U.S. patent application number 10/548895 was filed with the patent office on 2006-07-20 for hydrofluorocarbon compositions.
This patent application is currently assigned to Solvay S.A.. Invention is credited to Karsten Boerner, Pierre Dournel, Werner Kruecke, Dierk-Ingolf Recke, Lothar Zipfel.
Application Number | 20060160910 10/548895 |
Document ID | / |
Family ID | 32981922 |
Filed Date | 2006-07-20 |
United States Patent
Application |
20060160910 |
Kind Code |
A1 |
Zipfel; Lothar ; et
al. |
July 20, 2006 |
Hydrofluorocarbon compositions
Abstract
A composition which comprises 1,1,1,3,3-pentafluorobutane
(HFC-365mfc) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) in a
weight ratio HFC-365mfc/HFC-245fa of from 60:40 to 75:25.
Inventors: |
Zipfel; Lothar; (Laatzen,
DE) ; Kruecke; Werner; (Hannover, DE) ;
Boerner; Karsten; (Sehnde, DE) ; Dournel; Pierre;
(Brussels, BE) ; Recke; Dierk-Ingolf; (Wunstorf,
DE) |
Correspondence
Address: |
CONNOLLY BOVE LODGE & HUTZ, LLP
P O BOX 2207
WILMINGTON
DE
19899
US
|
Assignee: |
Solvay S.A.
Brussels
BE
B-1120
|
Family ID: |
32981922 |
Appl. No.: |
10/548895 |
Filed: |
March 12, 2004 |
PCT Filed: |
March 12, 2004 |
PCT NO: |
PCT/EP04/02656 |
371 Date: |
October 20, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60465979 |
Apr 28, 2003 |
|
|
|
Current U.S.
Class: |
521/131 ;
528/48 |
Current CPC
Class: |
C08J 9/146 20130101;
C08J 2205/10 20130101; C07C 19/08 20130101; C08G 2110/005 20210101;
C08G 18/1816 20130101; C08J 2205/052 20130101; C08G 18/3206
20130101; C08G 18/7671 20130101; C08G 2110/0025 20210101; C08J
2375/04 20130101; C08G 18/4018 20130101 |
Class at
Publication: |
521/131 ;
528/048 |
International
Class: |
C08G 18/16 20060101
C08G018/16; C08G 18/48 20060101 C08G018/48 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 13, 2003 |
EP |
03100641.4 |
Claims
1. A composition which comprises 1,1,1,3,3-pentafluorobutane
(HFC-365mfc) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) in a
weight ratio HFC-365mfc/HFC-245fa of from 60:40 to 75:25.
2. The composition according to claim 1, wherein the weight ratio
HFC-365mfc/HFC-245fa is from 65:35 to 73:27.
3. The composition according to claim 1, wherein the weight ratio
HFC-365mfc/HFC-245fa is from 67:33 to 72:28.
4. The composition according to claim 1, wherein the weight ratio
HFC-365mfc/HFC-245fa is about 70:30.
5. The composition according to claim 1, which consists essentially
of HFC-365mfc and HFC-245fa.
6. A premix intended for the preparation of polyurethane or
modified polyurethane foams comprising a) at least one polyol b) a
catalyst for the reaction of isocyanates with polyols c) a
composition according to claim 1.
7. A process for the manufacture of polyurethane or modified
polyurethane foams in which at least one isocyanate is reacted with
at least one polyol in the presence of at least one catalyst and in
the presence of the composition according to claim 1.
8. A polyurethane or modified polyurethane foam which is obtainable
according to the process of claim 7.
9. The polyurethane or modified polyurethane foam according to
claim 8, which is a rigid closed cell foam.
10. A thermal insulation material, which comprises a polyurethane
or modified polyurethane foam according to claim 8.
11. A thermal insulation material, which comprises the polyurethane
or modified polyurethane foam according to claim 9.
Description
[0001] The present invention relates to compositions of
1,1,1,3,3-pentafluorobutane HEC-365mfc) and
1,1,1,3,3-pentafluoropropane HFC-245fa), which are useful as
blowing agents for polymer foams.
[0002] Mixtures HFC-365mfc and HFC-245fa are suitable in particular
for the manufacture of polyurethane foams and modified polyurethane
foams such as polyisocyanurate foams. U.S. Pat. No. 6,080,799
discloses inter alia a blowing agent mixture of
HFC-365mfc/HFC-245fa.
[0003] It has been discovered that in certain formulated systems
for polyurethanes containing polyols and mixures of HFC-365mfc and
HFC-245fa, a flash point may be observed in spite of the
nonflammable nature of the poly6ls and of the mixtures of
HFC-365mfc and HFC-245fa respectively.
[0004] It was desirable to find a blowing agent composition which
does not display a flash point when used in fully formulated
systems and which allows for manufacture of foams which display
good insulation properties over a wide temperature range.
[0005] Consequently, the invention concerns a composition which
comprises 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and
1,1,1,3,3-pentafluoropropane (HFC-245fa) in a weight ratio
HFC-365mfcHFC-245fa of from 60:40 to 75:25.
[0006] It has been found, surprisingly, that the compositions
according to the invention allow for safe manufacture of (modified)
polyurethane foams with fully formulated systems having no flash
point whereas obtained closed-cell foams are particularly suitable
for thermal insulation at low temperatures, as condensation of the
cell gas can be substantially avoided.
[0007] Polyurethane is understood to mean the polymers resulting
essentially from the reaction of polyols and of isocyanates. These
polymers are typically obtained from formulations exhibiting an
isocyanate number from 100 to 180. Modified polyurethane is
understood to mean the polymers resulting from the reaction of
polyols and of isocyanates which contain, in addition to urethane
functional groups, other types of functional groups, in particular
triisocyanuric rings formed by trimerization of isocyanates. These
modified polyurethanes are normally known as polyisocyanurates.
These polymers are typically obtained from. formulations exhibiting
an isocyanate number from 180 to 550.
[0008] In the composition according to the invention, the weight
ratio HFC-365mfc/HFC-245fa is greaterthan or equal to 60:40. Often
the weight ratio HFC-365mfc/HFC-245fa is greater than or equal to
65:35. Preferably, the weight ratio HFC-365mfc/HFC-245fa is greater
than or equal to 67:33. A weight ratio HFC-365mfc/HFC-245fa of
about 70:30 is particularly preferred.
[0009] In the composition according to the invention, the weight
ratio HFC-365mfc/HFC-245fa is lower than or equal to 75:25. Often
the weight ratio HFC-365mfc/HFC-245fa is lower than or equal to
73:27. Preferably, the weight ratio HFC-365mfc/HFC-245fa is lower
than or equal to 72:28.
[0010] The compositions according to the invention, which consist
essentially of HFC-365mfc and HFC-245fa are particularly
preferred.
[0011] The invention concerns also a premix intended for the
preparation of polyurethane or modified polyurethane foams
comprising [0012] a) at least one polyol [0013] b) a catalyst for
the reaction of isocyanates with polyols [0014] c) a composition
according to the invention
[0015] For the purposes of the present invention, premix is
understood to mean any composition comprising at least one polyol,
at least one blowing agent and at least one catalyst.
[0016] Surprisingly, the compositions, according to the invention
are chemically stable in the premix. Consequently, the latter can
optionally be formulated without a stabilizer against the potential
degradation of the composition according to the invention.
[0017] For the purposes of the present invention, polyol is
understood to mean any compound containing at least two finctional
groups which react with isocyanates. These functional groups
contain at least one active hydrogen atom, such as defined by the
Zerewittinoff reaction. The active hydrogen atom is generally a
hydrogen atom bonded to an oxygen, nitrogen or sulphur atom. Any
polyol conventionally used to prepare polyurethane foams can be
used in the premixes according to the invention. Mention may in
particular be made of polyether polyols and polyester polyols.
[0018] The catalyst of the premixes according to the invention
comprises a compound with catalyses the formation of the
--NH--CO--O-- urethane bond by reaction between a polyol and an
isocyanate or which activates the reaction between an isocyanate
and water, such as tertiary amines and organic tin, iron, mercury
or lead compounds. Mention may in particular by made, as tertiary
amines, of triethylamine, N,N-dimethylcyclohexylamine (DMCHA),
N-methylmorpholine (NMM), N-ethylmorpholine, dimethylethanolamine,
diaza[2.2.2]bicyclooctane (triethylenediamine) and substituted
benzylamines, such as N,N-dimethylbenzylamine (DB). Mention may in
particular be made, as organic tin or lead compounds, of dibutyltin
dilaurate, stannous octanoate and lead octanoate.
[0019] The catalyst of the premixes according to the invention can,
in particular when the latter are intended for the manufacture of
modified polyurethane (polyisocyanurate) foams, comprise a compound
which catalyses the trimerization of isocyanates to
triisocyanurates. Compounds which catalyse the trimerization of
isocyanates which can be used in the premixes according to the
invention are in particular triazines.
[0020] In addition to the polyol, the composition according to the
invention and the catalyst, the premixes according to the invention
can additionally contain various additives commonly used to prepare
polyurethane or modified polyurethane foams, such as, in
particular, water, surface-active agents, antioxidizing agents,
flame-retardant agents and/or pigments. The more particularly
preferred premixes according to the invention are essentially
composed of at least one polyol the composition according to the
invention, at least one catalyst which promotes the
polyol/isocyanate reaction and at least one of the usual additives
mentioned above.
[0021] The proportions of polyol, catalyst, the composition
according to the invention and optional additives in the premixes
according to the invention vary, in particular according to the
application the type of foam prepared, the nature of the polyol and
the nature of the catalyst.
[0022] In practice, the amount of catalyst used generally varies
from approximately 0.05 to 10 parts by weight per 100 parts by
weight of polyol. In general the amount of the composition
according to the invention is from 1 to 80 parts by weight per 100
parts by weight of polyol. It is preferably from 10 to 60 parts by
weight per 100 parts by weight of polyol. The amounts of water,
surfaceactive agents, plasticizing agents and/or flame-retardant
agents are those conventionally used to prepare polyurethane or
modified polyurethane foams.
[0023] The invention also relates to a process for the manufacture
of polyurethane or modified polyurethane foams, in which at least
one isocyanate is reacted with at least one polyol in the presence
of the composition according to the invention, of at least one
catalyst and, optionally, of other usual additives.
[0024] Any isocyanate conventionally used to manufacture such foams
can be used in the process according to the invention. Mention may
be made, by way of example, of aliphatic isocyanates, such as
hexamethylene diisocyanate, and aromatic isocyanates, such as
tolylene diisocyanate or diphenylmethane diisocyanate.
[0025] Generally, the process according to the invention is carried
out in the presence of water. In this case the amount of water used
is preferably equal to or greater than 1 part by weight per 100
parts of polyol. More preferably, the amount of water used equal to
or greater than 1.5 parts by weight per 100 parts of polyol.
[0026] In this case the amount of water used is preferably equal to
or less than 2.5 parts by weight per 100 parts of polyol. More
preferably, the amount of water used equal to or less than 2 parts
by weight per 100 parts of polyol.
[0027] In the process according to the invention, the composition
according to the invention can be supplied to the reaction in the
form of the premix according to the invention. The composition
according to the invention can also be supplied to the reaction in
the form of a mixture of the composition with the isocyanate.
[0028] The invention concerns also a polyurethane or modified
polyurethane foam which is obtainable according to the process
according to the invention. The polyurethane or modified
polyurethane foam according to thie invention is preferably a rigid
closed-cell foam. The polyurethane or modified polyurethane foam
can also be selected from a flexible or semi-flexible foam, an
integral skin foam and a monocomponent foam.
[0029] The invention concerns also a thermal insulation material,
which comprises a polyurethane or modified polyurethane foam
according to the invention.
[0030] Specific examples of thermal insulation material according
to the invention include insulation panels, tubes for pipe
insulation, sandwich panels, laminates and block foams.
[0031] The thermal insulation material according to the invention
generally substantially keeps its insulating properties when used
in contact with an atmosphere having a temperature of 10.degree. C.
or lower. Often the temperature of use can be 5.degree.C. or lower.
The temperature can even be 0.degree. C. or lower without
substantial condensation. The thermal insulation material according
to the invention is particularly suitable when used in contact with
an atmosphere lhving a temperature of -10.degree. C. or higher.
[0032] The examples here afer are intended to illustrate the
invention in a non-limitative manner.
EXAMPLE 1
PUR Manufacture with a 70:30 Composition of HFC-365mfc and HFC-245
fa
[0033] A preparation of HFC-365mfc/HFC-245fa in a ratio 70:30
starts boiling at 27.degree. C. 100 g Polyol-composition of an
aromatic Polyesterpolyol and an aromatic Polyetherolyol with an OH
number of 450 and 15 g Tris-Chloroisopropylphosphate as a flame
retardant, 2 g Mimethylcyclohexylamine as a catalyst and 1.5 g of a
Siloxanepolyalkeneoxide-Copolymer as a stabilizer, 2 g of water and
20 g of HFC-365mfc/HFC-245fa in a ratio 70:30 were blended and then
mixed with 130 g of 4,4-Diisocyanatediphenylmethane. A rigid foam
was obtained with a density of 35 kg/m.sup.3.
EXAMPLE 2
PUR Manufacture with a 75:25 Composition of
BFC-365mfc/BFC-245fa
[0034] Example 1 was repeated with 20 g of HFC-365mfc/HFC-245fa in
a ratio 75:25 having a boiling start of 28.degree. C. The density
was the same as in Example 1.
EXAMPLE 3
[0035] Example 1 was repeated, adding the blowing agent composition
separately, at first 14 g HFC-365mfc and then 6 g of HFC-245fa,
using a dip tube. A rigid foam was obtained with a density of 35
kg/m.sup.3.
[0036] The compositions do not present any flash point when used in
a premix with polyols.
* * * * *