U.S. patent application number 14/532363 was filed with the patent office on 2015-02-26 for method for producing polyurethane foam.
This patent application is currently assigned to EVONIK DEGUSSA GMBH. The applicant listed for this patent is EVONIK DEGUSSA GMBH. Invention is credited to Christian EILBRACHT, Martin GLOS, Carsten SCHILLER.
Application Number | 20150057384 14/532363 |
Document ID | / |
Family ID | 43242535 |
Filed Date | 2015-02-26 |
United States Patent
Application |
20150057384 |
Kind Code |
A1 |
GLOS; Martin ; et
al. |
February 26, 2015 |
METHOD FOR PRODUCING POLYURETHANE FOAM
Abstract
A method for producing polyurethane foams by reacting at least
one organic isocyanate moiety, at least one polyol, a blowing agent
consisting of halogen-containing (fluorine-containing) olefins and
at least a siloxane of formula (I) ##STR00001## R, R.sup.1,
R.sup.2, R.sup.4, a, b, c, and d are defined herein, as well as
compositions made by said method are described.
Inventors: |
GLOS; Martin; (Borken,
DE) ; SCHILLER; Carsten; (Muelheim an der Ruhr,
DE) ; EILBRACHT; Christian; (Herne, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
EVONIK DEGUSSA GMBH |
ESSEN |
|
DE |
|
|
Assignee: |
EVONIK DEGUSSA GMBH
ESSEN
DE
|
Family ID: |
43242535 |
Appl. No.: |
14/532363 |
Filed: |
November 4, 2014 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
13378169 |
Dec 14, 2011 |
8906974 |
|
|
PCT/EP2010/059190 |
Jun 29, 2010 |
|
|
|
14532363 |
|
|
|
|
Current U.S.
Class: |
521/112 ;
521/172; 521/174 |
Current CPC
Class: |
C08L 83/12 20130101;
C08J 9/144 20130101; C08J 9/149 20130101; C08J 2375/06 20130101;
C08J 9/142 20130101; C08G 18/48 20130101; C08J 2483/12 20130101;
C08G 2101/0025 20130101; C08G 18/42 20130101; C08G 18/7664
20130101; C08G 18/61 20130101; C08G 2101/00 20130101; C08G 77/46
20130101; C08J 2375/08 20130101 |
Class at
Publication: |
521/112 ;
521/172; 521/174 |
International
Class: |
C08J 9/14 20060101
C08J009/14 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 29, 2009 |
DE |
102009028061.8 |
Claims
1. A method for producing polyurethane foams comprising reacting at
least one organic isocyanate containing two or more isocyanate
functions, at least one polyol containing two or more
isocyanate-reactive groups, and a blowing agent consisting of at
least one halogenated olefin and at least one siloxane of formula
(I): ##STR00004## wherein ##STR00005## a in each occurrence
independently is from 0 to 500, b in each occurrence independently
is from 0 to 60, c in each occurrence independently is from 0 to
10, d in each occurrence independently is from 0 to 10, with the
proviso that, per molecule of formula (I), the average number
.SIGMA.d of T-units and the average number .SIGMA.c of Q-units per
molecule are neither greater than 50, the average number .SIGMA.a
of D-units per molecule is not greater than 2000 and the average
number .SIGMA.b of R.sup.1-bearing siloxy units per molecule is not
greater than 100, R is methyl, the a/b ratio is not less than 7,
R.sup.2 in each occurrence independently is R.sup.1 or R, R.sup.1
is unlike R and in each occurrence independently is an organic
moiety and/or a moiety selected from the group consisting of:
--CH.sub.2--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub-
.2--CH(R')O--).sub.y--R''
--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub.2--CH(R')-
O--).sub.y--R'' --CH.sub.2--R.sup.IV
--CH.sub.2--CH.sub.2--(O).sub.x'--R.sup.IV
--CH.sub.2--CH.sub.2--CH.sub.2--O--CH.sub.2--CH(OH)--CH.sub.2OH
##STR00006## and
--CH.sub.2--CH.sub.2--CH.sub.2--O--CH.sub.2--C(CH.sub.2OH).sub.2--CH.sub.-
2--CH.sub.3, where x is from 0 to 100, x' is 0 or 1, Y is from 0 to
100, z is from 0 to 100, R' in each occurrence independently is an
alkyl or aryl group of 1 to 12 carbon atoms, wherein within an
R.sup.1 moiety and/or a molecule of formula I mutually different
substituents R' can be present, and R'' in each occurrence
independently is hydrogen or an alkyl group of 1 to 4 carbon atoms,
a --C(O)--R''' group where R'''=alkyl, a --CH.sub.2--O--R' group,
an alkylaryl group, or a --C(O)NH--R' group, R.sup.IV is a linear,
cyclic or branched, hydrocarbon moiety having 1 to 50 carbon atoms,
R.sup.4 in each occurrence independently may be R, R.sup.1 and/or a
heteroatom-substituted, functionalized, organic, saturated or
unsaturated moiety selected from the group consisting of alkyl,
aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl,
acryloyloxyaryl, acryloyloxyalkyl, methacryloyloxyalkyl,
methacryloyloxypropyl and vinyl, with the proviso that at least one
substituent from R.sup.1, R.sup.2 and/or R.sup.4 is other than
R.
2. The method according to claim 1 wherein a in each occurrence
independently is from 1 to 300, b in each occurrence independently
is from 1 to 50, c in each occurrence independently is >0 to 4,
d in each occurrence independently is >0 to 4, with the proviso
that, per molecule of formula (I), the average number .SIGMA.d of
T-units and the average number .SIGMA.c of Q-units per molecule are
neither greater than 20, the average number .SIGMA.a of D-units per
molecule is not greater than 1500 and the average number .SIGMA.b
of R.sup.1-bearing siloxy units per molecule is not greater than
50.
3. The method according to claim 2 wherein R.sup.1 in each
occurrence independently is an organic moiety
--CH.sub.2--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub-
.2--CH(R')O--).sub.y--R''
--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub.2--CH(R')-
O--).sub.y--R'', or --CH.sub.2--R.sup.IV where x is from 0 to 100,
y is from 0 to 100, R' in each occurrence independently may be
different and is methyl, ethyl and/or phenyl and, R'' in each
occurrence independently is hydrogen or an alkyl group of 1 to 4
carbon atoms, a --C(O)--R''' group where R'''=alkyl, a
--CH.sub.2--O--R' group, an alkylaryl group, a --C(O)NH--R' group,
R.sup.IV is a linear, cyclic or branched, hydrocarbon moiety having
1 to 50 carbon atoms.
4. The method according to claim 3 wherein R.sup.1 in each
occurrence independently is an organic moiety selected from the
group consisting of:
--CH.sub.2--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub-
.2--CH(R')O--).sub.y--R'',
--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub.2--CH(R')-
O--).sub.y--R'', --CH.sub.2--R.sup.IV, and mixtures thereof where x
is from 0 to 100, y is from 0 to 100, R' is methyl and R'' in each
occurrence independently is hydrogen or an alkyl group of 1 to 4
carbon atoms, a --C(O)--R''' group where R'''=alkyl, a
--CH.sub.2--O--R' group, an alkylaryl group, a --C(O)NH--R' group,
wherein the molar fraction of oxyethylene units comprises at least
70% of the oxyalkylene units, or the molar fraction of oxyethylene
units comprises at most 70% of the oxyalkylene units, and R'' is
hydrogen.
5. The method according to claim 1 wherein R.sup.1 consists of
--CH.sub.2--R.sup.IV to an extent of at least 20 mol %, wherein
R.sup.IV is a linear or branched hydrocarbon having 9 to 17 carbon
atoms.
6. The method according to claim 1 wherein at least 10% of the
R.sup.2 moieties are equal to R.sup.1.
7. The method according to claim 1 wherein each siloxane of formula
(I) is statistically on average at most 50%, of the entire average
molecular weight of the one or more siloxanes of formula (I) and is
accounted for by a summed molar mass of all R.sup.1 moieties in the
at least one siloxane of formula (I).
8. The method according to claim 1 wherein, in R.sup.1, y=0 and R''
is not hydrogen.
9. The method according to claim 1 wherein .SIGMA.c+.SIGMA.d is
<1.
10. The method according to claim 1 wherein .SIGMA.c+.SIGMA.d is
1.
11. A polyurethane foam obtained by a method according to claim
1.
12. The polyurethane foam according to claim 1, wherein said
polyurethane foam is closed-cell.
13. The polyurethane foam according to claim 12, wherein the
polyurethane foam is a rigid polyurethane foam, a flexible
polyurethane foam, a viscoelastic foam, an HR foam, a semirigid
polyurethane foam, a thermoformable polyurethane foam or an
integral foam.
14. The method according to claim 1, wherein each siloxane of
formula (I) is statistically on average at most 45% of the entire
average molecular weight of the at least one siloxane of formula
(I) and is accounted for by a summed molar mass of all R.sup.1
moieties in the at least one siloxane of formula (I).
15. The method according to claim 1, wherein each siloxane of
formula (I) is statistically on average at most 40% of the entire
average molecular weight of the at least one siloxane of formula
(I) and is accounted for by a summed molar mass of all R.sup.1
moieties in the at least one siloxane of formula (I).
16. The polyurethane foam according to claim 12, wherein said
polyurethane foam contains from 0.01% to 10% by weight of said at
least one siloxane of formula (I).
17. The polyurethane foam according to claim 12 wherein said
polyurethane foam contains from 0.1% to 3% by weight of said at
least one siloxane of formula (I).
18. A composition of matter, comprising a polyurethane foam and
from 0.01% to 10% by weight of at least one siloxane of formula (I)
##STR00007## a in each occurrence independently is from 0 to 500, b
in each occurrence independently is from 0 to 60, c in each
occurrence independently is from 0 to 10, d in each occurrence
independently is from 0 to 10, with the proviso that, per molecule
of formula (I), the average number .SIGMA.d of T-units and the
average number .SIGMA.c of Q-units per molecule are neither greater
than 50, the average number .SIGMA.a of D-units per molecule is not
greater than 2000 and the average number .SIGMA.b of
R.sup.1-bearing siloxy units per molecule is not greater than 100,
R is methyl, the a/b ratio is not less than 7, R.sup.2 in each
occurrence independently is R.sup.1 or R, R.sup.1 is unlike R and
in each occurrence independently is an organic moiety and/or a
moiety selected from the group consisting of:
--CH.sub.2--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub-
.2--CH(R')O--).sub.y--R''
--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub.2--CH(R')-
O--).sub.y--R'' --CH.sub.2--R.sup.IV
--CH.sub.2--CH.sub.2--(O).sub.x'--R.sup.IV
--CH.sub.2--CH.sub.2--CH.sub.2--O--CH.sub.2--CH(OH)--CH.sub.2OH
##STR00008## and
--CH.sub.2--CH.sub.2--CH.sub.2--O--CH.sub.2--C(CH.sub.2OH).sub.2--CH.sub.-
2--CH.sub.3, where x is from 0 to 100, x' is 0 or 1, y is from 0 to
100, z is from 0 to 100, R' in each occurrence independently is an
alkyl or aryl group of 1 to 12 carbon atoms, wherein within an
R.sup.1 moiety and/or a molecule of formula I mutually different
substituents R' can be present, and R'' in each occurrence
independently is hydrogen or an alkyl group of 1 to 4 carbon atoms,
a --C(O)--R''' group where R'''=alkyl, a --CH.sub.2--O--R' group,
an alkylaryl group, or a --C(O)NH--R' group, R.sup.IV is a linear,
cyclic or branched, hydrocarbon moiety having 1 to 50 carbon atoms,
R.sup.4 in each occurrence independently may be R, R.sup.1 and/or a
heteroatom-substituted, functionalized, organic, saturated or
unsaturated moiety selected from the group consisting of alkyl,
aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl,
acryloyloxyaryl, acryloyloxyalkyl, methacryloyloxyalkyl,
methacryloyloxypropyl and vinyl, with the proviso that at least one
substituent from R.sup.1, R.sup.2 and/or R.sup.4 is other than R.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S. patent
application Ser. No. 13/378,169, filed on Dec. 14, 2011, which is a
'371 of PCT Application PCT/EP2010/059190 filed on Jun. 29, 2010,
which claims the benefit of priority of German Patent Application
No. 102009028061.8, filed on Jul. 29, 2009, all of which are
incorporated by reference.
[0002] The present invention relates to a method for producing
polyurethane foam using compounds bearing olefinic double bonds as
blowing agents and polyether-siloxane copolymers, to polyurethane
foams containing these blowing agents and siloxane copolymers, and
also to the use of these polyurethane foams.
PRIOR ART
[0003] Halogenated hydrocarbons and particularly fluorinated
hydrocarbons have found wide utility as blowing agents for
production of foams. Yet these compounds have disadvantages with
regard to their Ozone Depletion Potential (ODP) and Global Warming
Potential (GWP). Alternative blowing agents with lower ODP and GWP
have therefore been developed. The current trend is to use
halogenated compounds having an olefinic double bond in the
molecule--that is, hydrohaloolefins (HHOs). More particularly,
hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) are
being described as new blowing agents.
[0004] US 2008/125505 and US 2008/125506 describe the use of
fluorinated olefins as blowing agents for foams. These blowing
agents have a low GWP and ODP.
[0005] WO 2008/121790 describes mixtures of hydrofluoroolefins
(HFOs) and hydrochlorofluoroolefin (HCFO) as blowing agents for
production of foams.
[0006] WO 2008/121779 describes a blowing agent composition
containing at least one hydrochloroolefin.
[0007] WO 2007/053670 describes blowing agents for production of
foams containing unsaturated fluorocarbons. Bromofluoroolefins are
also mentioned.
[0008] The WO 2009/073487 and WO 2009/089400 applications describe
cis-1,1,1,4,4,4-hexafluoro-2-butene and
2-chloro-3,3,3-trifluoropropene, respectively, as blowing agents in
the production or polyurethane and polyisocyanurate foams.
[0009] EP 2 004 773 describes a composition for use in
refrigeration, air-conditioning or heat pump apparatus, containing
a fluoroolefin and at least one further component. The use as
foam-blowing agent is also described inter alia.
[0010] U.S. Pat. No. 5,900,185 describes bromine-containing olefins
having short atmospheric lifetimes and inter alia the use thereof
as blowing agents for foams.
[0011] WO 2007/002703 and US 2008/207788 and WO 2009/067720
describe HFO-1234ze and HCFO-1233zd and, respectively, mixtures
containing these substances together with fluorinated ethers, in
various applications including the use as blowing agents for PU
foams.
[0012] WO 2009/003165 describes mixtures of hydrofluoroolefins
(HFOs) and/or hydrochlorofluoroolefin (HCFO) with stabilizers that
prevent degradation during storage, handling and use yet allow
degradation in the atmosphere. The stabilizers used are
free-radical scavengers, oxygen scavengers, acid scavengers and
also polymerization inhibitors.
[0013] Also described in this reference is a damaging effect of
blowing agent disintegration products on the siloxanes used.
[0014] However, there is no description of specific siloxane
structures, also called silicone surfactants.
[0015] US 2009/0099272 describes the use of acid/amine adducts as a
catalyst in systems comprising olefinic fluorinated blowing agents,
since free amines react with the blowing agents and these products
then decompose the silicone surfactants. This distinctly limits
possibilities in relation to the production of a foam formulation,
since the catalytic effect of the amines is weakened here, which
results in a longer reaction time for the PU foam formulation.
[0016] US 2009/0099273 describes the use of silicon-free
surfactants in order to avoid the problem with the reaction
products formed from amine and fluorinated blowing agents. This
means that only a limited number of surfactants can be used.
[0017] Both alternatives represent a substantial limitation in
relation to PU foam production. Therefore, there is a need for
siloxanes which are free of the disadvantages described above and
are useful as silicone surfactants in the production of PU
foam.
[0018] This invention has for its object to provide siloxanes
which, when halogenated olefins are used as blowing agents, do not
have the abovementioned disadvantages and hence lead to improved
results.
[0019] It has now been found that, surprisingly, this object is
achieved by siloxanes of formula (I).
[0020] The selected siloxanes of formula (I) do include the typical
structural elements of siloxanes already described in the prior
art, but differ in the selection range for the number of structural
features. It is utterly surprising to and unforeseeable by a person
skilled in the art that it was possible to find specific siloxanes
capable of performing siloxane-typical functions in foaming without
additional free-radical scavengers for example or even in the
presence of non-acid-blocked amines.
[0021] The present invention accordingly provides a method for
producing polyurethane foams using blowing agents consisting of
halogenated olefins and siloxanes of formula (I). These siloxanes
of formula (I) can also be generated as a mixture in a suitable
carrier medium. These mixtures can be present as-produced or else
be obtainable subsequently in order, for example, to facilitate
meterability of the siloxanes or else to improve incorporability of
the siloxanes into the mixture to be foamed.
[0022] The present invention further provides polyurethane foams
and a method for producing polyurethane foams in each of which the
subject compositions comprising the blowing agents and siloxanes
are used. The present invention also provides for the use of
polyurethane foams which are in accordance with the present
invention and/or are obtained in accordance with the present
invention.
[0023] The method of the present invention has the advantage that
optionally preformulated mixtures of polyols and/or catalysts,
water/blowing agents, the foam stabilizer and optionally further
additives, that are marketed as ready-to-use polyurethane foam
systems, survive the commercially customary storage periods without
deterioration in foam properties. This applies particularly to
1-component systems in which the isocyanate is also included in the
preformulated mixture.
[0024] The polyurethane foam of the present invention has the
advantage of consistently high quality, i.e., a particularly fine
cellular structure with particularly few foam defects (voids,
cracks, densifications). The siloxanes of the present invention
have the following structure:
##STR00002##
where [0025] a in each occurrence independently is from 0 to 500,
preferably from 1 to 300 and particularly from 2 to 150, [0026] b
in each occurrence independently is from 0 to 60, preferably from 1
to 50 and particularly from 1 to 30, [0027] c in each occurrence
independently is from 0 to 10, preferably 0 or >0 to 5, [0028] d
in each occurrence independently is from 0 to 10, preferably 0 or
>0 to 5, with the proviso that, per molecule of formula (I), the
average number .SIGMA.d of T-units and the average number .SIGMA.c
of Q-units per molecule are neither greater than 50, the average
number .SIGMA.a of D-units per molecule is not greater than 2000
and the average number .SIGMA.b of R.sup.1-bearing siloxy units per
molecule is not greater than 100, [0029] R in each occurrence
independently is one or more than one moiety from the group of
linear, cyclic or branched, aliphatic or aromatic, saturated or
unsaturated hydrocarbon moieties having 1 up to 20 carbon atoms,
but preferably methyl, [0030] R.sup.2 in each occurrence
independently is R.sup.1 or R, [0031] R.sup.1 is unlike R and in
each occurrence independently is an organic moiety and/or a moiety
selected from the group [0032]
--CH.sub.2--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub-
.2--CH(R')O--).sub.y--R'' [0033]
--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub.2--CH(R')-
O--).sub.y--R'' [0034] --CH.sub.2--R.sup.IV [0035]
--CH.sub.2--CH.sub.2--(O).sub.x--R.sup.IV [0036]
--CH.sub.2--CH.sub.2--CH.sub.2--O--CH.sub.2--CH(OH)--CH.sub.2OH
[0036] ##STR00003## or [0037]
--CH.sub.2--CH.sub.2--CH.sub.2--O--CH.sub.2--C(CH.sub.2OH).sub.2--CH.sub.-
2--CH.sub.3, where [0038] x is from 0 to 100, preferably >0 and
particularly from 1 to 50, [0039] x' is 0 or 1, [0040] y is from 0
to 100, preferably >0 and particularly from 1 to 50, [0041] z is
from 0 to 100, preferably >0 and particularly from 1 to 10,
[0042] R' in each occurrence independently is an alkyl or aryl
group of 1 to 12 carbon atoms which is optionally substituted, for
example with alkyl moieties, aryl moities or haloalkyl or haloaryl
moieties, wherein within an R.sup.1 moiety and/or a molecule of
formula (I) mutually different substituents R' can be present, and
[0043] R'' in each occurrence independently is hydrogen or an alkyl
group of 1 to 4 carbon atoms, a --C(O)--R''' group where
R'''=alkyl, a --CH.sub.2--O--R' group, an alkylaryl group, e.g.,
benzyl, a --C(O)NH--R' group, [0044] R.sup.IV is a linear, cyclic
or branched, including further substituted, e.g.,
halogen-substituted, hydrocarbon moiety having 1 to 50, preferably
9 to 45 and more preferably 13 to 37 carbon atoms, [0045] R.sup.4
in each occurrence independently may be R, R.sup.1 and/or a
heteroatom-substituted, functionalized, organic, saturated or
unsaturated moiety selected from the group of alkyl, aryl,
chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloyloxyaryl,
acryloyloxyalkyl, methacryloyloxyalkyl, methacryloyloxypropyl or
vinyl, with the proviso that at least one substituent from R.sup.1,
R.sup.2 and R.sup.4 is other than R.
[0046] The various monomer units of the siloxane and
polyoxyalkylene chains indicated in the formulae can have a
mutually blockwise construction with any number of blocks and any
sequence, or have a random distribution. The indices used in the
formulae shall be regarded as statistical averages.
[0047] The siloxane-containing mixtures of the present invention
may contain further substances. More particularly, the compositions
of the present invention may contain further additives/auxiliaries
of the type used in polyurethane foam production. Preferred
additives/auxiliaries for inclusion in the compositions of the
present invention are preferably selected from conventional SiOC
and SiC stabilizers, organic foam stabilizers, surfactants,
nucleating agents, cell-refining additives, cell-opening agents,
crosslinkers, emulsifiers, flame retardants, antioxidants,
antistats, biocides, color pastes, solid fillers, amine catalysts,
metal catalysts, polyols and/or buffers.
[0048] It may also be advantageous for the composition of the
present invention to contain a solvent, more particularly an
organic solvent, preferably a solvent selected from glycols,
alkoxylates and oils of synthetic and/or natural origin.
[0049] The siloxanes of formula (I) are prepared by the familiar
methods such as, for example, the noble metal catalyzed
hydrosilylation reaction of compounds containing a double bond with
appropriate hydrosiloxanes as described in EP 1 520 870, for
example. The EP 1 520 870 document is hereby incorporated by
reference and shall be deemed to form part of the disclosure
content of the present invention.
[0050] Useful compounds having one or more than one double bond per
molecule include .alpha.-olefins, vinylpolyoxyalkylenes and/or
allylpolyoxyalkylenes. Preference is given to using
vinylpolyoxyalkylenes and/or allylpolyoxyalkylenes. Particularly
preferred vinylpolyoxyalkylenes are, for example,
vinylpolyoxyalkylenes having a molecular weight in the range from
100 g/mol to 5000 g/mol, which may be constructed from the monomers
propylene oxide, ethylene oxide, butylene oxide, and/or styrene
oxide in blockwise or in random distribution and which may be not
only hydroxy functional but also endcapped by a methyl ether
function or an acetoxy function. Particularly preferred
allylpolyoxyalkylenes are, for example, allylpolyoxyalkylenes
having a molecular weight in the range from 100 g/mol to 5000
g/mol, which may be constructed from the monomers propylene oxide,
ethylene oxide, butylene oxide, and/or styrene oxide blockwise or
in random distribution and may be not only hydroxy functional but
also endcapped by a methyl ether function or an acetoxy function.
Particular preference for use as compounds having one or more than
one double bond per molecule is given to the exemplified
.alpha.-olefins, allyl alcohol, 1-hexenol, vinylpolyoxyalkylenes
and/or allylpolyoxyalkylenes and also allyl glycidyl ether and
vinylcyclohexene oxide.
[0051] The method of the present invention preferably utilizes
siloxanes of formula (I) where a in each occurrence independently
is from 1 to 300, b in each occurrence independently is from 1 to
50, c in each occurrence independently is from 0 to 4, din each
occurrence independently is >0 to 4, with the proviso that, per
molecule of formula (I), the average number .SIGMA.d of T-units and
the average number .SIGMA.c of Q-units per molecule are neither
greater than 20, the average number .SIGMA.a of D-units per
molecule is not greater than 1500 and the average number .SIGMA.b
of R.sup.1-bearing siloxy units per molecule is not greater than
50.
[0052] A particularly preferred embodiment of the method according
to the present invention utilizes siloxane of formula (I) where
R.sup.1 in each occurrence independently is an organic moiety
[0053]
--CH.sub.2--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(-
CH.sub.2--CH(R')O--).sub.y--R''
[0054]
--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub.2---
CH(R') O--).sub.y--R''
[0055] --CH.sub.2--R.sup.IV
where x is from 0 to 100, preferably >0 and particularly from 1
to 50 and y is from 0 to 100, preferably >0 and particularly
from 1 to 50, R' in each occurrence independently may be different
and is methyl, ethyl and/or phenyl. R'' in each occurrence
independently is hydrogen or an alkyl group of 1 to 4 carbon atoms,
a --C(O)--R''' group where R'''=alkyl, a --CH.sub.2--O--R' group,
an alkylaryl group, e.g., benzyl, a --C(O)NH--R' group, R.sup.IV is
a linear, cyclic or branched, optionally substituted, e.g.,
halogen-substituted, hydrocarbon moiety having 1 to 50, preferably
9 to 45 and more preferably 13 to 37 carbon atoms.
[0056] A further preferred embodiment of the method utilizes
siloxanes of formula (I) where R.sup.1 in each occurrence
independently is an organic moiety selected from the group
comprising
--CH.sub.2--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub-
.2--CH(R')O--).sub.y--R'' and/or
--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2O--).sub.x--(CH.sub.2--CH(R')-
O--).sub.y--R'' and/or --CH.sub.2--R.sup.IV, where x is from 0 to
100, preferably >0 and particularly from 1 to 50, y is from 0 to
100, preferably >0 and particularly from 1 to 50, R.sup.1 is
methyl and R'' in each occurrence independently is hydrogen or an
alkyl group of 1 to 4 carbon atoms, a --C(O)--R''' group where
R'''=alkyl, a --CH.sub.2--O--R' group, an alkylaryl group, e.g.,
benzyl, a --C(O)NH--R' group, wherein the molar fraction of
oxyethylene units comprises at least 70% of the oxyalkylene units,
i.e., x/(x+y) is >0.7. It may further be advantageous for the
polyoxyalkylene chain to bear a hydrogen at the end and at the same
time for the molar fraction of oxyethylene units to comprise at
most 70% of the oxyalkylene units, i.e., x/(x+y) is <0.7 and R''
is hydrogen.
[0057] A further preferred embodiment of the method according to
the present invention uses siloxanes of formula (I) in each of
which the hydrosilylation utilizes inter alia olefins whereby
R.sup.1 consists of --CH.sub.2--R.sup.IV to an extent of at least
10 mol %, preferably at least 20 mol % and more preferably at least
40 mol %, wherein R.sup.IV is a linear or branched hydrocarbon
having 9 to 17 carbon atoms.
[0058] A further preferred embodiment of the method according to
the present invention uses siloxanes of formula (I) in each of
which the end positions on the siloxane, i.e., the alpha and omega
positions, are at least partly functionalized with R.sup.1. At
least 10 mol %, preferably at least 30 mol % and more preferably at
least 50 mol % of the end positions are functionalized with R.sup.1
moieties.
[0059] A particularly preferred embodiment of the method according
to the present invention utilizes siloxanes of formula (I) in each
of which statistically on average at most 50%, preferably at most
45% and more preferably at most 40% of the entire average molecular
weight of the siloxane is accounted for by the summed molar mass of
all, optionally different, R.sup.1 moieties in the siloxane.
[0060] A further preferred embodiment of the method according to
the present invention uses siloxanes of formula (I) in each of
which R is methyl and the number of structural elements having the
index a is larger than the number of structural elements having the
index b such that the a/b ratio is not less than 7, preferably
above 10 and more preferably above 12.
[0061] A further preferred embodiment of the method according to
the present invention uses siloxanes of formula (I) in each of
which the oxyalkylene units in R.sup.1 are exclusively oxyethylene
units and R'' is not hydrogen.
[0062] A further preferred embodiment of the method according to
the present invention uses siloxanes of formula (I) having no or
statistically on average less than one branch in the siloxane
scaffold and which accordingly satisfy the inequality
.SIGMA.c+.SIGMA.d<1.
[0063] A further preferred embodiment of the method according to
the present invention uses siloxanes of formula (I) which have one
or more than one branch in the siloxane scaffold statistically on
average and hence satisfy the inequality
.SIGMA.c+.SIGMA.d.gtoreq.1.
[0064] The siloxanes of the present invention can also be used as
part of compositions comprising various carrier media. Examples of
possible carrier media are glycols, alkoxylates or oils of
synthetic and/or natural origin. The amount of composition added is
preferably sufficient for the mass fraction of compounds of formula
(I) in the final polyurethane foam to be in the range from 0.01% to
10% by weight and preferably in the range from 0.1% to 3% by
weight.
[0065] The compositions of the present invention are useful as foam
stabilizers in the customary formulations for production of
polyurethane foams, consisting of one or more organic isocyanates
having two or more isocyanate functions, one or more polyols having
two or more isocyanate-reactive groups, catalysts for the
isocyanate-polyol and/or isocyanate-water reactions and/or the
isocyanate trimerization, water, optionally physical blowing
agents, optionally flame retardants with or without further
additives.
[0066] Suitable isocyanates for the purposes of this invention are
any polyfunctional organic isocyanates, for example
4,4''-diphenylmethane diisocyanate (MDI), toluene diisocyanate
(TDI), hexamethylene diisocyanate (HMDI) and isophorone
diisocyanate (IPDI). What is particularly suitable is the mixture
of MDI and more highly condensed analogs having an average
functionality in the range from 2 to 4 which is known as "polymeric
MDI" (crude MDI) as well as the various isomers of TDI in pure form
or as isomeric mixture.
[0067] Suitable polyols for the purposes of this invention are any
organic substances having two or more isocyanate-reactive groups,
and also preparations thereof. Any polyether polyols and polyester
polyols customarily used for producing polyurethane foams are
preferred polyols. Polyether polyols are obtainable by reaction of
polyfunctional alcohols or amines with alkylene oxides. Polyester
polyols are based on esters of polybasic carboxylic acids (which
may be either aliphatic, as in the case of adipic acid for example,
or aromatic, as in the case of phthalic acid or terephthalic acid
for example) with polyhydric alcohols (usually glycols).
[0068] A suitable ratio of isocyanate to polyol, expressed as the
index of the formulation, i.e., as stoichiometric ratio of
isocyanate groups to isocyanate-reactive groups (e.g., OH groups,
NH groups) multiplied by 100 is in the range from 10 to 1000 and
preferably in the range from 80 to 350.
[0069] Suitable catalysts for the purposes of this invention are
substances that catalyze the gel reaction (isocyanate-polyol), the
blowing reaction (isocyanate-water) or the di- or trimerization of
isocyanate. Typical examples are the amines triethylamine,
dimethylcyclohexylamine, tetramethylethylenediamine,
tetramethylhexanediamine, pentamethyldiethylenetriamine,
pentamethyldipropylenetriamine, triethylenediamine,
dimethylpiperazine, 1,2-dimethylimidazole, N-ethylmorpholine,
tris(dimethylaminopropyl)hexahydro-1,3,5-triazine,
dimethylaminoethanol, dimethylaminoethoxyethanol and
bis(dimethylaminoethyl) ether, and also metal-containing compounds
such as, for example, tin compounds like dibutyltin dilaurate or
tin(II) 2-ethylhexanoate and potassium salts like potassium acetate
and potassium 2-ethylhexanoate.
[0070] Suitable use levels depend on the type of catalyst and lie
typically in the range from 0.05 to 5 pphp (=parts by weight per
100 parts by weight of polyol) or from 0.1 to 10 pphp for potassium
salts.
[0071] Suitable water contents for the purposes of this invention
depend on whether water is or is not used in addition to the
halogenated olefin. Typically, water quantities from 0.1 to 5 pphp
are used.
[0072] In addition to the abovementioned halogenated olefins,
further suitable physical blowing agents can also be used. These
are for example liquefied CO.sub.2 and volatile liquids, for
example hydrocarbons having 4 or 5 carbon atoms, preferably
cyclopentane, isopentane and n-pentane, hydrofluorocarbons,
preferably HFC 245fa, HFC 134a and HFC 365mfc,
hydrochlorofluorocarbons, preferably HCFC 141b, oxygen-containing
compounds such as methyl formate and dimethoxymethane, or
hydrochlorocarbons, preferably dichloromethane and
1,2-dichloroethane.
[0073] In addition to water and physical blowing agents, other
chemical blowing agents can also be used to react with isocyanates
by gas evolution, such as formic acid for example.
[0074] Suitable flame retardants for the purposes of this invention
are preferably liquid organophosphorus compounds, such as
halogen-free organic phosphates, e.g., triethyl phosphate (TEP),
halogenated phosphates, e.g., tris(1-chloro-2-propyl)phosphate
(TCPP) and tris(2-chloroethyl)phosphate (TCEP) and organic
phosphonates, e.g., dimethyl methanephosphonate (DMMP), dimethyl
propanephosphonate (DMPP), or solids such as ammonium polyphosphate
(APP) and red phosphorus. Suitable flame retardants further include
halogenated compounds, for example halogenated polyols, and also
solids such as melamine and expandable graphite.
[0075] The formulations of the present invention can be processed
into foams by any method familiar to a person skilled in the art,
for example by manual mixing or preferably means of high pressure
foaming machines. Batch processes can be used, for example for
manufacture of molded foams, refrigerators and panels, or
continuous processes, for example in the case of insulation plates,
metal composite elements, blocks or in the case of spraying
processes.
[0076] A special case is that of the 1- and 1,5-component can foams
which each employ a polyurethane prepolymer. The
siloxane-containing compositions of the present invention are also
useful as foam stabilizer in this application.
[0077] The polyurethane foams of the present invention are notable
for including/containing a siloxane-containing composition
according to the present invention. The mass fraction of compounds
of formula (I) in the final polyurethane foam is preferably in the
range from 0.01% to 10% by weight and more preferably in the range
from 0.1% to 3% by weight.
[0078] The polyurethane foams of the present invention may be for
example a rigid polyurethane foam, a flexible polyurethane foam, a
viscoelastic foam, an HR foam, a semirigid polyurethane foam, a
thermoformable polyurethane foam or an integral foam. Polyurethane
must here be understood as a generic term for a polymer obtained
from di- or polyisocyanates and polyols or other
isocyanate-reactive species, for example amines, in that the
urethane bond need not be the only or predominant type of bond.
Polyisocyanurates and polyureas are also expressly included.
[0079] In a preferred embodiment the foams obtained according to
the present invention are closed-cell foams.
[0080] The polyurethane foams of the present invention can be used
as constituent parts of or in and/or as, for example, refrigerator
insulation, insulation panels, sandwich elements, tube insulation,
spray foam, 1- and 1.5-component can foam, wood imitation,
modelling foam, packaging foam, mattresses, furniture cushioning,
automotive seat cushioning, headrest, dashboard, automotive
interior, automotive roof liner, sound absorption material,
steering wheel, shoe sole, carpet backing foam, filter foam,
sealing foam and adhesive.
[0081] Further subjects and embodiments of the invention will be
apparent from the claims, the disclosure content of which is fully
part of the description.
[0082] The subject method for producing the polyurethane foams, the
polyurethane foams themselves and also uses thereof are hereinbelow
described by way of example without the intention to restrict the
invention to these exemplary embodiments. Where ranges, general
formulae or classes of compounds are indicated in what follows,
they shall encompass not just the corresponding ranges or groups of
compounds that are explicitly mentioned, but also all sub-ranges
and sub-groups of compounds which are obtainable by extraction of
individual values (ranges) or compounds. Where documents are cited
in the context of the present description, their content shall
fully belong to the disclosure content of the present
invention.
[0083] The examples which follow describe the present invention by
way of example without any intention to restrict the invention, the
scope of which is apparent from the entire description and the
claims, to the embodiments mentioned in the examples.
EXAMPLES
Preparing Inventive Siloxanes
[0084] Inventive siloxanes of formula (I) are obtainable via the
prior art methods of reacting with appropriate hydrosiloxanes by
hydrosilylation.
[0085] Allyl polyethers and olefins were reacted to form compounds
of formula (I). The method used was similar to example 7 of DE
1020070554852 and hence in agreement with the prior art for
preparing SiC-linked polyether siloxanes as also described in EP
1520870 for example.
[0086] Table 1 summarizes the polyethers used.
TABLE-US-00001 TABLE 1 Allyl polyethers used for preparing the
compounds in table 2 (x = ethylene oxide units, y = propylene oxide
units, R'' = end group) Polyether Initiator R'' x= y= PE 1 allyl
alcohol --H 11 0 PE 2 allyl alcohol --H 9 3 PE 3 allyl alcohol --H
13 4 PE 4 allyl alcohol --H 12 9 PE 5 hydroxyethyl- --H 15 7 vinyl
ether PE 6 allyl alcohol --H 13 14 PE 7 allyl alcohol --CH.sub.3 10
0 PE 9 allyl alcohol --H 36 38
[0087] The structure of the resulting compound of formula (I) is
discernible from table 2. The parameters listed in table 2 relate
to formula (I) as mentioned above.
TABLE-US-00002 TABLE 2 Siloxanes of examples 1 to 10, containing
compounds of formula (I) Ex. R .SIGMA.a R.sup.1 R.sup.4 .SIGMA.b
.SIGMA.c .SIGMA.d R.sup.2 1 CH.sub.3 44 PE 2 CH.sub.3 5 0 <<1
R 2 CH.sub.3 65 PE 4 CH.sub.3 4 0 <<1 R 3 CH.sub.3 50 .sup.
PE 1 ).sup.1 CH.sub.3 8 0 <<1 .sup. R.sup.1 4 CH.sub.3 20 PE
1 CH.sub.3 2 0 <<1 R 5 CH.sub.3 40 PE 7 CH.sub.3 5 0
<<1 R 6 CH.sub.3 65 PE 6/PE 8 ).sup.2 CH.sub.3 5 0 <<1
.sup. R.sup.1 7 CH.sub.3 40 PE 4/PE 1 ).sup.3 CH.sub.3 3 0.5 2
.sup. R.sup.1 8 CH.sub.3 40 PE 3 CH.sub.3 3 0 1 R 9 CH.sub.3 40 PE
3 C.sub.8H.sub.17 3 0.5 2 .sup. R.sup.1 10 CH.sub.3 40 PE 5
CH.sub.3 4 0 <<1 .sup. R.sup.1 ).sup.1 mixture consisting of
80 eq % PE 1 + 20 eq % C.sub.16-olefin ).sup.2 mixture consisting
of 60 eq % PE 6 + 40 eq % PE 8 ).sup.3 mixture consisting of 50 eq
% PE 4 + 50 eq % PE 1
Foaming Examples
[0088] The following foam formulation was used to performance-test
the inventive formulations:
TABLE-US-00003 TABLE 3 Formulations for rigid foam applications
(rigid foam panel/insulation plate) in parts by mass A: PUR flow B:
PIR Formulation formulation insulation panel polyol polyether
Stepanpol .RTM. PS polyol mixture 2352* 100 parts 100 parts
tris(1-chloro-2-propyl) -- 15 parts phosphate N,N,N',N'',N''-- 0.2
part 0.2 part pentamethyldiethylene triamine
N,N-dimethylcyclohexylamine 2.0 parts -- potassium octoate (75 wt %
in -- 4.0 parts diethylene glycol) water 2.0 parts 0.8 part
1,3,3,3-tetrafluoropropene 3.0 parts 4.0 parts (E-isomer)
1-chloro-3,3,3- 12.0 parts 18.0 parts trifluoropropene (E isomer)
1,2,3,3,3-pentafluoropropene 3.0 parts 4.0 parts siloxane 2.0 parts
2.0 parts Desmodur 44V20L** 140 parts 200 parts *polyester polyol
from Stepan **polymeric MDI from Bayer, 200 mPa*s, 31.5% NCO,
functionality 2.7
[0089] Foaming tests were carried out by hand mixing. For this
purpose, the A and B formulations described in table 3 were
prepared with various siloxanes and weighted into a beaker. The MDI
was then added, the reaction mixture was stirred with a 6 cm
diameter plate stirrer at 3000 rpm for 5 seconds and immediately
transferred into a thermostated 50 cm.times.25 cm.times.5 cm
aluminum mold lined with polyethylene film at 50.degree. C. The
amount of foam formulation used was determined such that it was 10%
above the minimum quantity necessary to fill the mold.
[0090] One day after foaming, the foams were analyzed. They were
inspected from the top and the bottom to evaluate the surfaces and,
after cutting open, the internal defects against a subjective scale
from 1 to 10, where 10 represents an undisrupted foam and 1
represents an extremely disrupted foam. The pore structure (average
number of cells per 1 cm) was visually assessed on a cut face by
comparison with reference foams.
[0091] The results are compiled in table 4. The siloxanes used, the
foam formulations, and also the visual assessment and the pore
structure of the foams are summarized.
TABLE-US-00004 TABLE 4 Results of foaming tests Siloxane Foam
Assessment Cells/ Example from Ex. formula top/bottom/inside cm 11
1 A 7/9/8 46-50 12 2 B ) .sup.4 8/8/7 46-50 13 3 B ) .sup.4 7/9/8
46-50 14 4 B 6/8/9 46-50 15 5 B 7/7/9 46-50 16 6 B ) .sup.4 6/7/8
41-45 17 7 B 8/8/7 41-45 18 8 B 8/9/8 46-50 19 9 B 7/9/8 46-50 20
10 A 7/9/8 46-50 ) .sup.4 The foam formulation was stored together
with the siloxane at 50.degree. C. for 3 days before foaming
[0092] The data of table 4 show that siloxanes according to the
present invention lead to high-quality foams when used in
formulations containing halogenated olefins as blowing agents. Even
after aging the ready-formulated polyol component with stabilizer,
flawless foams were obtained. Such a result was unattainable
according to Example 2 of US 2009/0099272.
* * * * *