 10
Setting time (s) : 40
Free density (kglm3) : 22
Cell structure : fine.
I~e A 26" 654 - 11 -
'. CA 02303709 2000-04-11
Example 3
100 g of a polyether with a hydroxyl value of 380 which
- results~from the addition of propylene oxide to
a solution of saccharose, propylene glycol and
water,
2 g of a siloxane polyether copolymer as foam
stabilizer,
3.8 g of water and
3 g of dimethylcyclohexylamine were mixed.
100 g of this mixture were thoroughly mixed with
15 g of 2,2,4,4-tetrafluorobutane as propellant, using
a laboratory stirrer.
This mixture was foamed with 152 g of crude 4,4'~
diisocyanatodiphenylmethane. A rigid polyurethane foam
was obtained. Foaming and physical dates
Induction time (s) s 10
Setting time (s) : 39
Free density (kg/m~) : 21
dell structure s fine.
Example 4
60 g of a polyether with a hydroxyl value of 950 which
resulted from the addition of propylene oxide to
trimethylpropane,
40 g of a polyether with a hydroxyl value of 56 which
Le A 26 654 - 12 -
CA 02303709 2000-04-11
resulted from the addition of propylene oxide to
trimethylpropane,
0.5 g of water and
2 g of a siloxane polyether copolymer as foam stabi-
lizer were mixed.
100 g of this mixture was thoroughly mixed with
g of 1,1,1,3,3,3-hezafluoro-2-methylpropane as
propellant, using a laboratory stirrer.
This mixture was foamed with 164 g of crude 4,4'-
10 diisocyanatodiphenylmethane. A rigid solid polyurethane
plastic was obtained. Foaming and physical data:
Induction time (8) _ ~5
Setting time (s) s 120
Free density (kg/m3) s 75
Total density compacted (kg/m'j : 350
Cell structure : fine.
Example 5
- 60 g of a polyether with a hydroxyl value of 950 which
resulted from the addition of propylene oxide to
trimethylpropane,
40 g of a polyether with a hydroxyl value of 56, which
resulted from the addition of propylene oxide to
trimethylolpropane,
0.5 g of water and
2 g of a siloxane polyother copolymer as foam stabi-
lizer were mixed.
100 g of this mixture were thoroughly mixed with
Ire A 26 654 - 13 -
-. CA 02303709 2000-04-11
g of the 1,1,1,3,3,3-hexafluoropropane according to
the invention as propellant, using a laboratory
stirrer.
This mixture was foamed with 164 g of crude 4,4'-
5 diisocyanatodiphenylmethane. A rigid solid polyurethane
plastic was obtained. Foaming and physical data:
Induction time (s) s 88
Setting time (s) s 136
Free density (kg/m3) s 70
10 Total density compacted (kg/m') s 350
Cell structure s fine.
Fxample 6
60 g of a polyether with a hydroxyl value of 950 which
resulted from the addition of propylene oxide to
trimethylolpropane,
40 g of a polyether with a hydroxyl value of 56 which
resulted from the addition of propylene oxide to
trimethylolpropane,
0.5 g of water and
2 g of a siloxane polyether copolymer as foam stabi-
lizer were mixed.
100 g of this mixture were thoroughly mixed with
10 g of 2,2,4,4-tetrafluorobutane as propellant, using
a laboratory stirrer.
This mi~cture was foamed with 164 g of crude 4,4'-
dii:ocyanatodiphenylmethane. A rigid solid polyurethane
plastic was obtained. Foaming and physical data:
I~e A 26 654 - 14 -
'- CA 02303709 2000-04-11
Induction time (s) . 83
Setting time (s) s 138
Free density (kg/m') s 68
Total density compacted (kg/m') s 350
Cell structure s fine.
Example 7
91 g of a polyether with a hydroxyl value of 56 which
resulted from the addition of propylene oxide to
trimethylolpropane,
9 g of monoethylene glycol and
0.1 g of water were mixed.
100 g of this mixture were thoroughly mixed with
g of 1,1,1,3,3,3-hexafluoro-2-methylpropane as
propellant, using a laboratory stirrer.
This mixture was foamed with 56 g of crude 4,4~-
15 diisocyanatodiphenylmethane. A tough and resilient
polyurethane foam was obtained. Foaming and physical
data:
Induction time (s) s 33
Setting time (s) s 112
Free density (kg/m') s 131
Total density compacted (kg/m3) s 350
Cell structure s fine.
Example 8
91 g of a polyether with a hydroxyl value of 56, which
resulted from the addition of propylene oxide to
trimethylolpropane,
- 9 _ g of monoethylene glycol and
0.1 g of water were mixed.
he A 26 654 - 15 -
CA 02303709 2000-04-11
100 g of this mixture were thoroughly mixed with
15 g of, 1,1,1,3,3,3-hexafluoropropane as propellant,
using a laboratory stirrer.
This mixture was foamed with 56 g of crude 4,4'-
diisocyanatodiphenylmethane. A tough and resilient
polyurethane foam was obtained. Foaming and physical.
data:
Induction time (s) s 36
Setting time (s) s 108
Free density (kg/m3) s 121
Cell structure s fine.
Example 9
91 g of a polyether with a hydroxyl value of 56, which
resulted from the addition of propylene oxide to
trimethylolpropane,
9 g of monoethylene glycol and
0.1 g of water were mixed.
100 g of this mixture were thoroughly mixed with
15 g of 2,2,4,4-tetrafluorobutane as propellant, using
a laboratory stirrer.
This mixture was foamed with 56 g of crude 4,4'-
diisocyanatodiphenylmethane. A tough and resilient
polyurethane foam was obtained. Foaming and physical
data: .
Induction time (a) s 38
Setting time (s) : 108
Free density (kg/m~) s 117
Cell structure : fine
Le A 26 654 - 16 -
CA 02303709 2000-04-11
Example 10
100 g of a polyether with a hydroxyl value of 56,
which resulted from the addition of propylene
oxide~to trimethylolpropane,
3 g of water,
1 g of a siloxane polyether copolymer as foam
stabilizer,
0.05 g of dibutyltin dilaurate were mixed.
100 g of this mixture were thoroughly mixed with
10 g of 1,1,1,3,3,3-hexafluoro-2-methylpropane as
propellant, using a laboratory stirrer.
This mixture was foamed with 41 g of toluylene
diisocyanate. A flexible polyurethane foam was obtained.
Foaming and physical data:
Induction time (s) s 8
Setting time (s) z 105
Free density (kg/m3) s 28 -
Cell structure z fine.
Example 11
100 g of a polyether with a hydroxyl value of 56,
which resulted from the addition of propylene
oxide to trimethylolpropane,
3 g of water,
1 g of a ailoxane polyether copolymer as foam
stabilizer,
0.05 g of d3butyltin dilaurate werre mixed.
I~e A 26 654 - 17 -
CA 02303709 2000-04-11
100 g of this mixture were thoroughly mixed with
g of 1,1,1,3,3,3-hexafluoropropane as propellant,
using a laboratory stirrer.
This mixture was foamed with 41 g of toluylene
5 diisocyanate. A flexible polyurethane foam was obtained.
Foaming and physical data:
Induction time (s) s 8
Setting time (s) s 103
Free density (kg/m') s 26
10 Cell structure s fine.
,Lxample 12
100 g of a polyether with a hydroxyl value of 56,
which resulted from the addition of propylene
oxide to trimethylolpropane,
3 g of water,
1 g of a siloxane polyether copolymer as foam
stabilizer,
0.05 g of dibutyltin dilaurate were mixed.
100 g of this mixture were thoroughly mixed with
10 g of 2,2,4,4-tetrafluorobutane as propellant,
using a laboratory stirrer.
This mixture was foamed with 41 g of toluylene
diisocyanate. A flexible polyurethane foam was obtained.
Foaming and physical data:
Induction time (8) s 8
Setting time (s) s 108
Free den8ity (kg/m') s 25
Cell structure s fine.
?~e A 2b 654 ~ 18 -
